CLS_ResearchReport_2014_WEB

Canadian Light SourCe inC.

ReseaRch RepoRt 2014

www.lightsource.ca

Canadian Light Source Research Report 2014

Editor: Victoria Martinez

ISBN 978-0-9783761-5-4

© 2014 Canadian Light Source Inc. All rights reserved.

Canadian Light Source, Inc. 44 Innovation Boulevard Saskatoon, SK, Canada S7N 2V3 Telephone: +1-306-657-3500 Fax: +1-306-657-3535 E-mail: [email protected]

www.lightsource.ca

Layout and Cover Design: Reach Communications

2 0 1 4 r e s e a r c h r e p o r t 1

Table of Contents

Acknowledgements . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2

Message from the CEO . . . . . . . . . . . . . . . . . . . . . . . . . . 2

2014 Year in Review Timeline. . . . . . . . . . . . . . . . . . . . . . 4

ChemiCal & materials

1 impact of the selenolate ligand on the bonding properties of au25 nanoclusters . . . . . . . . . . . . . . . . . . 8

2 aluminum-phosphate binder formation in zeolites as probed with X-ray absorption microscopy . . . . . . . . 11

3 the metallic nature of epitaxial silicene monolayers on ag(111) . . . . . . . . . . . . . . . . . . . . . . 14

4 Sudden reversal in the pressure dependence of tc in the iron-based superconductor CsFe2as2: a possible link between inelastic scattering and pairing symmetry . . . . . . . . . . . . . . . . . . . . . . . 17

5 Pursuit of quantum monodromy in the far-infrared and mid-infrared spectra of nCnCS using synchrotron radiation . . . . . . . . . . . . . . . . . . . . . . . 20

instrumentation & teChniques

1 development of a bent Laue beam-expanding double-crystal monochromator for biomedical X-ray imaging . . . . . . . . . . . . . . . . . . . . . . . . . . 23

life sCienCes

1 Crystal structures of wild type and disease mutant forms of the ryanodine receptor SPrY2 domain . . . . . . . . . . . . . . . . . . . . . . . . . . 26

2 Modification and periplasmic translocation of the biofilm exopolysaccharide poly-β-1,6-n-acetyl-d-glucosamine . . . . . . . . . . . . 29

earth & environmental

1 Arsenic speciation in newberyite (MgHPO4•3H2O) determined by synchrotron X-ray absorption and electron paramagnetic resonance spectroscopies: implications for the fate of arsenic in green fertilizers . . . . . . . . . . . . . . . . . 32

2 nitrogen input quality changes the biochemical composition of soil organic matter stabilized in the fine fraction: a long-term study . . . . . . . . . . . 35

Cls innovations

industrial Science update . . . . . . . . . . . . . . . . . . . . . . . 38

Saving lives with light: the Medical isotopes Project . . . . . . 40

Students On the Beamline. . . . . . . . . . . . . . . . . . . . . . . 42

Bancroft Award Winner: riccardo Comin’s high-tc Superconductivity insight . . . . . . . 44

Beamlines. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46

Photon Port Allocation . . . . . . . . . . . . . . . . . . . . . . . . . 48

Facts and Figures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 50

2014 Publications . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52

50 Years of Accelerator Science . . . . . . . . . . . . . . . . . . . 61

C a n a d i a n L i g h t S o u r C e2

AcknowledgementsFunding PartnerS

the Canadian Light Source thanks all of our funding partners for their commitment to the advancement of science and technology.

Canadian user universities

operating

Capital

RMC CMR

Message from the CEOthis year’s research report showcases the depth and breadth of scientific exploration and discovery taking place at the CLS. included are 10 of this year’s most significant and exciting publications spanning a range of areas. in health sciences there have been breakthroughs in the investigation of genetic heart conditions and bacterial biofilms. there have been exciting new results in materials science involving 2-dimensional silicon, high temperature superconductors and gold nanoparticles. new discoveries about arsenic in green fertilizers and nitrogen in soils show the growth of work in the environmental sector. these results, along with chemical studies of novel catalysts and the fundamental behaviour of large organic molecules, make it clear that the CLS continues to grow scientifically. Significant technical innovation continues with enhancement of our imaging capabilities, and in a world first the CLS has developed a beam expander that turns short beamlines into virtual long ones.

of course, a report like this one cannot include every 2014 science highlight. after all, over 250 publications using CLS data came out this year alone. a more detailed overview of these stories can be found on our website. these include studies of embryonic teeth, african sleeping sickness and cystic fibrosis; investigations of innovative materials such as graphene, nanogold and carbon nanotubes; a unique study of a Siberian Bronze age skull; and a celebration of the 500th protein structure deposited into the Protein data Bank from the CMCF beamlines.

great science breeds ideas, innovations and unanticipated impacts. Within these pages, you will also find updates from two of our landmark innovations in synchrotron science: the world-leading industrial science program, and the Medical

isotope Project (MiP). Working with customers in the mining, oil and gas, pharmaceutical, and aerospace sectors, we have made advancements in tracking environmental effects, innovative and efficient methods for oil extraction, and providing essential data for products and drug development.

the MiP facility commenced production in november 2014. it is the world’s first electron linear accelerator facility dedicated to the production of medical radioisotopes. Mo-99, the precursor to the important medical isotope tc-99m, is now being shipped to the Prairie isotope Production enterprise.

none of this would be possible without the commitment of our partners and the passion of our community, our employees and our users.

as we turn the corner into a new decade of science, we are reconnecting with our local communities, reengaging our users, renewing our commitment to our vision and mission, and refocusing our operations to ensure maximum impact and output. together with our funding partners, users, customers and local communities, we will ensure a very bright future for all.

2015 will be an even bigger, brighter and better year!

Rob Lamb Ceo

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an exhibit of stunning imagery from cMcF is featured at the saskatoon Mendel art Gallery LUGo 2014, in conjunction with the United Nations educational, scientific and cultural organization (UNesco) launch of the Year of crystallography.

the cLs welcomes Huan-hua Wang from the Institute of high energy physics at the chinese academy of sciences for a six-month visit. Wang brings many years of

experience as a research scientist developing and operating beamlines at the Beijing synchrotron Radiation Facility. During his visit he will participate in beamline capability development on the VespeRs beamline.

the cLs is a key partner in the consortium for Research and Innovation in aerospace in Quebec’s (cRIaQ) 100th project, entitled additive Manufacturing technologies for aerospace components, which aims to generate knowledge about design, transformation and high-strength aluminum alloy properties for additive manufacturing of aerospace components.

the cLs says farewell to Josef Hormes (right) who served as executive director for five and a half years. Dr. hormes leaves to pursue his research interests and to spend more time with family, splitting his time between Germany and Louisiana. Mark de Jong (left), cLs director of accelerators, assumes the role of acting executive director.

sGM Beamline scientist Tom Regier (left) is named one of cBc saskatchewan’s Future 40. Under tom’s leadership, his beamline has been one of the most successful at the cLs and is recognized as one of the best in the world.

the honourable Rob Norris, saskatchewan advanced education Ministerand the Government of saskatchewan announce continued investment in health and life science research, with direct benefits to the research capabilities of the BioXas beamline.

University of saskatchewan graduate student Michael Greschner joins the cLs in the area of condensed matter physics. Michael completed his undergraduate courses at Queen’s University and the University of Victoria and originally hails from New Brunswick.

Rajivsingh (Kiran) Mundboth begins his work as a postdoctoral fellow on VespeRs to study enhanced X-ray micro-diffraction capabilities. he obtained his phD degree from Université Joseph Fourier in Grenoble, France and previously worked at Diamond Light source as a Research associate in the optics Group. Kiran recently relocated to saskatoon from Mauritius.

Adam Gillespie joins the cLs as a research associate in soil chemistry with sGM, with a focus on developing and applying XaNes for the characterization of soil samples. adam completed his phD at the University of saskatchewan and has been working in ottawa for agriculture and agri-Food canada as an NseRc Visiting Fellow.

University of saskatchewan graduate student Samira Sumaila joins the cLs in green mining. samira obtained her degree in environmental science in Ghana before starting her Master’s degree in Urban environmental engineering at École centrale de Nantes in France.

the honourable Michelle Rempel, Minister of state responsible for Western economic Diversification canada, visits the cLs January 15 to learn more about synchrotron research and the ongoing Medical Isotope project.

JanuarY feBruarY marCh

2014 Timeline

Research associate Adam Leontowich works to implement the detailed design of a new cryo-cooled scanning transmission X-ray microscope (stXM) for the sM beamline upgrade project. this microscope will allow cLs users to study a wider range of materials, especially biological, medical and other soft matter through spectromicroscopy and spectro-tomography techniques on cryogenically cooled samples.

Year in revieW

the 2013 G. Michael Bancroft phD thesis award, for the strongest published phD work using cLs data, presented to University of British columbia student Riccardo Comin. comin uses the ReIXs beamline to study correlated oxide materials and high-temperature superconductors.

Kee Eun Lee joins the sXRMB beamline team where she develops new synchrotron techniques related to the characterization of nanostructured catalysts

under in situ conditions. Kee eun held a postdoctoral position at the Department of chemistry at the University of saskatchewan prior to joining the cLs at the beginning of March. Kee eun obtained her phD in materials engineering at McGill University and her Msc. in inorganic chemistry at sogang University in seoul, Korea.

theory Day, april 11, is a chance for staff and users to showcase innovative techniques and new research, like the work presented by hXMa beamline scientist, Ning Chen.

on June 3, the cLs signs a memorandum of understanding with Mitacs, a national, not-for-profit organization that brings together academia, industry and the public sector to develop cutting edge tools and technologies vital to canada’s knowledge-based economy.

the application of synchrotron Imaging for crop Improvement Workshop, held in saskatoon June 10-12, explores the application of synchrotron light to imaging plants to support the selection and development of superior crop lines. the workshop looks at ways plants can be

structurally and functionally imaged, in vivo to in situ, and applying this information to aid in the development and selection of higher yielding crop varieties.

the cLs community thanks Dr. Walter Davidson, chair of the Board of Directors, 2010-2014, for his service and dedication to promoting scientific research in canada.

a beautiful sculpture by renowned artist and University of saskatchewan professor emeritus Eli Bornstein is reinstalled on the cLs grounds. this work was designed so its appearance would change in response to daily shifts in sunlight and shadow, as well as seasonal variations.

the cLs is welcomes Peter Blanchard, industrial science research associate. peter joins the cLs after returning to canada from australia where he held a postdoctoral research associate position at the University of sydney. peter obtained his phD in chemistry from the

University of alberta and did his undergraduate studies at Memorial University in Newfoundland. In addition to supporting industrial research clients, peter will be working on a collaborative project with andrew Grosvenor from the University of saskatchewan and aReVa Resources canada Inc. to improve understanding of the long term disposal of mill tailings, important in future mine site reclamation.

cLs annual Users’ Meeting takes place May 1-2 on the University of saskatchewan campus with keynote speaker Adam Hitchcock, professor of materials research at McMaster University.

toby Bond joins the cLs as the new industrial science associate. toby obtained his chemistry degree from the University of saskatchewan before heading off to Dalhousie University for his Msc. toby returned to saskatoon in october 2012 and was working as an analytical chemist for the saskatchewan Isotope Laboratory before joining the cLs.

Saroj Kumar joins the cLs as the thRUst Mid-IR postdoctoral Fellow. saroj joined the Mid-IR team from the Laboratory for structure and Function of Biological Membranes where he was

a postdoctoral Fellow at the Université Libre de Bruxelles in Brussels, Belgium.

the 2014 User advisory committee User support award is given to BMIt staff scientist George Belev (right).

Installation and testing begins on the new QMsc beamline monochromator.

april JunemaY

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T I M E L I N E

5


JulY august septemBer

the new chair and Vice chair for the User's advisory committee (2014-15) are, respectively, Andrew Grosvenor (University of saskatchewan, right) and Jeff Warner (cameco corp., not pictured). Both terms begin sept. 1. Rob scott (University of saskatchewan), Robert McKellar (National Research council), and Aimy Bazylak (University of toronto) have been elected to the Uac to serve three-year terms beginning in september. Mercedes Martinson (U of s) has been elected as a student member, serving a two-year term. the following regular members' terms ended august 2014: Ken Burch (Boston college), Kirk Michaelian (Natural Resources canada), and Jennifer van Wijngaarden (University of Manitoba). the Uac and cLs thank these individuals for their service to the user community and their work on behalf of the facility.

Jarvis Stobbs joins the experimental facilities division as a science associate, experimental floor. Jarvis relocated to saskatoon from estevan, sK, where he

was completing a work term for his chemical technology diploma at the Boundary Dam power station.

our new BMIt ID line during testing. the glowing window show the X-ray beam passing through a carbon window to remove soft X-rays.

Robert Lamb joins the cLs as the new ceo and executive director. Rob has been a light source user in europe, the U.s. and asia for over 25 years. he was also the founding director of the australian Light source. educated at Melbourne and cambridge Universities, Rob has held academic appointments in england, Germany, the United states, hong Kong and australia, as well as senior administrative positions in both university and government.

the cLs is honoured to host former saskatchewan premier Lorne Calvert and former canadian prime Minister Paul Martin, with ceo Robert Lamb and saskatchewan MLa Rob Norris.

the cLs is on display at Nuit Blanche saskatoon sept. 27. Using images and sound recording from several beamlines, the installation shows the audience some of the outstanding research at the cLs.

saskatchewan advanced education Minister, the honourable Kevin Doherty, holds a medical isotope sample cartridge during a visit to the cLs.

2014 TimelineYear in revieW

R e s e a R c h h i g h l i g h t s

oCtoBer deCemBernovemBer

T i m e l i n e

on oct. 18 the cLs opened its doors to the public to showcase health research using synchrotron technology. the event was hosted by the cIhR-thUst program at the University of saskatchewan and was supported by cLs staff and scientists.

In order to work together and coordinate our efforts as a facility, the energy storage working group was formed to encourage inter-beamline discussion and collaboration in this area. their inaugural meeting was held on Nov. 14 and was attended by 15 participants from all around the cLs.

BioXas beamteam leaders Graham George, U of s professor and canada Research chair in X-ray absorption spectroscopy and Ingrid Pickering, University of saskatchewan professor, and canada Research chair in Molecular environmental science, announce the first data collected on the beamline, Dec. 19.

Scott Rosendahl joins the cLs as the Mid-IR staff scientist. scott is a familiar face around the cLs, having assisted the Mid-IR beamline as a technical assistant for the past four years while working

towards his phD. In 2013, he received his phD in chemistry from the University of saskatchewan.

Mp Kelly Block and the honourable Jeremy Harrison, saskatchewan Minister for Innovation, join cLs scientists to announce the first shipment of medical isotopes produced in its dedicated linear accelerator Nov. 14. the Medical Isotope project (MIp) facility at the cLs is the first of its kind in the world, relying on powerful X-rays to produce isotopes, unlike traditional nuclear reactor-based methods. Natural Resources canada’s Isotope technology acceleration program (Itap ) and the Government of saskatchewan funded the project.

NseRc president Mario pinto (r) arriving safe and sound Nov. 28., despite the weather, to meet with ceo Rob Lamb.

the cLs celebrates the 10-year anniversary of the official grand opening (oct. 22, 2004). after five and a half years of construction and $174-million invested, the switch was flipped and science in canada would never be the same again.

cMcF announces the successful solution of 500 protein structures using the cLs. the 3-dimensional structures of proteins can be determined using powerful synchrotron X-ray light, and these structure models are deposited in the protein Data Bank—a worldwide repository describing and showcasing proteins and other biological macromolecules. Many of these structures have been critical to the publication of 286 peer-reviewed journal articles.

the undulator for our new QMsc photoemission beamline moves into the magnet mapping room where the machine will be calibrated before being moved into the storage ring.

2 0 1 4 r e s e a r c h r e p o r t 7


PRINCIPAL CONTACT:

peng Zhang associate professor Department of chemistry and the school of Biomedical engineering Dalhousie University [email protected] 902-494-3323

JOuRNAL/PRINCIPAL PuBLICATION:

Journal of Physical Chemistry C, august 21 2014, Issue 37, Volume 118, pp. 21730-21737. DoI: dx.doi.org/10.1021/jp508419p

AuThORS:

Daniel M. chevrier Department of chemistry Dalhousie University

Xiangming Meng Department of chemistry anhui University

Dr. Qing tang Department of chemistry University of california Riverside

Dr. De-en Jiang Department of chemistry University of california Riverside

Dr. Manzhou Zhu Department of chemistry anhui University

Dr. amares chatt Department of chemistry Dalhousie University

Dr. peng Zhang Department of chemistry and the school of Biomedical engineering Dalhousie University

Impact of the selenolate ligand on the bonding properties of Au25 nanoclusters

introductionResearch on thiolate-protected gold nanoclusters (thiolate-Au NCs) has made a profound impact on our understanding of thiolate-Au nanomaterial structure and properties [1, 2]. Since the determination of its total structure [3, 4], the Au25(SR)18 NC has served as an excellent model system to elucidate more refined details on luminescence [5], heteroatom doping [6, 7], and catalytic activity [8, 9]. Continuing to correlate such properties with the total structure of Au25(SR)18 NCs is an important steppingstone for exposing the potential thiolate-Au NCs hold for applications in such areas as catalysis and biomedical-related technologies. Atomically precise selenolate-protected gold nanoclusters (selenolate-Au NCs or Aun(SeR)m) have recently surfaced in this field of Au NC research. Earlier studies have pursued selenium-based ligands for the protection of larger Au NPs to improve the stability or to investigate the surface structure of selenolate-Au nanomaterials [10-12]. In particular, the Au-Se bond is expected to be more covalent in nature than the Au-S bond because of the larger covalent radius of Se and the almost identical electronegativities of Se and Au. Exchanging the thiolate ligands for selenolate ligands could therefore enhance the stability of Au NCs.

SciencePhenylethanethiolate-protected Au25

(Au25(SC2H4Ph)18) and benzeneselenolate-protected Au25 (Au25(SePh)18) NCs studied herein were synthesized according to a modified Brust two-phase method and a previously published ligand-exchange protocol, respectively [13]. Both Au25(SeR)18 and Au25(SR)18 were synthesized in the anionic state (counterion: [N(C8H17)4]

+) and were thoroughly characterized to confirm the chemical composition [13]. Au L3- and Se K-edge X-ray absorption spectroscopy (XAS) measurements were collected in transmission mode at the PNC/XSD beamline of the Advanced Photon Source (Argonne National Laboratory, Argonne, IL, USA) using a Si(111) monochromator and a rhodium mirror. Powdered samples of Au25(SR)18 and Au25(SeR)18 were packed into kapton film pouches, sealed, and folded until an ample absorption edge jump

(Δµ0>~0.5) was obtained. Multiple measurements were collected for each XAS experiment to ensure reproducibility of fine structure oscillations. Au foil or Se mesh reference materials were measured simultaneously with the Au25 NC sample for calibration of the absorption edge energy (11.919 and 12.658 keV for Au and Se, respectively). Measurements were conducted at 300 K under ambient conditions and at 50 K using a helium-cooled cryostat chamber.

Figure 1 (a) displays the Au L3-edge EXAFS oscillations at 50 K in k-space for Au25(SeR)18 along with Au25(SR)18 for direct comparison of the Au local structure. By comparing the k-space spectra, it is evident that exchanging the thiolate for the selenolate ligand dramatically changes fine structure oscillations in the early k-space region (2-6 Å−1) due to Au−Se bonding. The late k-space oscillations (8-13 Å−1) also increase in intensity, possibly from more tightly ordered Au−Au bonding. For the Fourier transform (FT) to radial space (R-space) (shown in Figure 1 (b)), a k-space region from 3-13 Å−1 was used for both samples to allow the incorporation of multiple scattering shells with enough spatial resolution to distinguish different Au−Au scattering paths (ΔR=~0.2 Å, the approximate difference between core and surface Au−Au bond lengths).

A detailed multishell Au L3-edge EXAFS fitting analysis was conducted following a similar data treatment protocol to our previous work on phenylethanethiolate-protected Au19(SR)13 and Au25(SR)18 NCs [14, 15]. Four scattering shells were used to fit Au L3-edge EXAFS along with two shells to fit the Se K-edge EXAFS. Together, this offers a site-specific investigation of Se−C, Au−Se (from both edges), Au−Au core (Au−Au1), Au−Au surface (Au−Au2), and Au−Au aurophilic (Au−Au3) environments.

DiscussionThe effect of temperature on the ligand shell of Au25(SeR)18 NCs was first investigated from the Se K-edge perspective. EXAFS fitting of the R-space spectrum, as shown in Figure 1 (d), indicates the Se−Au bonding at 300 K is almost identical to 50 K. Se−C bonding, on the other hand, increases in length by 0.08 Å, from 1.87(3) to 1.95(2)Å, when

1 ChemiCal aND materials sCieNCe


2 0 1 4 r e s e a r c h r e p o r t 9

the temperature rises to 300 K (depicted in Figure 2). Lengthening of the Se−C bond at higher temperature could be related to a previous stability study on Au25(SeR)18 NCs that found Se−C bonds to be weaker than S−C bonds under high temperature treatment [16].

Multishell EXAFS fitting of the Au L3-edge spectra (Figure 1 (c)) indicates a very small decrease in Au−Se bonding (similar to Se K-edge results) at the higher temperature. A dramatic thermal contraction of all three Au−Au shells is observed (plotted in Figure 2), where Au–Au1 decreases from 2.775(9)Å to 2.70(1)Å, Au–Au2 from 2.98(1)Å to 2.87(2)Å, and Au–Au3 from 3.60(3)Å to 3.45(4)Å. This is contrary to our previous EXAFS temperature-dependent study on Au25(SR)18 NCs15 (and reproduced with the Au25(SR)18 sample in this work), where Au-thiolate and Au−Au core interactions slightly increase with temperature and aurophilic interactions remain similar in average distance. We hypothesize that since the average Au–Se bond length does not decrease at the higher measured temperature, contraction of aurophilic bonding on the surface must originate from a change in the Ausurface–Se–Austaple

bond angle to bring staple and surface Au atoms closer together, accounting for the decrease found in the Au−Au3 distance. To confirm this hypothesis of aurophilic-induced thermal contraction, we performed first-principles molecular dynamics (MD) simulation based on DFT (details reported in original publication). Starting with the DFT-optimized structure of the Au25(SePh)18 NC (that is at 0 K) shown in Figure 3, we heated up the cluster to 300 K in the MD simulation to investigate our proposed mechanism of negative thermal expansion. Figure 3 displays the isolated dimeric staple unit and surface environment of Au25(SePh)18 from optimized DFT structures at each temperature along with the average bond angles for each structure. Consistent with our proposal, the angle between Ausurface–Se–Austaple (indicated as (i)) becomes more acute at 300 K by ca. 7° and is as small as 70.4° (smallest angle for 0 K was found to be 78.1°). Along with this, the Austaple–Se–Austaple angle (indicated as (ii)) becomes more obtuse at 300 K by ca. 2° which helps to bring the staple Au closer to the Au13 surface.

Figure 1. au L3-edge (a) k-space spectra and (b) Ft r-space spectra of au25(Sr)18 and au25(Ser)18 nCs measured at 50 K. (c) au L3-edge and (d) Se K-edge multi-shell eXaFS fit of au25(Ser)18 nCs at different temperatures.

Figure 2. temperature-dependent plots of (a) au25(Ser)18 site-specific bond distances (models and circled regions correspond to the bond type).


ConclusionTo summarize, selenolate-protected Au25

NCs were studied with a detailed site-specific, multishell EXAFS analysis from both Au and Se perspectives at varied temperatures. Significantly longer aurophilic interactions from staple Au to surface Au sites were identified for Au25(SeR)18 which become shorter with increasing temperature, inducing a contraction of the entire Au−Au framework in Au25. Temperature-dependent structural changes were also observable from Au and Se electronic properties (details reported in original publication), providing further evidence of the Au−Au framework contraction. These experimental findings are consistent with results from MD-DFT structural modeling and ab initio simulations of X-ray spectra. This work brings to light the remarkable bonding behaviour of Au25 nanoclusters induced by the selenolate ligand and implies that the selenolate-protected Au NCs behave differently from their thiolate counterparts in the context of aurophilic bonding.

References [1] Jin, r. Quantum sized, thiolate-protected gold nanoclusters. (2010). Nanoscale 2, 343-362.

[2] Jiang, d. (2013). the expanding universe of thiolated gold nanoclusters and beyond. Nanoscale 5, 7149-7160.

[3] heaven, M. W.; dass, a.; White, P. S.; holt, K. M.; Murray, r. W. (2008). Crystal structure of the gold nanoparticle [n(C8h17)4][au25(SCh2Ch2Ph)18]. J. Am. Chem. Soc. 130, 3754-3755.

[4] Zhu, M.; aikens, C. M.; hollander, F. J.; Schatz, g. C.; Jin, r. (2008). Correlating the crystal structure of a thiol-protected au25 cluster and optical properties. J. Am. Chem. Soc. 130, 5883-5885.

[5] Wu, Z.; Jin, r.(2010). on the ligand’s role in the fluorescence of gold nanoclusters. Nano Lett. 10, 2568-2573.

[6] Kumara, C.; aikens, C. M.; dass, a. (2014). X-ray crystal structure and theoretical analysis of au25-xagx(SCh2Ch2Ph)18- alloy. J. Phys. Chem. Lett. 5, 461-466.

[7] gottlieb, e.; Qian, h.; Jin, r. (2013). atomic-level alloying and de-alloying in doped gold nanoparticles. Chemistry. 19, 4238-4243.

[8] Zhu, Y.; Qian, h.; Jin, r. (2011). Catalysis opportunities of atomically precise gold nanoclusters. J. Mater. Chem. 21, 6793-6799.

[9] Shivhare, a.; ambrose, S. J.; Zhang, h.; Purves, r. W.; Scott, r. W. J. (2013). Stable and recyclable au25 Clusters for the reduction of 4-nitrophenol. Chem. Commun. (Camb). 49, 276-278.

[10] Yee, C. K.; ulman, a.; ruiz, J. d.; Parikh, a.; White, h.; rafailovich, (2013). M. alkyl selenide- and alkyl thiolate-functionalized gold nanoparticles: Chain packing and bond nature. Langmuir. 19, 9450-9458.

[11] Zelakiewicz, B. S.; Yonezawa, t.; tong, Y. (2004). observation of selenium-77 nuclear magnetic resonance in octaneselenol-protected gold nanoparticles. J. am. Chem. Soc. 126, 8112-8113.

[12] Li, Y.; Zaluzhna, o.; Xu, B.; gao, Y.; (2011). Modest, J. M.; tong, Y. J. Mechanistic insights into the Brust-Schiffrin two-phase synthesis of organo-chalcogenate-protected metal nanoparticles. J. Am. Chem. Soc. 133, 2092-2095.

[13] Meng, X.; Xu, Q.; Wang, S.; Zhu, M. (2012). Ligand-exchange synthesis of selenophenolate-capped au25 nanoclusters. Nanoscale. 4, 4161-4165.

(14) Chevrier, d. M.; Macdonald, M. a.; Chatt, a.; Zhang, P.; Wu, Z.; Jin, r. (2012). Sensitivity of Structural and electronic Properties of gold−thiolate nanoclusters to the atomic Composition : a Comparative X-ray Study of au19(Sr)13 and au25(Sr)18. J. Phys. Chem. C. 116, 25137-25142.

Figure 3. Md-dFt simulated structure of the au25(SePh)18 nC. a typical structural change of the dimeric motif in the au25(SePh)18 nC from 0 K (after dFt geometry optimization) (bottom left) to 300 K (after heating up in dFt-based Md simulation) (bottom right) with average bond angles.

(15) Macdonald, M. a.; Chevrier, d. M.; Zhang, P.; Qian, h.; Jin, r. (2011). the Structure and Bonding of au25(Sr)18 nanoclusters from eXaFS: the interplay of Metallic and Molecular Behavior. J. Phys. Chem. C. 115, 15282-15287.

(16) Kurashige, W.; Yamaguchi, M.; nobusada, K.; negishi, Y. (2012). Ligand-induced Stability of gold nanoclusters: thiolate versus Selenolate. J. Phys. Chem. Lett. 3, 2649-2652.

AcknowledgementsP.Z. acknowledges funding support from dalhousie university and nSerC in the form of discovery grants. PnC/XSd facilities at the advanced Photon Source (aPS) (argonne national Laboratory) and research at these facilities are supported by the u.S. department of energy − Basic energy Sciences, a Major resources Support grant from nSerC, the university of Washington, the CLS and the aPS. use of the aPS and office of Science user Facility operated for the u.S. department of energy office of Science by argonne national Laboratory, was supported by the u.S. doe under Contract no. de-aC02-06Ch11357. the authors are thankful for the technical assistance provided by dr. robert gordon at PnC/XSd facilities. d.J. would like to acknowledge the dFt-Md simulation support by the university of California, riverside Startup Fund.

Beamline information au L3-edge and Se K-edge XaFS data were collected in transmission mode using gas ionization chambers at PnC/XSd facilities (Sector 20-BM), advanced Photon Source, argonne national Laboratory, iL, uSa.


2 0 1 4 r e s e a r c h r e p o r t 11

PRINCIPAL CONTACT:

prof. Dr. Ir. Bert M. Weckhuysen Inorganic chemistry and catalysis Group Utrecht University [email protected] +31 30-253-4328


Journal of the American Chemical Society, November 21, 2014, Issue 51, Volume 136, pp. 17774-17787. DoI: 10.1021/ja508545m

AuThORS:

hendrik e. van der Bij1 Dimitrije cicmil1 Jian Wang2 Florian Meirer1 Frank M. F. de Groot1

Bert M. Weckhuysen1

1 Inorganic chemistry and catalysis Group Utrecht University

2 canadian Light source

Aluminum-phosphate binder formation in zeolites as probed with X-ray absorption microscopy

introductionCatalysis performed over the crystalline microporous alumino-silicates known as zeolites is of enormous importance to the oil and gas industry, as their use saves billions of dollars in process and energy costs [1]. Due to their wide and valuable application range in catalytic cracking and potential use in catalytic fast pyrolysis of biomass, (bio-) alcohol dehydration and (bio-) alcohol conversion to hydrocarbons, there is a great academic interest in zeolites as heterogeneous catalysts [2-5]. As was recently pointed out in two reviews, academic research has focused mainly on the performance of pure zeolite materials. However, the application of binders and matrices used in industrially relevant catalyst bodies to increase mechanical strength and attrition resistance also exert huge influences on performance [6,7].

One such interaction between binder and zeolite is with the addition of aluminum-phosphate (AlPO4). Especially in the field of catalytic hydrocarbon cracking, the addition of AlPO4 to zeolites, often in combination with a zeolite phosphatation step, leads to an enhanced light olefin selectivity, hydrothermal stabilization, improved mechanical strength, and attrition resistance [8-12]. Furthermore, it has been shown that AlPO4 can form from a zeolite’s own aluminum supply by applying a dealumination and subsequent phosphorus modification (phosphatation) step [13-17]. By combining chemical imaging at the SM beamline at the CLS with bulk characterization techniques, it was possible to study the formation of an AlPO4 phase in three different industrially relevant zeolites (H-USY, H-mordenite and H-ferrierite). X-ray tomography was used to visualize, for the first time, a 3-dimensional nanoscale chemical reconstruction of the AlPO4 phase in a single H-mordenite aggregate.

ScienceAn amorphous AlPO4 phase was synthesized in H-mordenite by applying a pre-steam treatment, followed by the addition of phosphoric acid. In situ Scanning Transmission X-ray Microscopy (STXM) was then carried out to follow the crystallization of the AlPO4 phase during heating (Figure 1) using the

peak at 1570.4 eV in the recorded X-ray absorption near edge structure (XANES) as an indicator for the annealing of the amorphous AlPO4 into the more crystalline AlPO4 structures. The 2-dimensional chemical maps also suggest that the AlPO4 is present on the external surface of the zeolite indicated by the fact that the concentrations of Si (gray intensities) and Al (coloured intensities) show no significant spatial correlation. This observation was further studied by soft X-ray tomography, visualizing morphology and chemical nature of a single zeolite particle (Figure 2). The results revealed that the particle (AlPO4/Mordenite) consists of an aggregate of smaller crystals and contains specific islands with high concentrations of phosphorus and aluminum. Statistical analysis of the tomography data confirmed the 2-D STXM results, indicating that the islands are indeed located on the external surface of the zeolite material. Inside the aggregate, phosphorus and aluminum are also present, but at lower concentrations. Furthermore, two distinct types of Al K-edge XANES were observed: type 1 represents the aluminum found in AlPO4/Mordenite after crystallization (highly crystalline AlPO4) and type 2 the one before crystallization (amorphous AlPO4), as shown in Figure 1. While Al of type 1 is more dominant in the high aluminum, high phosphorus regions at the external surface, type 2 is found in the medium aluminum, low phosphorus regions inside the denser parts of the zeolite.

Highly crystalline AlPO4 was also detected at high concentrations for zeolite H-Y, while the AlPO4 phase was not observed in the zeolitic interior of this sample, indicated by the XANES, which resembled that of aluminum-silicates and not that of AlPO4 structures. Finally, crystalline AlPO4 was not detected in H-ferrierite.

DiscussionDuring thermal or hydrothermal treatment of the amorphous AlPO4 phase (Al-O-P)n linkages anneal, which leads to the crystallization of the amorphous AlPO4 phase. In order for the AlPO4 phase to grow as 3-D crystal structures, sufficient space is needed. Therefore, it is assumed that if AlPO4 is located inside the zeolite micropores crystallization is inhibited, leading to the higher concentration




of amorphous AlPO4 found inside the zeolite H-mordenite. Such an effect was not observed for zeolite H-USY, as the AlPO4 phase was found exclusively outside of the crystal for the samples under study.

The results reported by Corma and co-workers are in agreement with this observation, as they showed by 27Al MAS NMR that the spectroscopic signals for amorphous AlPO4 were almost eliminated after the crystallization of the AlPO4 phase in H-USY [13]. It is postulated that the pore dimensionality of the framework plays a role: the 1-dimensional pore structure of zeolite H-mordenite is prone to pore-blockage, causing parts of the AlPO4 phase to be trapped inside the channel system and therefore hindering subsequent crystallization. In the 3-D channel system of zeolite H-Y, these constrains are not as dominant resulting in a stronger segregation between (i) AlPO4 outside the zeolite and (ii) framework aluminum inside the zeolite. However, further studies will be necessary to fully substantiate these claims.

In the case of H-ferrierite, due to the inaccessible nature of the extra-framework aluminum species, the formation of a crystalline AlPO4 phase is unlikely to take place. Phosphoric acid readily reacts with extra-framework aluminum, and it has been suggested that extra-framework aluminum species in H-ferrierite are trapped in the structure; these species are therefore not available to react and an AlPO4 phase cannot form [18].

ConclusionA detailed study has been performed on the formation of an aluminum-phosphate (AlPO4) binder from the framework aluminum supply of three industrially relevant zeolites, namely H-USY, H-mordenite and H-ferrierite. The amorphous AlPO4 phase was found to consist of four-, and six-coordinated aluminum connected to PO4- units. The majority of the amorphous AlPO4 phase was heterogeneously distributed on the external zeolitic surface, while only small concentrations were detected in the zeolitic interior. During a subsequent thermal or hydrothermal treatment the amorphous AlPO4 phase crystallizes into AlPO4 with no observable migration during crystallization.

The formation of an AlPO4 binder by using part of the framework aluminum supply is an interesting method for multiple

Figure 1. in situ crystallization of the aluminum-phosphate (alPo4) phase within h-mordenite monitored by Scanning transmission X-ray Microscopy (StXM). Chemical maps of sample alPo/Mordenite (a and d) before and (b and c) after heating at 400 °C. greyscale masks are constructed from the Si map and indicate the particle area. Brighter regions have a higher optical density. the colored al K-edge XaneS in (e) and (f ) correspond to the coloured masks in (a) and (b). (c-d) Mask of the highest phosphorus optical density.

Figure 2. (a) 3-d representation of a steamed, phosphated, and subsequently post-steamed h-mordenite aggregate, alPo4, reconstructed from the soft X-ray tomography data. voxel size is 63x63x63 nm3. grey colored voxels correspond to data collected at an energy measured before the aluminum K-edge (1555 ev) and relates to the particle density. Blue-coloured voxels represent the aluminum distribution and green colored voxels the phosphorus distribution. Low intensity voxels are not shown. the average al K-edge XaneS is shown in black, and was obtained by 2-d StXM of the particle. it should be noted that voxels do not contain a full al K-edge XaneS. tomography data was collected only at 1555 ev (particle density), 1565 ev (peak a) and at 1570.4 (peak B). the ratios between the recorded peak a and peak B intensities were used to identify corresponding al phases (type 1 and type 2). the blue box highlights a high aluminum and high phosphorus island on the surface with corresponding al K-edge XaneS, while the red box highlights aluminum present in the crystal interior. (b, c) Statistical analysis of the voxel data, showing correlations of aluminum, phosphorus and particle densities. it can be observed that there are regions that contain high phosphorus, high aluminum and high type 1 aluminum and regions that contain low phosphorus, medium aluminum and high type 2 aluminum.


2 0 1 4 r e s e a r c h r e p o r t 13

reasons. First, it requires zeolites with high aluminum content, which are cheaper and more environmentally friendly to produce, since the use of organic templates is not required [19-20]. Second, the pre-dealumination step leads to the formation of mesopores, creating a hierarchical material, facilitating access to reactant and product molecules during catalysis [21, 22]. And third, a thorough understanding of the formation of AlPO4 from extra-framework aluminum should allow one to form AlPO4 species inside the zeolite channel/cage system, altering its shape-selective effects [23].

As this is, to our best knowledge, one of the few works that explores the creation of a zeolite binder material made from components of the zeolite itself, it is too premature to present a fully unified view on AlPO4 formation in zeolite materials. However, we do hope that this work may stimulate future characterization studies that further explore these promising avenues.

References [1] vermeiren, W., & gilson, J. P. (2009). impact of zeolites on the petroleum and petrochemical industry. Topics in Catalysis, 52(9), 1131-1161.

[2] guisnet, M., & gilson, J. P. (eds.). (2002). Zeolites for cleaner technologies (vol. 3). London: imperial College Press.

[3] olsbye, u., Svelle, S., Bjørgen, M., Beato, P., Janssens, t. v., Joensen, F., ... & Lillerud, K. P. (2012). Conversion of methanol to hydrocarbons: how zeolite cavity and pore size controls product selectivity. Angewandte Chemie International Edition, 51(24), 5810-5831.

[4] Caro, J., noack, M., & Kölsch, P. (2005). Zeolite membranes: from the laboratory scale to technical applications. Adsorption, 11(3-4), 215-227.

[5] Jae, J., Coolman, r., Mountziaris, t. J., & huber, g. W. (2014). Catalytic fast pyrolysis of lignocellulosic biomass in a process development unit with continual catalyst addition and removal. Chemical Engineering Science, 108, 33-46.

[6] Mitchell, S., Michels, n. L., & Pérez-ramírez, J. (2013). From powder to technical body: the undervalued science of catalyst scale up. Chemical Society Reviews, 42(14), 6094-6112.

[7] hargreaves, J. S. J., & Munnoch, a. L. (2013). a survey of the influence of binders in zeolite catalysis. Catalysis Science & Technology, 3(5), 1165-1171.

[8] Cao, g., Martens, L. r., White, J. L., Chen, t. J., & Shah, M. J. (2000). U.S. Patent No. 6,080,303. Washington, dC: u.S. Patent and trademark office.

[9] a. Corma, Wo1999002260 a1, 1999.

[10] Kirker, g. W., Landis, M. e., & Yen, J. h. (1988). U.S. Patent No. 4,724,066. Washington, dC: u.S. Patent and trademark office.

[11] roberie, t. g., & John, F. t. i. (1994). U.S. Patent No. 5,286,369. Washington, dC: u.S. Patent and trademark office.

[12] Lee, Y. J., Kim, Y. W., viswanadham, n., Jun, K. W., & Bae, J. W. (2010). novel aluminophosphate (alPo) bound ZSM-5 extrudates with improved catalytic properties for methanol to propylene (MtP) reaction. Applied Catalysis A: General, 374(1), 18-25.

[13] Corma, a., Fornes, v., Kolodziejski, W., & Martineztriguero, L. J. (1994). orthophosphoric acid interactions with ultrastable zeolite-Y: infrared and nMr studies. Journal of Catalysis, 145(1), 27-36.

[14] Costa, a. F., Cerqueira, h. S., Ferreira, J. M. M., ruiz, n. M., & Menezes, S. M. (2007). Bea and Mor as additives for light olefins production. Applied Catalysis A: General, 319, 137-143.

[15] Lischke, g., eckelt, r., Jerschkewitz, h. g., Parlitz, B., Schreier, e., Storek, W., ... & Öhlmann, g. (1991). Spectroscopic and physicochemical characterization of P-modified h-ZSM-5. Journal of Catalysis, 132(1), 229-243.

[16] Zhuang, J., Ma, d., Yang, g., Yan, Z., Liu, X., Liu, X., ... & Liu, Z. (2004). Solid-state MaS nMr studies on the hydrothermal stability of the zeolite catalysts for residual oil selective catalytic cracking. Journal of Catalysis, 228(1), 234-242.

[17] van der Bij, h. e., aramburo, L. r., arstad, B., dynes, J. J., Wang, J., & Weckhuysen, B. M. (2014). Phosphatation of Zeolite h-ZSM-5: a Combined Microscopy and Spectroscopy Study. ChemPhysChem, 15(2), 283-292.

[18] Pellet, r. J., Casey, d. g., huang, h. M., Kessler, r. v., Kuhlman, e. J., oyoung, C. L., ... & ugolini, J. r. (1995). isomerization of n-butene to isobutene by ferrierite and modified ferrierite catalysts. Journal of Catalysis, 157(2), 423-435.

[19] Majano, g., delmotte, L., valtchev, v., & Mintova, S. (2009). al-rich zeolite beta by seeding in the absence of organic template. Chemistry of materials, 21(18), 4184-4191.

[20] Machado, F. J., López, C. M., Centeno, M. a., & urbina, C. (1999). template-free synthesis and catalytic behaviour of aluminium-rich MFi-type zeolites. Applied Catalysis A: General, 181(1), 29-38.

[21] hartmann, M. (2004). hierarchical zeolites: a proven strategy to combine shape selectivity with efficient mass transport. Angewandte Chemie International Edition, 43(44), 5880-5882.

[22] Perez-ramirez, J., Christensen, C. h., egeblad, K., Christensen, C. h., & groen, J. C. (2008). hierarchical zeolites: enhanced utilisation of microporous crystals in catalysis by advances in materials design. Chemical Society Reviews, 37(11), 2530-2542.

[23] Janardhan, h. L., Shanbhag, g. v., & halgeri, a. B. (2014). Shape-selective catalysis by phosphate modified ZSM-5: generation of new acid sites with pore narrowing. Applied Catalysis A: General, 471, 12-18.

[24] Creemer, J. F., helveg, S., hoveling, g. h., ullmann, S., Molenbroek, a. M., Sarro, P. M., & Zandbergen, h. W. (2008). atomic-scale electron microscopy at ambient pressure. Ultramicroscopy, 108(9), 993-998.

[25] hitchcock, a. P., dynes, J. J., Lawrence, J. r., obst, M., Swerhone, g. d. W., Korber, d. r., & Leppard, g. g. (2009). Soft X-ray spectromicroscopy of nickel sorption in a natural river biofilm. Geobiology, 7(4), 432-453.

[26] Liu, Y., Meirer, F., Williams, P. a., Wang, J., andrews, J. C., & Pianetta, P. (2012). tXM-Wizard: a program for advanced data collection and evaluation in full-field transmission X-ray microscopy. Journal of synchrotron radiation, 19(2), 281-287.

AcknowledgementsJoris goetze, Mustafa al Samarai and ramon oord of utrecht university are kindly thanked for their help during the StXM measurements. Prof. dr. henny Zandbergen and dr. Meng-Yue Wu from tu delft are thanked for supplying a MeMS in situ nanoreactor. n2-physisorption measurements were performed at utrecht university by arjan den otter, nazila Masoud and dr. Ying Wei.

Beamline information StXM experiments were performed at the Canadian Light Source (CLS) Beamline 10id-1. Samples were dispersed in h2o and a droplet was placed on a silicon nitride window. after drying in air the sample was placed in the StXM chamber, which was subsequently evacuated to 10-1 mbar. a polarized X-ray beam was obtained using a 1.6 m long, 75 mm period apple ii undulator. the X-ray beam was focused to ~30 nm spot size on the sample plane using a Fresnel zone plate (ZP). the beam from the ZP passed through a molybdenum-based order-sorting aperture (oSa), with a 50 µm pinhole. the oSa allowed only first-order ZP diffracted light to pass. Spectral image sequences (stacks) are measured by recording images over a range of photon energies. after aligning the image sequence, spectra of the whole or a subregion were extracted for comparison. For the in-situ measurements a micro-electromechanical system (MeMS) designed nanoreactor was used [24]. all StXM data analysis was performed using aXis2000 [25]. Sinograms and binslices were constructed and reconstructed using the tXM-Wizard software [26] and using the iterative algebraic reconstruction technique (iart) algorithm. the 3-dimensional data was analyzed using avizo 8.0 and MatLaB.


PRINCIPAL CONTACT:

Neil Johnson, B.sc. ph.D. candidate Department of physics and engineering physics University of saskatchewan [email protected] 306-966-6380


Advanced Functional Materials, Issue 33, Volume 24, september 2, 2014, pp. 5253-5259. DoI: 10.1002/adfm.201400769

AuThORS:

Neil W. Johnson, Dr. Israel perez, Dr. David Muir, prof. alexander Moewes Department of physics and engineering physics University of saskatchewan

Dr. David Muir canadian Light source

Dr. patrick Vogt technische Universität Berlin

Dr. andrea Resta, prof. Guy Le Lay aix-Marseille University

Dr. andrea Resta soLeIL synchrotron

Dr. paola De padova consiglio Nazionale della Ricerche-IsM

prof. ernst Z. Kurmaev M.N. Mikheev Institute of Metal physics Ural Federal University

The metallic nature of epitaxial silicene monolayers on Ag(111)

introductionSilicene is the silicon-based cousin to the 2-dimensional “wonder material” graphene. When it is freestanding, it is expected to possess many of the characteristics that make graphene such an attractive candidate material for next-generation electronic devices. However, freestanding silicene is yet to be observed. Atom-thick honeycomb silicon sheets have been grown on the surface of extremely flat silver crystals through physical vapour deposition [1], but whether these sheets are of any practical use was matter of significant debate. While some experiments indicated that these epitaxial silicene sheets were metallic [2], others reported observing the hallmarks of a “Dirac cone” in the electronic structure [3], a feature that is associated with the exciting electronic characteristics of graphene.

One of the main reasons for the disagreement over the true electronic nature of epitaxial silicene sheets was that no “element-specific” measurements had been performed on the material. That is, the existing experimental studies did not distinguish between electrons belonging to the silicene sheet and those belonging to the underlying silver substrate, leading to multiple interpretations of the data.

ScienceUsing the X-ray emission spectroscopy (XES) endstation of the REIXS beamline, we performed Si L2,3-edge soft X-ray emission and Si 2p absorption spectroscopy—XES and X-ray absorption spectroscopy (XAS), respectively—on monolayer epitaxial silicene samples. These samples were grown at the CLS using the thin-film deposition chamber located just outside the REIXS hutch. This chamber is outfitted with LEED, RHEED and a quartz crystal growth monitor for characterizing deposition rates and sample quality.

As silicene is extremely oxygen-sensitive, once the samples were grown in ultra-high vacuum they had to be transferred from the deposition chamber to the XES endstation without breaking vacuum. This was accomplished with the use of a custom vacuum transfer cart, which prevented the samples from seeing more than 10-7 Torr of pressure from the moment of deposition all the way through to measurement.

XES and XAS serve as element- and orbital-specific probes of the occupied valence and unoccupied conduction states, respectively. At the Si L2,3 emission and 2p absorption edge, we primarily measure Si states with s and d character, according to the dipole selection rules. While it may have been preferable to attempt to probe the Si p states using Si K XES and Si 1s XAS, the penetration depth of the required photons would be far too large to be sensitive to a single layer of Si atoms.

To complement these measurements, we also performed full-potential density functional theory (DFT) calculations using the WIEN2k program suite. Our calculations allowed us to evaluate structural models of epitaxial silicene monolayers on the Ag(111) surface, to calculate the electronic structures of these monolayers and to simulate the results of our soft X-ray spectroscopy measurements.

DiscussionOur DFT calculations predicted a wide variety of stable structures for epitaxial silicene monolayers. However, for each of these structures we calculated very similar electronic characteristics. Namely, they were found to be metallic and exhibited significant interaction with the underlying substrate. Silver was initially chosen as a growth platform for silicene because it was expected to have minimal interaction with the sheets, but our calculations showed that this was not the case for any of the monolayers we considered.

XES and XAS measurements supported the conclusions of our DFT calculations. The overlap between the measured valence and conduction states were found to be consistent with metallic silicon, and the good general agreement between calculated and measured spectra validated our structural models and electronic structure calculations. These measurements also demonstrated how extremely oxygen-sensitive silicene really is, as the emission spectra began to show SiO2-like features after 15 minutes of beam exposure at 10-9 Torr. Whatever little residual oxygen remained in the measurement chamber after it was flushed with dry nitrogen gas and pumped down to ultra-high vacuum (UHV) conditions was still enough to somewhat oxidize the monolayer.



2 0 1 4 r e s e a r c h r e p o r t 15

ConclusionOur soft X-ray study of epitaxial silicene monolayers on the Ag(111) surface confirmed that they are indeed metallic and interact significantly with their substrates. As such, they are not suitable candidates for 2-D electronic applications. We also showed that these samples have a strong tendency to oxidize, even doing so under UHV conditions. This would suggest that any useful silicene device would have to be passivated by some form of chemical modification in order to prevent oxidation, which would inevitably change its electronic properties.

There are still a large number of promising avenues to explore in silicene research. Alternate, non-metallic growth substrates have been proposed [4], silicene multilayers [5] and nanoribbons [6] on silver substrates are yet to be fully understood, and functionalization and chemical modification of silicene monolayers may lead to oxidation resistance and weakened interaction with growth substrates [8].

Recently, the first silicene-based transistor was created [8]. The silicene monolayer used in this device was initially derived from physical vapour deposition on Ag(111), much like the process we used to obtain

Figure 1. (a) the structure of low-buckled freestanding silicene. note the sublattice inversion symmetry of the upper and lower layers. the relaxed structures of (b) (3 × 3)/(4 × 4) and c-e) (√7 × √7)/(√13 × √13) epitaxial silicene. (3 × 3)/(4 × 4) silicene has 18 Si atoms per unit cell for a coverage ratio of 1.125 Si:ag, while the (√7 × √7)/(√13 × √13) silicene structures contain 14 Si sites per unit cell for a coverage ratio of 1.077 Si:ag. visualization provided by the veSta software package.

Figure 2. (a) theoretical XeS and XaS spectra obtained from the calculated Si pdoS for epitaxial and freestanding silicene. the Fermi energy is marked by a dashed vertical line. Calculated XaS spectra including a Si 2p core-hole are indicated by a dashed line. (b) XeS and XaS measurements of epitaxial silicene and Si references (a sputtered crystalline Si wafer in fuchsia and an amorphous Sio2 crystal (XeS) and native Sio2 oxide on a Si wafer (XaS) in black). dotted lines indicate peaks in the XeS spectrum and the calculated or measured features they are attributed to. the overlaps of the measured and calculated XeS and XaS spectra, which are used as a metric for the degree to which the substances are metallic, are shown in the rightmost panels, magnified 2× vertically and on an enlarged horizontal range.


our epitaxial monolayers. While the device’s performance was not up to the standards of bulk silicon or graphene-based transistors and it oxidized in a matter of minutes, this achievement represents an important first step toward silicene-based electronics.

References [1] vogt, P., de Padova, P., Quaresima, C., avila, J., Frantzeskakis, e., asensio, M. C., ... & Le Lay, g. (2012). Silicene: compelling experimental evidence for graphenelike two-dimensional silicon. Physical review letters, 108(15), 155501.

[2] tsoutsou, d., Xenogiannopoulou, e., golias, e., tsipas, P., & dimoulas, a. (2013). evidence for hybrid surface metallic band in (4× 4) silicene on ag (111). Applied Physics Letters, 103(23), 231604.

[3] huang, S., Kang, W., & Yang, L. (2013). electronic structure and quasiparticle bandgap of silicene structures. Applied Physics Letters, 102(13), 133106.

[4Kaloni, t. P., Schreckenbach, g., & Freund, M. S. (2014). Large enhancement and tunable Band gap in Silicene by Small organic Molecule adsorption. The Journal of Physical Chemistry C, 118(40), 23361-23367.

[5] vogt, P., Capiod, P., Berthe, M., resta, a., de Padova, P., Bruhn, t., ... & grandidier, B. (2014). Synthesis and electrical conductivity of multilayer silicene. Applied Physics Letters, 104(2), 021602.

[6] de Padova, P., Quaresima, C., ottaviani, C., Sheverdyaeva, P. M., Moras, P., Carbone, C., ... & Le Lay, g. (2010). evidence of graphene-like electronic signature in silicene nanoribbons. Applied Physics Letters, 96(26), 261905.

[7] huang, B., Xiang, h. J., & Wei, S. h. (2013). Chemical Functionalization of Silicene: Spontaneous Structural transition and exotic electronic Properties. Physical review letters, 111(14), 145502.

[8] tao, L., Cinquanta, e., Chiappe, d., grazianetti, C., Fanciulli, M., dubey, M., ... & akinwande, d. (2015). Silicene field-effect transistors operating at room temperature. Nature nanotechnology, 10(3), 227-231.

Acknowledgementsthe authors gratefully acknowledge financial support from the natural Sciences and engineering research Council of Canada (nSerC) and the Canada research Chair Program, the “2d-nanoLattiCeS” project of the Future and emerging technologies (Fet) program within the 7th framework program for research of the european Commission under Fet grant no. 270749, the deutsche Forschungsgemeinschaft (dFg) under grant no. vo1261/3–1, support from ConaCYt Mexico under grant 186142, and the russian Foundation for Basic research (Projects 14–02–00006). Calculations used Compute Canada's Westgrid hPC consortium.

Beamline information We used the XeS endstation of the reiXS beamline (10-id2). our measurements consisted of Si 2p XaS in teY-mode and Si L2,3 XeS (non-resonant) using a microchannel plate detector.

Figure 3. (a) high-resolution StM topograph (6×6 nm, ubias=-1.12 v, i = 0.65 na) of the (4×4) silicene monolayer. Clearly visible is the “flowerlike” pattern that results from the upward displacement of 6 of the 18 Si atoms in the honeycomb structure. (b) StM topograph (21.6×21.6 nm, ubias

= -1.20 v, i = 1.08 na) of “(√13×√13)” silicene. StM topographs were obtained under uhv conditions (< 2×10-10 torr).


2 0 1 4 r e s e a r c h r e p o r t 17

PRINCIPAL CONTACT:

Dr. Fazel Fallah tafti post-Doctoral Fellow princeton University [email protected]


Physical Review B, Issue 13, Volume 89, pp. 134502. DoI: 10.1103/physRevB.89.134502

AuThORS:

F. F. tafti1,* J. p. clancy2 M. Lapointe-Major1 c. collignon1 s. Faucher1 J. a. sears2 a. Juneau-Fecteau1 N. Doiron-Leyraud1 a. F. Wang3 X.-G. Luo3 X. h. chen3 s. Desgreniers4 Young-June Kim2 Louis taillefer1,5,†

1 Département de physique & RQMp Université de sherbrooke

2 Department of physics University of toronto

3 hefei National Laboratory for physical sciences at Microscale and Department of physics University of science and technology of china

4 Faculty of science University of ottawa

5 canadian Institute for advanced Research

Sudden reversal in the pressure dependence of Tc in the iron-based superconductor CsFe2As2: A possible link between inelastic scattering and pairing symmetry

introductionFew superconductors can host more than one pairing state. Such superconductors bring the possibility of a transition from one pairing symmetry to another in the same material: an extremely rare event of fundamental importance, since the transition temperature can respond differently to tuning parameters in different pairing states. The multi-band nature of superconductivity in iron-based superconductors brings these materials one step closer to the possibility of hosting more than one pairing symmetry. However, to tune the same material from one pairing state to another, it should also allow for near degeneracy between different pairing states. Several theoretical proposals suggested such an intriguing possibility in the over-electron-doped chalchogenides, but in 2013 we discovered this rare transition in over-hole-doped pnictide KFe2As2 by observing a sudden reversal in the pressure dependence of Tc in this material [1]. In the present work, we report our finding of the same phenomenon in another system CsFe2A2 shown in Figure 1. This finding establishes the change of pairing symmetry as a common trend amongst over-hole-doped iron-pnictides. This time we try to push our understanding of the parameters that control this transition by comparing CsFe2A2 and KFe2As2.

Our work encompasses a thorough investigation of lattice parameters of KFe2As2 under pressure up to 60 kbar via high pressure X-ray measurements as well as resistivity and Hall measurements under pressure on both CsFe2A2 and KFe2As2 up to 18 and 25 kbar, respectively. We show that lattice parameters and disorder do not play a role in controlling the critical pressure Pc where Tc reversal occurs. By analyzing the response of resistivity to pressure we find a link between inelastic scattering processes encoded in the resistivity data and the Tc reversal.

ScienceSeveral studies on the Ba1−xKxFe2As2 series suggest that lattice parameters, in particular the As-Fe-

As bond angle, control Tc [2-4]. To explore this hypothesis, we measured the lattice parameters of KFe2As2 as a function of pressure up to 60 kbar in order to find out how much pressure is required to tune the lattice parameters of CsFe2As2 so they match those of KFe2As2. Cs has a larger atomic size than K; hence one can view CsFe2As2 as a negative-pressure version of KFe2As2. The four panels of Figure 2 show the pressure variation of the lattice constants a and c, the unit cell volume (V = a2c), and the intraplanar As-Fe-As bond angle (α) in KFe2As2. The red horizontal line in each panel marks the value of the corresponding lattice parameter in CsFe2As2. In order to tune a, c, V, and α in KFe2As2 to match the corresponding values in CsFe2As2, a negative pressure of approximately -10, -75, -30, and -30 kbar is required, respectively. Adding these numbers to the critical pressure for KFe2As2 (Pc=17.5 kbar), we would naively estimate that the critical pressure in CsFe2As2 should be Pc+30 kbar or higher.

We find instead that Pc=14 kbar, showing that other factors are involved in controlling Pc. It is possible that the lower Pc in CsFe2As2 could be due to the fact that Tc itself is lower than in KFe2As2 at zero pressure, i.e., that the low-pressure phase is weaker in CsFe2As2. One hypothesis for the lower Tc in CsFe2As2 is a higher level of disorder. To test this idea, we studied the pressure dependence of Tc in a less pure KFe2As2 sample. Figure 1 compares the T–P phase diagram in three samples: (1) a high-purity KFe2As2 sample, with ρ0=0.2µΩcm; (2) a less pure KFe2As2 sample, with ρ0=1.3µΩcm, measured here; (3) a CsFe2As2 sample with ρ0=1.5 µΩcm. Different disorder levels in our samples are due to growth conditions, not deliberate chemical substitution or impurity inclusions. First, we observe that a six-fold increase of ρ0 has negligible impact on Pc in KFe2As2. Second, we observe that Pc is 4 kbar smaller in CsFe2As2 than in KFe2As2, for samples of comparable ρ0. These observations rule out the idea that disorder could be responsible for the lower value of Pc in CsFe2As2 compared to KFe2As2.



Figure 1. Pressure dependence of Tc in three samples: pure KFe2as2 (black circles), less pure KFe2as2 (gray circles), and CsFe2as2 (sample 2, red circles). even though the Tc values for the two KFe2as2 samples are different due to different disorder levels, measured by their different residual resistivity ρ0, the critical pressure is the same (Pc=17.5kbar). this shows that the effect of disorder on Pc in KFe2as2 is negligible. For comparable ρ0, the critical pressure in CsFe2as2 , Pc=14 kbar, is clearly smaller than in KFe2as2.

Figure 2. Structural parameters of KFe2as2 as a function of pressure, up to 60 kbar: (a) lattice constant a; (b) lattice constant c; (c) unit cell volume V=a2c; (d) the intraplanar as-Fe-as bond angle α as defined in the inset. experimental errors on lattice parameters are smaller than symbol dimensions. the black dotted line in panels (a), (b), and (c) is a fit to the standard Murnaghan equation of state extended smoothly to negative pressures. the black dotted line in panel (d) is a third-order power-law fit. in each panel, the horizontal red line marks the lattice parameter of CsFe2as2, and the vertical red line gives the negative pressure required for the lattice parameter of KFe2as2 to reach the value in CsFe2as2.

DiscussionIn a recent theoretical work by Fernandes and Millis, it is demonstrated that different pairing interactions in 122 systems can favour different pairing symmetries [5]. In their model, SDW-type magnetic fluctuations with wave vector (π, 0) favour s± pairing, whereas Neel-type fluctuations, with wave vector (π, π), strongly suppress the s± state and favour d-wave pairing. A gradual increase in the (π, π) fluctuations eventually causes a phase transition from an s± superconducting state to a d-wave state, producing a V-shaped Tc vs. P curve [5]. In KFe2As2 and CsFe2As2, it is conceivable that two such competing interactions are at play, with pressure tilting the balance in favour of one versus the other. We explore such a scenario by looking at how the inelastic scattering evolves with pressure, measured via the inelastic resistivity, defined as ρ(T )−ρ0, where ρ0 is the residual resistivity.

Figure 3(a) shows raw resistivity data from the KFe2As2 sample with ρ0=1.3µΩcm below 30 K. To extract ρ(T )−ρ0 at each pressure, we make a cut through each curve at T=20 K and subtract from it the residual resistivity ρ0 that comes from a power-law fit ρ=ρ0+AT n to each curve. ρ0 is determined by disorder level and does not change as a function of pressure. The resulting ρ(T=20 K)−ρ0 values for this sample are then plotted as a function of normalized pressure P/Pc in Figure 3(b). Through a similar process we extract the pressure dependence of ρ(20 K)−ρ0 in CsFe2As2 and the purer KFe2As2 sample with ρ0 =0.2µΩcm in Figures 3(c) and (d). In all three samples, at P/Pc > 1, the inelastic resistivity varies linearly with pressure. As P drops below Pc, the inelastic resistivity in (K,Cs)Fe2As2 shows a clear rise below their respective Pc, over and above the linear regime. Figure 3 therefore suggests a connection between the transition in the pressure dependence of Tc and the appearance of an additional inelastic scattering process.

ConclusionIn summary, we discovered a pressure-induced reversal in the dependence of the transition temperature Tc on pressure in the iron-based superconductor CsFe2As2, similar to our previous finding in KFe2As2. We interpret the Tc reversal at the critical pressure Pc as a transition from one pairing state to another. The fact that Pc is smaller in CsFe2As2 than in KFe2As2, even though all lattice parameters would suggest otherwise, shows that structural parameters alone do not control Pc. We also demonstrate


2 0 1 4 r e s e a r c h r e p o r t 19

Figure 3. (a) resistivity data for the KFe2as2 sample with ρ0=1.3 μΩcm at five selected pressures. the black vertical arrow shows a cut through each curve at T=20 K and the dashed line is a power-law fit to the curve at P=23.8 kbar from 5 to 15 K that is used to extract the residual resistivity ρ0. inelastic resistivity, defined as ρ(T=20 K)−ρ0, is plotted vs. P/Pc in (b) the less pure KFe2as2 sample, (c) the purer KFe2as2 sample, and (d) CsFe2as2, where Pc=17.5 kbar for KFe2as2 and Pc=14 kbar for CsFe2as2. in panels (b), (c), and (d) the dashed black line is a linear fit to the data above P/Pc=1.

that disorder has negligible effect on Pc. Our study of the pressure dependence of resistivity in CsFe2As2 and KFe2As2 reveals a possible link between Tc and inelastic scattering. Our proposal is that the high-pressure phase in both materials is an s± state that changes sign between Γ-centered pockets. As the pressure is lowered, the large-Q inelastic scattering processes that favour d-wave pairing in pure KFe2As2 and CsFe2As2 grow until at a critical pressure Pc they cause a transition from one superconducting state to another, with a change of pairing symmetry from s wave to d wave. The experimental evidence for this is the fact that below Pc the inelastic resistivity, measured as the difference ρ(20 K)−ρ0, deviates upwards from its linear pressure dependence at high pressure.

References [1] tafti, F. F., Juneau-Fecteau, a., delage, M. e., de Cotret, S. r., reid, J. P., Wang, a. F., ... & taillefer, L. (2013). Sudden reversal in the pressure dependence of tc in the iron-based superconductor KFe2as2. Nature Physics,9(6), 349-352.

[2] rotter, M., Pangerl, M., tegel, M., & Johrendt, d. (2008). Superconductivity and crystal structures of (Ba1− xKx) Fe2as2 (x= 0–1). Angewandte Chemie International Edition, 47(41), 7949-7952.

[3] Kimber, S. a., Kreyssig, a., Zhang, Y. Z., Jeschke, h. o., valentí, r., Yokaichiya, F., ... & argyriou, d. n. (2009). Similarities between structural distortions under pressure and chemical doping in superconducting BaFe2as2. Nature Materials, 8(6), 471-475.

[4] Chu, J. h., analytis, J. g., Kucharczyk, C., & Fisher, i. r. (2009). determination of the phase diagram of the electron-doped superconductor Ba (Fe 1− x Co x) 2 as 2. Physical Review B, 79(1), 014506.

[5] Fernandes, r. M., & Millis, a. J. (2013). Suppression of superconductivity by neel-type magnetic fluctuations in the iron pnictides. Physical review letters,110(11), 117004.

AcknowledgementsWe thank a.v. Chubukov, r.M. Fernandes, and a. J. Millis for helpful discussions, and S. Fortier for his assistance with the experiments. the work at Sherbrooke was supported by the Canadian institute for advanced research and a Canada research Chair and it was funded by nSerC, FrQnt, and CFi. Work done in China was supported by the national natural Science Foundation of China (grant no. 11190021), the Strategic Priority research Program (B) of the Chinese academy of Sciences, and the national Basic research Program of China. research at the university of toronto was supported by the nSerC, CFi, ontario Ministry of research and innovation, and Canada research Chair program.

Beamline information high-pressure X-ray experiments were performed on polycrystalline powder specimens of KFe2as2 up to 60 kbar with the hXMa beam line at the Canadian Light Source, using a diamond anvil cell with silicon oil as the pressure medium. Pressure was tuned blue with a precision of 2 kbar using the r1 fluorescent line of a ruby chip placed inside the sample space. Xrd data were collected using angle-dispersive techniques, employing high-energy X-rays (Ei=24.35 kev) and aMar345 image plate detector. Structural parameters were extracted from full profile rietveld refinements using gSaS software.


PRINCIPAL CONTACT:

Dennis tokaryk professor Department of physics University of New Brunswick [email protected] 506 458 7933


Physical Chemistry Chemical Physics, 2014, Issue 33, Volume 16, pp.17373-17407. DoI: 10.1039/c4cp01443j

AuThORS:

Manfred Winnewisser1 Brenda p. Winnewisser1 Frank c. De Lucia1 Dennis W. tokaryk2 stephen c. Ross2 Brant e. Billinghurst3

1 Department of physics the ohio state University

2 Department of physics and centre for Laser, atomic, and Molecular sciences University of New Brunswick

3 canadian Light source

Pursuit of quantum monodromy in the far-infrared and mid-infrared spectra of NCNCS using synchrotron radiation

introductionQuantum monodromy has a dramatic and defining impact on all those physical properties of chain molecules that depend on a large-amplitude bending coordinate, including in particular the distribution of the ro-vibrational energy levels. As revealed by its pure rotational (a-type) spectrum [1], cyanogen iso-thiocyanate, NCNCS (Figure 1 illustrates its structure), is a particularly illuminating exemplar of quantum monodromy: it clearly shows the distinctive monodromy-induced dislocation of the ro-vibrational energy level pattern for its low-lying bending mode labelled ν7. This dislocation centers on a lattice defect in the energy vs. momentum map of the ro-vibrational levels at the top of the barrier to linearity, and represents an example of an excited state quantum phase transition [2, 3].

The large amplitude ro-vibrational dynamics of the low-lying bending mode in NCNCS is intimately linked to the topology of the surfaces of constant energy in the four-dimensional phase space associated with motion constrained by the potential function. Monodromy resulting from the champagne-bottle bending potential [4] is strongly imprinted on the wavefunctions and patterns of energy levels associated with this mode. Generalized-SemiRigid-Bender (GSRB) Hamiltonian calculations show that all important physical quantities, including effective rotational constants, ro-vibrational energies, and the expectation values of the electric dipole moment components, show the effects of quantum monodromy [1].

Before conducting our experiments at the CLS, data were limited to pure-rotational ΔJ=+1 transitions within a selection of ν7 bending vibrational levels. We have now obtained high-resolution far-infrared spectra of transitions between the large-amplitude ν7 bending vibrations, and to several mid-infrared levels. Initial analyses of the data demonstrate the accuracy of the previous GSRB calculations, and provide a direct measurement of the energy level positions plotted on the energy-momentum map shown in Figure 4.

scienceCyanogen iso-thiocyanate, NCNCS, is the best model system found so far for a molecule that clearly exhibits a distinctive monodromy-induced dislocation in the energy level pattern. The large-amplitude ν7 bending mode of NCNCS, which has a bent equilibrium structure (see Figure 1), can be studied from the ground state to levels above the barrier to linearity, with very little interference from other vibrational excitations [1, 5-7]. The connection between the bending motion of NCNCS and the champagne bottle potential function can be understood by considering the schematic potential shown on the left-hand side of Figure 1. There the radial coordinate can represent the ν7 bending motion of the molecule with the origin (where the hump of the potential lies) corresponding to the linear configuration. For NCNCS the angular coordinate in this schematic figure then represents rotational motion around the long-axis (a-or z-axis) of the molecule. It is the nature of the coupling between these two motions that leads to monodromy in NCNCS.

The large amplitude of the ν7 (CNC bending) vibration means that the inverse moments of inertia of the molecule cannot be treated as constants during this motion, which is why the ν7 vibrational mode cannot be separated from the rotational motion [1]. It is because of this that we have used the GSRB to model the ν7 bending + rotational energy levels of NCNCS, and to calculate the intensities of the transitions in the ν7 sequence.

Ab initio calculations of the transition moments in NCNCS [5] indicated that the ν7 band we were seeking was one of the weakest fundamental transitions in the molecule. Nonetheless, over four two- to three-week campaigns at the CLS, we learned how to synthesize S(CN)2 under the constraints of working in a remote lab (the CLS wet labs), and how to effectively pyrolyze this precursor to form the more stable isomer NCNCS. In the end, we successfully acquired the far-infrared bending-mode spectra of both NCNCS (see Figure 2) and S(CN)2 between 60-200 cm-1 at high resolution using the synchrotron radiation. The data permitted an interesting comparison between the rather rigid bent molecule S(CN)2 [8, 9] and the much floppier isomer NCNCS.



2 0 1 4 r e s e a r c h r e p o r t 21

discussionThe GSRB calculations (Figure 3), based on the calculated dipole moment [5], indicated that both b-type and a-type transitions would be observed in the spectrum of the ν7 band sequence in NCNCS. This would be desirable, since the a-type transitions connect points on the energy-momentum map with the same rotational quantum number Ka but with different vibrational quantum number (vertical transitions on the map shown in Figure 4), while the b-type transitions connect points with a change of both a rotational quantum and a vibrational quantum (diagonal transitions (not shown) in Figure 4). However, a comparison of Figures 2 and 3 clearly shows that only a-type transitions were observed in our data. A similar situation was previously reported in the pure rotational spectra, for which both a- and b-type transitions were predicted to occur, but in which only the a-type transitions have so far been identified [1]. The transitions assigned at the time of publishing the paper that is the subject of this report are shown as vertical purple arrows in Figure 4. These transitions allow us to determine for the first time absolute intervals between some vibrational levels, provided that they share a common angular momentum Ka.

To find the absolute energy of all levels relative to the lowest possible level, b-type transitions with ΔKa=±1 must be observed and assigned. While neither the pure-rotational nor the far-infrared spectra appear suitable for this purpose, a mid-infrared band that we observed near 1185 cm-1 shows evidence of both a- and b-type transitions. Analysis of this spectrum could allow us to determine the relative energy between vertical stacks of levels shown in

Figure 1. the concept of monodromy (greek for “once around”) for the dynamics of a particle in a potential energy function shaped like the bottom part of a champagne bottle was introduced by Larry Bates [10] in 1991. this potential energy function is circularly symmetric with two conserved physical quantities: energy and angular momentum. the left-hand panel of this figure shows a schematic champagne bottle potential energy function for the quasi-linear in-plane bending mode of nCnCS. the large-amplitude coordinate ρ is defined on the molecular structure in the right-hand panel. the critical point of the potential function is indicated together with the topologies of phase-space surfaces of constant energy above and below this point [5]. the equilibrium structure of nCnCS from ab initio calculations with CCSd(t)/cc-pv5Z level of theory is given in the right-hand panel [5].

Figure 2. the experimentally-observed spectrum of the ν7 band sequence, taken in absorption against the continuum provided by synchrotron radiation from the Canadian Light Source. 121 mtorr of nCnCS was admitted into the 2 m-long sample cell, through which the synchrotron light passed 36 times.

Figure 4, thereby completing the energy-momentum map. Further, perturbations between levels within the ν7 sequence, observed in the original pure-rotational spectrum, can be used to corroborate intervals obtained via the 1185 cm-1 band, and to determine intervals that this band may not provide.

ConclusionOur investigation of the effects of quantum monodromy on the spectrum of NCNCS is nearly complete. We have found that this elusive species is more stable than its isomer S(CN)2, in agreement with our recent ab initio calculation which has it more stable by about 50 kJ mol−1 [9], and that we can produce it reliably and consistently in the requisite quantities at the CLS. Further, we have found that it exhibits remarkable chemical and kinetic stability in a 2 m-long stainless steel White cell if the cell is cooled

below 0°C. In addition to acquiring spectra of several higher-frequency small-amplitude vibrational modes in NCNCS, we have attained our main goal of observing the large-amplitude far-infrared bending mode ν7 and its associated sequence bands through its ro-vibrational spectrum near 80 cm−1.

However, the question remains: where are the b-type rotational or ro-vibrational transitions (Figure 2)? Perhaps they are considerably weaker than predicted, and the signal-to-noise ratio of our data is not yet sufficient to reveal them. It is important to note that the intensities calculated using the GSRB rely on the ab initio dipole moment functions as described in [1]. Any inaccuracy in those results will be reflected here.

Our GSRB calculations concerning energy levels, line positions, wave functions, expectation values of dipole moment components and line intensities together


with initial results presented in this work indicate that the unusual structure of the large-amplitude bending fundamental band system of NCNCS is a very specific signature of monodromy. Such signatures must appear in the spectrum of any molecule that is excited above its barrier to linearity.

References [1] Winnewisser, B. P., Winnewisser, M., Medvedev, i. r., de Lucia, F. C., ross, S. C., & Koput, J. (2010). analysis of the FaSSSt rotational spectrum of nCnCS in view of quantum monodromy. Physical Chemistry Chemical Physics,12(29), 8158-8189.

[2] Larese, d., & iachello, F. (2011). a study of quantum phase transitions and quantum monodromy in the bending motion of non-rigid molecules. Journal of Molecular Structure, 1006(1), 611-628.

[3] Larese, d., Pérez-Bernal, F., & iachello, F. (2013). Signatures of quantum phase transitions and excited state quantum phase transitions in the vibrational bending dynamics of triatomic molecules. Journal of Molecular Structure, 1051, 310-327.

[4] Bates, L. M. (1991). Monodromy in the champagne bottle. Zeitschrift für angewandte Mathematik und Physik ZAMP, 42(6), 837-847.

[5] Winnewisser, B. P., Winnewisser, M., Medvedev, i. r., Behnke, M., de Lucia, F. C., ross, S. C., & Koput, J. (2005). experimental confirmation of quantum monodromy: the millimeter wave spectrum of cyanogen isothiocyanate nCnCS. Physical review letters, 95(24), 243002.

[6] Winnewisser, M., Winnewisser, B. P., Medvedev, i. r., de Lucia, F. C., ross, S. C., & Bates, L. M. (2006). the hidden kernel of molecular quasi-linearity: quantum monodromy. Journal of molecular structure, 798(1), 1-26.

[7] King, M. a., Kroto, h. W., & Landsberg, B. M. (1985). Microwave spectrum of the quasilinear molecule, cyanogen isothiocyanate (nCnCS). Journal of Molecular Spectroscopy, 113(1), 1-20.

[8] Kisiel, Z., dorosh, o., Winnewisser, M., Behnke, M., Medvedev, i. r., & de Lucia, F. C. (2007). Comprehensive analysis of the FaSSSt rotational spectrum of S(Cn)2. Journal of Molecular Spectroscopy, 246(1), 39-56.

[9] Kisiel, Z., Winnewisser, M., Winnewisser, B. P., de Lucia, F. C., tokaryk, d. W., & Billinghurst, B. e. (2013). Far-infrared Spectrum of S(Cn)2 Measured with Synchrotron radiation: global analysis of the available high-resolution Spectroscopic data. The Journal of Physical Chemistry A, 117(50), 13815-13824.

Acknowledgements the experimental work of the ohio State university team was supported by the army research office, nSF, and naSa. B. Billinghurst would like to thank all of his colleagues at the Canadian Light Source for their advice particularly dr. J. C. Bergstrom for endless discussions about the physics of synchrotrons. damien Forthomme and Colin Sonnichsen are thanked for their help with the initial experiments. dr. Sylvestre twagirayezu is recognized and thanked for all his help in setting up the chemical laboratory in May 2013. dWt acknowledges financial support from the natural Sciences and engineering research Council of Canada (nSerC). SCr would like to thank dr. K. M. t. Yamada for many helpful discussions with regard to the calculation of intensities. the authors thank Professor Zbigniew Kisiel for critically reading the manuscript.

Beamline InformationFar-infrared Beamline 02B1-1 using the iFS 125hr Bruker Fourier transform spectrometer.

Figure 3. the top panel shows all predicted a-type parallel sub-bands for the CnC in-plane large amplitude bending mode ν7 for nCnCS. the middle panel displays all predicted b-type perpendicular sub-bands including Δvb=0, 1, 2, 3 transitions. in the bottom panel the superposition of all a-type and b-type transitions displays the entire hybrid band system of the large-amplitude bending mode ν7 for a limited range of J and Ka values. this means an enormous number of weak thz- and/or Fir ro-vibrational transitions if we include the fully extended P-, Q- and r-branches in a spectral range of roughly 130 cm-1 centered around 100 cm-1. this hybrid band system has a calculated total band intensity of only 4 km mol-1.

Figure 4. excerpt of the energy-momentum map for J=Ka with the 7 assigned sub-bands of the ν7 large amplitude in-plane bending mode of nCnCS for Ka=0 and vb=1 0, 2 1, 3 2; for Ka=1 and vb=1 0, 2 1, 3 2; for Ka=2 and vb=1 0. as of this writing 48 Loomis–Wood strands have been identified, allowing us to start building a fully experimental version of the ro-vibration energy-momentum map.


2 0 1 4 r e s e a r c h r e p o r t 23

PRINCIPAL CONTACT:

Mercedes Martinson phD candidate in physics & engineering physics University of saskatchewan [email protected]


Journal of Synchrotron Radiation, Volume 21, 2014, pp. 479-483. DoI: 10.1107/s1600577514003014

AuThORS:

Mercedes Martinson1 Nazanin samadi2 George Belev3 Bassey Bassey1 Rob Lewis4 Gurpreet aulakh5 Dean chapman1

1 physics and engineering physics University of saskatchewan

2 Biomedical engineering University of saskatchewan

3 Biomedical Imaging and therapy Beamlines canadian Light source

4 Medical Imaging University of saskatchewan

5 anatomy and cell Biology University of saskatchewan

Development of a bent Laue beam-expanding double-crystal monochromator for biomedical X-ray imaging

introductionBiomedical X-ray imaging techniques using synchrotron light sources has been well established [1-7]. Biomedical beamlines are in use around the world for a variety of imaging techniques including in-line phase contrast and micro-CT. At the CLS in Saskatoon, two biomedical beamlines have been commissioned. While both of these beamlines offer high flux, they suffer the drawback of small beam heights. BMIT-BM produces a maximum beam height of approximately 7 mm at the 23 m source-to-sample distance; BMIT-ID produces a maximum beam height of 11 mm at the 55 m source-to-sample distance. As a result, most samples must be scanned vertically through the beam to image the entire region of interest.

Vertical scanning poses severe limitations in two major areas. CT scans must be made in small vertical sections, and consecutive sections require enough overlap to reliably stitch the projections together, so regions of the subject are imaged repeatedly, a time-consuming process. In addition to longer scan times, the resulting vertical sections must then be stitched together during processing, which increases both processing time and likelihood of error.

The second, and more important, limitation is in dynamic imaging [8]. Many important physiological processes can only be understood by capturing movies of live systems. Examples include coronary angiography and functional lung imaging [9-13]. Scanning subjects using synchrotron beam makes it impossible to capture entire processes in one shot, which represents a major limitation for cutting-edge studies into physiological processes.

ScienceWhen a crystal wafer is cylindrically bent with the concave side facing the source, the diffracted beam will diverge with a virtual focus on the incident side of the crystal. Two such crystals placed in a non-dispersive divergent geometry [14] (Figure 1) produce a beam with a vertical height proportional to the distance between the second crystal and the

virtual focal point of the first crystal. The bending radius of the second crystal must be such that its focal point is the same as that of the first crystal in order to allow maximum reflection from the planes in the second crystal.

The focal point of a crystal is a function of bending radius, asymmetry and Bragg angles (χ and θΒ, respectively). The relationships between focal points, fij, and bending radii, ρi, are given below.

cos(χ – θΒ) –

cos(χ + θΒ) =

2 (1)

f11 f12 ρ1

cos(χ + θΒ) –

cos(χ – θΒ) =

2 (2)

f21 f22 ρ2

The expansion factor is determined by the ratio of bending radii. For the preliminary attempt, the following parameters were chosen: bending radius of first crystal: ρ1=1 m (f12= -0.5 m), bending radius of second crystal: ρ2=3 m (f21= 1.5 m), distance between crystals: Δf =1 m.

A preliminary experiment was performed using (1,1,1) silicon crystal wafers with a (1,1,1)-type reflection such that χ=19.47°. The beam size and shape were imaged on burn paper at three locations. Expansion was calculated as the ratio between the diffracted and incident beam.

DiscussionThe beam was expanded vertically to a maximum height 7.7x larger than the incident beam. The beam quality was evaluated using both absorption and phase-based imaging modalities. Absorption imaging tests were conducted for both projection and CT imaging. Flat-dark corrected images were devoid of artefacts, despite a visible line of lower intensity due to another competing reflection diffracting away intensity.

The expanded beam was used to capture live animal dynamic images using the flat panel detector running at 30 frames per second. This setup allowed an entire adult mouse to be imaged laterally in a single shot (Figure 2).

1 InstrumentatIon & technIques

~~


Flux was measured at 20.0 keV as confirmed by the absorption K-edge using a molybdenum filter. The measured flux was calculated to be 1.2×107 ph/s·mm2·mA without a filter. This would produce a surface dose of 2 mGy/s·mA. In contrast, the beamline’s Bragg double crystal monochromator produced a flux of 5.7×106 ph/s·mm2·mA under the same conditions.

A knife-edge placed horizontally in the expanded beam (Figure 3) revealed significant vertical blurring, which increased with the distance between the edge and detector. The blurring was not present in the horizontal direction, as a knife-edge placed vertically produced a sharp image at

all distances. These results indicate that the X-rays exiting the second crystal are parallel horizontally but not vertically. The vertical beam divergence can be explained by diffraction occurring in-depth within both crystals producing a polychromatic focus and allowing multiple rays to exit the same point in the second crystal but at different angles.

Conclusion The expanded beam was capable of completely filling the high-resolution (8.75 µm) Hamamatsu detector (FOV 31.08 mmH x 23.31 mmV) regularly used for micro-CT. This expansion would allow

objects up to about 21 mm in height to be imaged in a single rotation, rather than the vertical scanning method traditionally used at BMIT. This improvement would reduce scan times by as much as 85%.

This proof-of-principle study was made to determine whether a bent Laue beam expander could be developed for biomedical imaging applications. Beam expansion was successfully performed under a variety of conditions with expansions ranging from 2x to 7.7x (Table 1). The measured flux per unit area was comparable to that available with the flat Bragg double crystal monochromator currently used in the beamline. The increase in total photon count while expanding the beam size is made possible by the enhanced bandwidth of the bent Laue double crystal monochromator.

Some initial experiments were performed to demonstrate the viability and usefulness of the method. Problems that were identified include beam divergence after the second crystal as well as non-uniformity of the beam. The latter problem will be addressed by better control over the crystal and bending process but the beam divergence effect will require further study.

Table 1: Summary of expansion results and energy parameters.

Attempt Incident height (mm)

Diffracted height (mm)

Expansion factor

Silicon Wafer

Reflection type

Bragg angle

Energy (keV)

Proof-of-principle 2.5 9.0 3.6 (1,1,1) (1,1,1) 3.42° 33.16

target of 3x 2.1 4.2 2.0 (5,1,1) (2,2,0) 6.56° 28.3

target of 5x 2.9 15.0 5.2 (5,1,1) (2,2,0) 6.56° 28.3

target of 7x 3.0 23.0 7.7 (5,1,1) (2,2,0) 6.56° 28.3

µCt imaging 4.0 28.0 7.0 (1,1,1) (1,1,1) 6.56° 17.3

dynamic imaging 6.5 40 6.2 (1,1,1) (1,1,1) 6.31° 18.0

Flux 0.54 3.8 7.0 (1,1,1) (1,1,1) 5.67° 20.0

Figure 1. Schematic of the crystal geometry and orientation, ray-tracing diagrams and focal lengths.


2 0 1 4 r e s e a r c h r e p o r t 25

references [1] Suortti, P., & thomlinson, W. (2003). Medical applications of synchrotron radiation. Physics in medicine and biology, 48(13), r1.

[2] r.a. Lewis, Medical phase contrast X-ray imaging: current status and future prospects, Physics in Medicine and Biology, 49 (2004) 3573-3583.

[3] W. thomlinson, P. Suortti, d. Chapman, recent advances in synchrotron radiation medical research, Nuclear Instruments & Methods in Physics Research Section a-Accelerators Spectrometers Detectors and Associated Equipment, 543 (2005) 288-296.

[4] Y. Liu, J. nelson, C. holzner, J.C. andrews, P. Pianetta, recent advances in synchrotron-based hard X-ray phase contrast imaging, Journal of Physics D: Applied Physics, 46 (2013) 494001.

[5] P. Suortti, J. Keyriläinen, W. thomlinson, analyser-based X-ray imaging for biomedical research, Journal of Physics D: Applied Physics, 46 (2013) 494002.

[6] P. Coan, a. Bravin, g. tromba, Phase-contrast X-ray imaging of the breast: recent developments towards clinics, Journal of Physics D: Applied Physics, 46 (2013) 494007.

[7] a. Bravin, P. Coan, P. Suortti, X-ray phase-contrast imaging: from pre-clinical applications towards clinics, Physics in Medicine and Biology, 58 (2013) r1.

[8] r.a. Lewis, n. Yagi, M.J. Kitchen, M.J. Morgan, d. Paganin, K.K.W. Siu, K. Pavlov, i. Williams, K. uesugi, M.J. Wallace, C.J. hall, J. Whitley, S.B. hooper, dynamic imaging of the lungs using X-ray phase contrast, Physics in Medicine and Biology, 50 (2005) 5031-5040.

[9] K. hyodo, M. ando, Y. oku, S. Yamamoto, t. takeda, Y. itai, S. ohtsuka, Y. Sugishita, J. tada, development of a two-dimensional imaging system for clinical applications of intravenous coronary angiography using intense synchrotron radiation produced by a multipole wiggler, Journal of Synchrotron Radiation, 5 (1998) 1123-1126.

[10] S.B. hooper, M.J. Kitchen, M.L.L. Siew, r.a. Lewis, a. Fouras, a. B te Pas, K.K.W. Siu, n. Yagi, K. uesugi, M.J. Wallace, imaging Lung aeration and Lung Liquid Clearance at Birth using Phase Contrast X-ray imaging, Clinical and Experimental Pharmacology and Physiology, 36 (2009) 117-125.

[11] L. Porra, h. Suhonen, P. Suortti, a.r.a. Sovijärvi, S. Bayat, effect of positive end-expiratory pressure on regional ventilation distribution during bronchoconstriction in rabbit studied by synchrotron radiation imaging*, Critical Care Medicine, 39 (2011) 1731-1738 1710.1097/CCM.1730b1013e318218a318375.

[12] e. Schültke, M.e. Kelly, C. nemoz, S. Fiedler, L. ogieglo, P. Crawford, J. Paterson, C. Beavis, F. esteve, t. Brochard, M. renier, h. requardt, d. dallery, g. Le duc, K. Meguro, dual energy Ct at the synchrotron: a piglet model for neurovascular research, European Journal of Radiology, 79 (2011) 323-327.

[13] a. astolfo, e. Schültke, r.h. Menk, r.d. Kirch, B.h.J. Juurlink, C. hall, L.-a. harsan, M. Stebel, d. Barbetta, g. tromba, F. arfelli, in vivo visualization of gold-loaded cells in mice using X-ray computed tomography, Nanomedicine: nanotechnology, biology, and medicine, 9 (2013) 284-292.

[14] P. Suortti, C. Schulze, Fixed-exit Monochromators for high-energy Synchrotron radiation, Journal of Synchrotron Radiation, 2 (1995) 6-12.

Figure 2. Flat-dark-corrected frame from a movie of a live mouse captured with a 200 mm flat-panel detector (hamamatsu C9252dK-14) at 30 frames/s. the movie is available online in the supporting information. the vertical line on the right is an artefact of the detector, not the beam.

Figure 3. vertical and horizontal knife-edge placed at (a) 140 mm and (b) 5135 mm sample-detector distance.

acknowledgements: the authors wish to acknowledge Melanie van der Loop for overseeing the live animal imaging test. Mercedes Martinson, nazanin Samadi, Bassey Bassey, and gurpreet aulakh are Fellows, and dean Chapman and rob Lewis are Mentors in the Canadian institutes of health research training grant in health research using Synchrotron techniques (Cihr-thruSt). this work is supported in part by a discovery grant from the natural Sciences and engineering research Council of Canada (nSerC) and Canada research Chair.

Beamline information: BMit-BM beamline.


PRINCIPAL CONTACT:

Filip Van petegem associate professor Department of Biochemistry and Molecular Biology University of British columbia [email protected] 604-761-6017


Nature Communications, article 5397, Volume 5, November 5 2014. DoI: 10.1038/ncomms639

AuThORS:

Kelvin Lau (phD) Filip Van petegem (phD) Department of Biochemistry and Molecular Biology University of British columbia

Crystal structures of wild type and disease mutant forms of the ryanodine receptor SPRY2 domain

introductionWhen our muscles are stimulated to contract, an electrical signal is rapidly transformed into a chemical one: calcium. Calcium ions are important in many signalling processes, and are typically maintained at exquisitely low levels in the cytosol, the fluid within cells. They can enter either from the outside of the cell or from intracellular compartments, such as the sarcoplasmic reticulum (SR). The membranes that surround cells and the SR are intrinsically impermeable to calcium: these ions only get access through specialized channels that can open or close in response to stimuli. The main channel that conducts calcium ions from the SR to the cytosol is a huge protein called the Ryanodine Receptor (RyR) [1]. This channel consists of over 20,000 amino acids, and is a target for hundreds of genetic disease mutations. Different flavours of the channel are found in heart and skeletal muscle. Mutations in the cardiac channel (RyR2) can lead to potentially lethal arrhythmias, typically associated with stress [2]. These arrhythmias can lead to sudden cardiac death. Mutations in the skeletal muscle channel (RyR1), on the other hand, can result in several disorders [3,4]. One of these is known as malignant hyperthermia, a peculiar condition whereby a patient can remain healthy throughout life. However, under conditions of general anaesthesia, typically during surgery, the condition can cause life-threatening rises in body temperatures and muscle rigidity. Most mutations have been found to cause a gain-of-function: the channels open prematurely or remain open for longer periods of time, thus leaking calcium ions in the cytosol [5].

ScienceHere we set out to solve high-resolution structures of a portion of the RyR that harbours the positions of several disease-causing mutations [6]. We collected X-ray diffraction data of a crystallized domain, and used this to solve the structure of the domain of both the cardiac and skeletal muscle variants. This domain, also known as the ‘SPRY2’ domain, had been studied intensively in the past, and was thought to mediate important interactions between the RyR and another calcium channel in

skeletal muscle [7]. The core of the domain consists of two β-sheets (Figure 1). Unique insertions, as well as a ‘lid’ give it a unique shape. The structure looks very similar in RyR1 (skeletal muscle) and in RyR2 (cardiac variant). Importantly, the SPRY2 domain is ~50 residues longer than previously assumed, and this directly questions previous biochemical experiments that were performed with shorter constructs.

The structures map the locations of several disease-causing mutations. Of special interest is a mutation in RyR2 that was found to cause a rare loss-of-function (T1107M) [8]. Indeed, the mutation introduces a bulky methionine residue into a hydrophobic core where there is limited space for it. However, the mutation is not completely disruptive and we were able to purify the corresponding protein. Thermal stability measurements showed that the protein is indeed destabilized. A high-resolution structure of the mutant form allowed us to look at the detailed effects of the mutation on the structure (Figure 2). In order to accommodate the bulky side chain, the main chain is displaced, which results in several changes at the surface of the domain, including a disruption of a salt bridge. Most likely, these changes affect interactions with other RyR domains.

In order to figure out which other RyR domains interact with the SPRY2 domain, we used 6-dimensional docking approaches to locate the high-resolution crystal structure into available cryo-electron microscopy maps of the intact RyR. Consistently, we obtained the same location and orientation in different available maps (Figure 3). This position is located in the so-called ‘clamp’ region, an area of the RyR that has been shown to undergo substantial conformational changes. Several disease mutations seem to cluster at domain-domain interfaces involving the SPRY2 domain.

DiscussionThe ryanodine receptor is a large ~2.2MDa channel-forming protein that consists of many domains. These domains form individual modules that can mediate interactions with other proteins and small molecules. Here we determined a high-

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2 0 1 4 r e s e a r c h r e p o r t 27

resolution crystal structure of the SPRY2 domain, a module previously thought to mediate interactions with the voltage-gated calcium channel in skeletal muscle. Such an interaction is of prime interest, as a prevailing model in the field suggests a direct mechanical coupling between the voltage-gated calcium channel (located in the plasma membrane) and the Ryanodine Receptor (located in the SR membrane) in skeletal muscle tissue [9,10]. This would allow for changes in the voltage across the plasma membrane to directly allow calcium release from the SR. However, in direct contrast with multiple previous reports, we found that the SPRY2 domain does not mediate significant interactions with the voltage-gated calcium channel. Isothermal titration calorimetry experiments with the SPRY2 domain did not show any significant heat signals upon adding a cytosolic loop of Caν1.1, the voltage-gated calcium channel isoform expressed in skeletal muscle. In retrospect, multiple reports that previously used the SPRY2 domain for pull-down experiments had used an incomplete construct, missing the ‘lid’ and extensions on the N-terminus and C-terminus of the domain. Our own size exclusion chromatograms showed that such an incomplete construct readily aggregates, suggesting it is misfolded and that any experiment using such a construct is likely to give false results. It is therefore crucial to use full domains containing all subdomains required for proper folding.

The high-resolution structure, docked into full-length low-resolution cryo-electron microscopy maps, allowed us to look at the detailed environments of several mutations linked to disease. Of prime interest was a mutation in the cardiac variant that has been linked to stress-induced cardiac arrhythmias and to hypertrophic cardiomyopathy. Previous functional experiments had suggested that this mutation (T1107M) causes a loss-of-function, leading to reduced release of calcium. Interestingly, we find that the mutation can be tolerated, but induces conformational changes that likely couple to neighbouring domains in the Ryanodine Receptor. This confirms a prevailing theme that RyR disease mutations mostly affect domain-domain interactions. In addition, the mutation destabilizes the domain, to the extent that a significant amount would be unfolded at body temperature.

Figure 1. overall structure of the SPrY2 domain of the skeletal muscle ryanodine receptor (ryr1). Shown are secondary structure elements in cartoon representation. the ‘core’, which was previously assumed to constitute the entire SPrY2 domain, is shown in yellow. however, several additional elements are required for proper folding, including an n-terminal extension strand, and a ‘lid’ that mediates hydrophobic contacts with the core. an extended ‘tail’ mediates crystal contacts. a typical beta strand in SPrY folds is cut in two halves by an insertion (‘insertion loop’) that is strictly conserved in all ryr sequences. We also solved the structure of the ryr2 variant of the same domain, which displays a similar fold.

Figure 2. Structural changes induced by the a1107M disease-causing mutation. Superposition of the wild type (white) SPrY2 domain of the cardiac ryanodine receptor (ryr2) from mouse and the a1107M mutant (orange), which mimics the human mutation t1107M, linked to hypertrophic cardiomyopathy and catecholaminergic polymorphic ventricular tachycardia. the Met (black) is already modeled into the wild type structure, showing that it would clash with the W1156 side chain. in order to accommodate the bulky residue, the main chain beta strand is pushed outwards, which affects surface residues. e1106 and r1214 normally engage in a salt bridge, but this is now disrupted, resulting in disorder for the r1214 side chain. as a result, this buried disease-causing mutation results in changes at the surface, which likely affects domain-domain interactions within ryr2. in addition, the mutation causes a significant decrease in thermal stability, such that a significant portion is likely unfolded at physiological temperatures.


Conclusion Obtaining high-resolution structures of individual domains of the Ryanodine Receptor has been a successful approach for the past six years. Together with available cryo-electron microscopy (EM) maps of intact protein, this has allowed us to build pseudo-atomic models. Recently, since the original publication of our SPRY2 domain structure, three new cryo-EM studies have been published, describing the structures at improved resolution [11-13]. These new studies provide major strides forward, especially in our understanding the transmembrane area. However, the local resolution in multiple parts of the cytosolic portion, which includes the SPRY2 domain, is much lower, leading to ambiguity on the identity of individual domains for which no crystal structure is available. As such, obtaining high-resolution crystal structures of individual domains and domain clusters will continue to be of use, especially when detailed insights regarding disease-causing mutations are needed.

In addition, we still know very little about the mechanisms through which auxiliary proteins and small molecules affect RyRs. A long list of ligands is known, but their exact binding sites are mostly obscure.

Figure 3. Location of the SPrY2 domain within full-length ryanodine receptor. the black mesh represents a cryo-electron microscopy map, determined at ~10Å resolution (eMdB accession number 1606). the cartoons represent crystal structures of the n-terminal disease hot spot, the phosphorylation domain, and the SPrY2 domain, fit within the ryr1 tetramer. these positions were obtained using unbiased 6-dimensional docking, and correspond to the positions with the highest cross-correlation coefficients (Laplacian filtered for the SPrY2 domain). the same position for the SPrY2 domain is obtained in two other maps (eMdB 1607 and 5014). the bar graph on the right shows a correlation plot, displaying the normalized correlation coefficients for the top 10 hits for the SPrY2 domain in the eMdB 5014 map. importantly, the top hit stands out from other solutions down the ranking.

Finally, by comparing detailed structural changes induced by disease-causing mutations, it should be possible to devise novel compounds that can stabilize the native state, thus reversing the effects of the mutations. High-resolution structures will be invaluable in devising and optimizing potential therapeutics.

references [1] van Petegem, F. (2015). ryanodine receptors: allosteric ion channel giants. Journal of molecular biology, 427(1), 31-53.

[2] Priori, S. g., napolitano, C., tiso, n., Memmi, M., vignati, g., Bloise, r., ... & danieli, g. a. (2001). Mutations in the cardiac ryanodine receptor gene (hryr2) underlie catecholaminergic polymorphic ventricular tachycardia. Circulation,103(2), 196-200.

[3] Fujii, J., otsu, K., Zorzato, F., de Leon, S., Khanna, v. K., Weiler, J. e., ... & MacLennan, d. h. (1991). identification of a mutation in porcine ryanodine receptor associated with malignant hyperthermia. Science, 253(5018), 448-451.

[4] Zhang, Y., Chen, h. S., Khanna, v. K., de Leon, S., Phillips, M. S., Schappert, K., ... & MacLennan, d. h. (1993). a mutation in the human ryanodine receptor gene associated with central core disease. Nature genetics, 5(1), 46-50.

[5] Priori, S. g., & Chen, S. W. (2011). inherited dysfunction of sarcoplasmic reticulum Ca2+ handling and arrhythmogenesis. Circulation research, 108(7), 871-883.

[6] Lau, K., & van Petegem, F. (2014). Crystal structures of wild type and disease mutant forms of the ryanodine receptor SPrY2 domain. Nature communications, 5.

[7] tae, h.S. et al. (2011). Cyclisation of the intrinsically disordered α1s dihydropyridine receptor ii-iii loop enhances secondary structure and in vitro function. J Biol Chem 286, 22589-22599.

[8] tang, Y., tian, X., Wang, r., Fill, M. & Chen, S.r. (2012). abnormal termination of Ca2+ release is a common defect of ryr2 mutations associated with cardiomyopathies. Circulation research 110, 968-977.

[9] rios, e. & Brum, g. (1987). involvement of dihydropyridine receptors in excitation-contraction coupling in skeletal muscle. Nature 325, 717-720.

[10] Block, B.a., imagawa, t., Campbell, K.P. & Franzini-armstrong, C. (1988).Structural evidence for direct interaction between the molecular components of the transverse tubule/sarcoplasmic reticulum junction in skeletal muscle. J Cell Biol 107, 2587-2600.

[11] efremov, r.g., Leitner, a., aebersold, r. & raunser, S. (2014).architecture and conformational switch mechanism of the ryanodine receptor. Nature.

[12] Zalk, r. et al. (2014). Structure of a mammalian ryanodine receptor. Nature.

[13] Yan, Z. et al. (2014). Structure of the rabbit ryanodine receptor ryr1 at near-atomic resolution. Nature.

acknowledgements We thank the support staff at the advanced Photon Source gM/CaCat beamline 23-id-d, the Stanford Synchrotron radiation Lightsource and at the Canadian Light Source. this work is supported by an operating grant from the Cihr (MoP-119608, application # 259009) to F.v.P.

Beamline information CLS beamline CMCF; aPS beamline 23-id-d-gM/Ca. technique: Macromolecular X-ray diffraction (Sulphur-Sad and Mr).


2 0 1 4 r e s e a r c h r e p o r t 29

PRINCIPAL CONTACT:

p. Lynne howell senior scientist and associate chief the hospital For sick children professor, University of toronto [email protected] (416) 813-5378


Proceedings of the National Academy of Sciences of the United States of America, July 29 2014, Issue 20, Volume 111, pp. 11013-11018. DoI: 10.1073/pnas.1406388111

AuThORS:

Dustin J. Little1,2 Grace Li1,2 christopher Ing1,2 Benjamin R. DiFrancesco3 Natalie c. Bamford1,2 howard Robinson4 Mark Nitz3 Régis pomès1,2 p. Lynne howell1,2

1 program in Molecular structure & Function, Research Institute the hospital for sick children

2 Department of Biochemistry University of toronto

3 Department of chemistry University of toronto

4 photon sciences Division Brookhaven National Laboratory

Modification and periplasmic translocation of the biofilm exopolysaccharide poly-β-1,6-N-acetyl-d-glucosamine

introductionExtracellular polysaccharides are a main component of bacterial biofilms and have been shown to play an important role in cellular aggregation, surface attachment, and serve as a protective barrier against antibiotics and host defense mechanisms [1, 2]. A key exopolysaccharide required for biofilm formation by a number of pathogenic bacteria is poly-β-1,6-N-acetyl-D-glucosamine (PNAG). In E. coli, proteins encoded by the pgaABCD operon are responsible for PNAG biosynthesis [3]. PgaB is a two-domain outer-membrane lipoprotein that partially deacetylates PNAG, a modification required for polymer export and subsequent biofilm formation [4]. The N-terminal domain of PgaB (PgaB22-309) belongs to the family four carbohydrate esterases (CE4s) but has a unique circularly permuted arrangement of the canonical CE4 motifs [5, 6]. This results in the absence of a conserved aspartic acid residue required for catalysis [5], and has been proposed to attenuate PgaB activity to maintain the low levels of PNAG deacetylation (~3-5% of the residues) observed in vivo [3-5]. The C-terminal domain of PgaB (PgaB310-672) is required for PNAG deacetylation and export [4], however the roles it plays in these processes are unknown.

In addition to the function of PgaB310-672, what remains poorly understood during biosynthesis is whether PNAG is free or protected throughout periplasmic transport. As the length and insolubility of PNAG make it challenging to study in vitro, we characterized the structure and function of PgaB with short synthetic PNAG oligomers and used molecular dynamics (MD) simulations to study the binding of N-acetylglucosamine (GlcNAc) and glucosammonium (GlcNH3

+).

ScienceTo characterize the role of PgaB310-672 in PNAG deacetylation, activity assays were conducted on PgaB22-672, PgaB22-309, and PgaB310-672. PgaB22-672 displayed deacetylase activity, whereas PgaB22-309 and PgaB310-672 did not (Figure 1 (a)). Furthermore, activity could not be rescued when PgaB310-672 was added to PgaB22-309, suggesting that the association of both domains is required for activity. Docking studies with β-1,6-(GlcNAc)5 showed the oligomer

makes contacts with both the N- and C-terminal domains (Figure 1 (b)). Three of the nine interacting residues on PgaB310-672 (W387, T391, and R392) are 100 per cent conserved amongst PgaB homologs and reside on a helix preceding the deacetylase active site (Figure 1(b)).

The structure of PgaB310-672 reveals a (β/α)8-barrel fold that contains a β-hairpin loop (βHL) that extends over the top of the (β/α)8 barrel (Figure 1 (c)). This results in a highly electronegative pronounced narrow groove (Figure 1 (c)), suggesting it may bind PNAG along this domain. Structural comparison of PgaB310-672 revealed similarities to members of various glycoside hydrolase families. However, we were unable to demonstrate hydrolase activity with PNAG oligomers or artificial para-nitrophenyl (pNP) glycoside substrates. The domain could bind PNAG oligomers and displayed a dissociation constant of 1.3±0.2 mM for β-1,6-(GlcNAc)6 (Figure 1 (d)). To understand how PNAG binds to PgaB310-

672 we determined the structure in the presence of β-1,6-(GlcNAc)6. We were able to model a β-1,6-(GlcNAc)4 oligomer into the density from sites 9 to 12 (Figure 2 (a)). Interestingly, only GlcNAc molecules in sites 9 and 11 make contacts with PgaB310-672.

Studying PNAG binding to PgaB in vitro is challenging due to the polymer’s limited solubility and inherent flexibility. To overcome these issues, we conducted molecular dynamics simulations on PgaB in the presence of GlcNAc and GlcNH3

+ (Figure 3). The binding probability density of GlcNAc shows significant occupation of three different regions (purple density, Figure 3). Region 1 is located along the cleft formed between the N- and C-terminal domain, region 2 extends from underneath the inter-domain linker (IDL) towards binding site 1 on PgaB310-672, and region 3 occupies binding sites 6 to 11 on PgaB310-672. The binding density of GlcNH3

+ was found to be predominantly along the electronegative groove of PgaB310-672 (taupe density, Figure 3). To validate the results of the MD simulations, structures of PgaB310-672 in complex with GlcNAc and glucosamine (GlcN) were determined, and showed a similar mode of binding along the domain (Figure 2 (b)).

3 Life ScienceS


DiscussionOur deacetylase assays, docking studies, and simulation data suggest that PgaB310-

672 is vital for deacetylase activity, forming a molecular cleft with the N-terminal domain that binds PNAG to allow catalysis to occur. Furthermore, we identified a conserved patch of residues on PgaB310-672 that we propose assists in extending PNAG into a conformation that can be efficiently deacetylated. After deacetylation, our simulation data shows contiguous binding density for GlcNAc along the cleft and under the IDL around to subsite 1 on PgaB310-672 where GlcNH3

+ density predominates. The fact that GlcNH3

+ density is only located along the electronegative groove of PgaB310-672 suggests this domain likely prefers deacetylated PNAG (dPNAG) as a substrate. This may be the reason why no PNAG hydrolase activity could be demonstrated under the conditions tested, and the weak dissociation constants observed for the PNAG oligomers.

The PgaB310-672 structure in complex with β-1,6-(GlcNAc)6 shows an alternating pattern of binding with GlcNAc residues at sites 9 and 11 contacting the domain. This alternating binding pattern was also found in the GlcNAc and GlcN structures with carbohydrate bound at sites 5, 7, 9, and 11. The simulation data further supports this binding pattern as little to no binding density was seen at sites 2, 6, 8, 10, and 12. This binding mechanism would be able to accommodate both GlcNAc and GlcN residues and would allow for continual movement of dPNAG across the electronegative groove in a processive manner. Thus, a low affinity for PNAG may be needed to slide dPNAG in a screw-like mechanism across the domain to prevent the net loss of binding energy to PgaB310-672 as it is continuously synthesized and transported through the periplasm. This type of mechanism may be essential for efficient biosynthesis and transport as the only known source of energy in the system is from polymerization and any interruptions may impair biosynthesis.

Figure 1. PgaB310-672 is required for deacetylation and can bind Pnag oligomers. (a) deacetylase assay for PgaB22-672, PgaB22-309, PgaB310-672, and PgaB22-309 mixed with PgaB310-672, incubated with β-1,6-(glcnac)5 at 37°C for 24 h. (b) the top docked β-1,6-(glcnac)5 tetrahedral intermediate shows PgaB310-672 is required for Pnag binding to the active site. the n-terminal and C-terminal domains of PgaB are coloured light and dark grey, respectively. residues involved in ligand binding are coloured blue, except for conserved residues on PgaB310-672, which are coloured green. the nickel ion, idL, and βhL are collared teal, red, and yellow, respectively. (c) electrostatic surface potential of PgaB310-672 shows the βhL extends over an electronegative groove pinching off the binding pocket to ~7 Å. Quantitative electrostatics are collared from red (-10 kt/e) to blue (+10 kt/e). (d) PgaB intrinsic fluorescence quenching binding curves for titrations with ( ) β-1,6-(glcnac)3, ( ) β-1,6-(glcnac)4, ( ) β-1,6-(glcnac)5, and (*) β-1,6-(glcnac)6. data points are mean values with error bars representing the standard deviation between triplicate experiments.

Conclusion The structural, functional, and simulation data presented herein address a number of key questions related to the biosynthesis, modification, and translocation of PNAG/dPNAG through the periplasmic space. PgaB’s C-terminal domain is crucial for the binding and deacetylation of PNAG at the N-terminal domain. In vitro data suggests that PgaB functions as a periplasmic PNAG chaperone, continually associating with the polymer during deacetylation, and wrapping around the protein to the C-terminal domain. The interplay between PgaB’s two domains and their PNAG binding capabilities suggests that PgaB is the key component to transport PNAG between the inner and outer-membrane machinery. This first crystallographic structure of PNAG bound to PgaB310-672 shows an alternating binding pattern which is in an energetically favourable form, and we propose that this is necessary for efficient handoff of the dPNAG polymer to PgaA for export across the outer membrane.


2 0 1 4 r e s e a r c h r e p o r t 31

This study also demonstrates the utility of a brute-force molecular dynamics approach to define binding sites using monosaccharides for polysaccharides or other polymers with limited solubility.

references [1] Sutherland i (2001) Biofilm exopolysaccharides: a strong and sticky framework. Microbiology 147(Pt 1):3-9.

[2] vu B, Chen M, Crawford rJ, & ivanova eP (2009) Bacterial extracellular polysaccharides involved in biofilm formation. Molecules 14(7):2535-2554.

[3] Wang X, Preston JF, 3rd, & romeo t (2004) the pgaaBCd locus of escherichia coli promotes the synthesis of a polysaccharide adhesin required for biofilm formation. J Bacteriol 186(9):2724-2734.

[4] itoh Y, et al. (2008) roles of pgaaBCd genes in Synthesis, Modification, and export of the escherichia coli Biofilm adhesin, Poly-{beta}-1,6-n-acetyl-d-glucosamine (Pga). J Bacteriol 190(10):3670-3680.

[5] Little dJ, et al. (2012) the Structure- and Metal-dependent activity of escherichia coli PgaB Provides insight into the Partial de-n-acetylation of Poly-beta-1,6-n-acetyl-d-glucosamine. J Biol Chem 287(37):31126-31137.

[6] nishiyama t, noguchi h, Yoshida h, Park SY, & tame Jr (2013) the structure of the deacetylase domain of escherichia coli PgaB, an enzyme required for biofilm formation: a circularly permuted member of the carbohydrate esterase 4 family. Acta Crystallogr D Biol Crystallogr 69(Pt 1):44-51.

acknowledgementsWe thank Patrick Yip for technical assistance, dr. alaji Bah for help with fluorescence quenching experiments, dr. varvara Pokrovskaya for 1h nMr analysis, dr. nilu Chakrabarti for help with parameterization of glcnac and glcnh3+ for the Md simulations, dr. Shaun Labiuk at the Canadian Light Source for data collection, and Compute Canada and CLuMeQ for providing the computational resources for the Md simulations. research described in this paper is supported by grants from the Canadian institutes of health research (Cihr) (#43998, #43949 and #89708 to P.L.h., r.P., and M.n., respectively). P.L.h. is the recipient of a tier 1 Canada research Chair in Structural Biology. d.J.L. has been supported in part by graduate scholarships from the university of toronto, the ontario graduate Scholarship Program, and Cihr. n.C.B has been supported in part by graduate scholarships from the natural Sciences and engineering research Council of Canada and the Mary h. Beatty, and dr. James a. and Connie P. dickson Scholarships from the university of toronto.

Beamline informationnative diffraction data were collected on PgaB310-672 crystals in complex with glcnac and β-1,6-(glcnac)6 at a wavelength of 1.08 Å on CMCF beamline 08id-1 at the CLS using a rayonix MX300 CCd detector. the structures were solved using molecular replacement.

Figure 3. Md simulations show a continuous monosaccharide binding surface. glcnac (purple) and glcnh3+ (taupe)

densities are overlapped with a cartoon representation of the PgaB43-667 structure (n- and C-terminal domains coloured light and dark grey, respectively). in each view, binding densities are depicted at occupancies of 0.15; nickel ion is coloured teal; idL is coloured red; W387, t391, and r392 are coloured green; βhL is coloured yellow; and predicted C-terminal domain binding sites are shown as dashed circles. glcnac density binds (a) along the cleft formed between the n- and C-terminal domains from the deacetylation active site to the idL. (b) a continuous stretch of density for glcnac is seen underneath the idL. (b) Slightly discontinuous density for glcnac and glcnh3

+ extends from the idL to binding site 1 of PgaB310-672. (d) glcnh3

+ density extends across the entire length of PgaB310-672 and overlaps with glcnac density from binding site 6 to 11.

Figure 2. Structure of PgaB310-

672 in complex with β-1,6-(glcnac)6 and comparison to Md simulations. (a) Surface representation of PgaB310-672 and the modelled β-1,6-(glcnac)4 oligomer (magenta, stick representation) shown with the corresponding unbiased |Fo−Fc| density omit map displayed as a blue mesh contoured at 2.20σ. (b) Binding densities of glcnac (purple) and glcnh3

+ (taupe) from Md simulations depicted at occupancies of 0.15 are overlapped with the glcnac (orange), glcn (green), and β-1,6-(glcnac)4 (magenta) molecules from the PgaB310-672 crystal structures. residues 614-619 were omitted for clarity, and Y432, W552, and W613 highlighted in yellow. Binding sites are labeled 1 to 12, with predicted sites shown as dashed black circles.


PRINCIPAL CONTACT:

Yuanming pan, professor Department of Geological sciences University of saskatchewan [email protected] 306-966-5699


Environmental Science & Technology, 2014, Issue 12, Volume 48, pp. 6938-6946. DoI: 10.1021/es405735p

AuThORS:

Jinru Lin1 Ning chen1,2 Yuanming pan1

1 Department of Geological sciences University of saskatchewan

2 canadian Light source University of saskatchewan

Arsenic speciation in newberyite (MghPO4•3H2O) determined by synchrotron X-ray absorption and electron paramagnetic resonance spectroscopies: Implications for the fate of arsenic in green fertilizers

introductionPhosphorus (P) is an element of fundamental importance to humans for the creation of energy in cells, control of metabolic reactions and, as an essential nutrient for crops, promotion of food production [1, 2]. Marine phosphorites are the principal source of P and are mainly used as fertilizers in agriculture [3]. In this context, phosphorus is a non-renewable resource. Global phosphate reserves are limited and, at the present rate of consumptions, the existing phosphate reserves could be exhausted in less than 100 years [1, 3-5]. Other phosphate-rich rocks are available but cannot be extracted economically at present due to their lower quality and hence higher cost to process [3]. Therefore, phosphorus recovery from waste products as a renewable source is an important alternative in reducing our reliance on limited natural resources and relieving the pressure of increasing demands of phosphorus consumption.

One commercial technology for recovering P from wastewaters is the precipitation of magnesium phosphates such as struvite (Mg(NH4)PO4·6H2O), newberyite (MgHPO4•3H2O), bobierrite (Mg3(PO4)2•8H2O), and cattiite (Mg3(PO4)2•22H2O). Of these, struvite, involving recovery of both phosphorus and nitrogen, is particularly promising [3-5]. However, struvite formed from this process can contain elevated levels of various heavy metals and metalloids, which are common in wastewaters [5-11]. Our recent study confirmed that struvite precipitated at ambient pressure and temperature conditions and pH values from 6 to 9 is capable of accommodating up to 547±15 ppm As [12]. Therefore, precipitation of struvite from wastewaters is, on the one hand, a useful method for remediating P and As contamination. On the other hand, direct use of recovered struvite as a fertilizer, without removal of As and other heavy metals and metalloids, possesses a potential source of contamination [11].

ScienceNewberyite, a biomineral and common constituent in guano deposits, often co-precipitates with struvite in urine as well as calculi and has long been known to transform from the latter under both sub aerial and aqueous environments. For example, at room temperature, struvite completely decomposes to newberyite after approximately half a year [13]. Also, newberyite is an important decomposition product of struvite fertilizers when they are applied to moderately acidic soils [14-16]. Therefore, the question of arsenic uptake and speciation in newberyite is of significant importance to understanding the fate of this toxic metalloid in soils.

Accordingly, we have investigated arsenic doped newberyite by the use of synchrotron X-ray absorption spectroscopy (XAS) and single-crystal electron paramagnetic resonance (EPR) spectroscopy. Results are compared with those from struvite and other phosphates to provide insights into the uptake and speciation of arsenic in newberyite. Also investigated in this study are As and transition metals in natural newberyite from guano deposits in Skipton Caves, Australia and at Paoha Island, Mono Lake, California, USA. These are two classic localities where the transformation of struvite to newberyite was first documented [13]. Moreover, newberyite (and its struvite precursor) from Mono Lake, which is a hypersaline and alkaline water body containing exceptionally high concentrations of As (averaging ~200 µM) [17], is expected to contain the upper limit of this metalloid in guano deposits. These data from natural newberyite are interpreted in light of new results from its synthetic counterpart, with implications for the fate of As in green fertilizers and potentially useful for the remediation of arsenic contamination in aqueous environments.

DiscussionCrystals of newberyite from two experiments with Na2HAsO4•7H2O and NaAsO2 as the dopant (denoted as Synthesis #1 and #2) contain 1099 and

1 Earth & EnvironmEntal


2 0 1 4 r e s e a r c h r e p o r t 33

25 ppm As, respectively. Two samples of natural newberyite from Skipton Caves and one from Paoha Island contain 2-3 ppm As, whereas another sample from the latter locality contains 6.7 ppm As.

Arsenic K edge XANES and EXAFS spectra

The dominant whiteline peak position of newberyite at ~11,874 eV is consistent with those of scorodite and As2O5, suggesting the As5+ oxidation state only, which is evident in the first-derivative spectra as well (Figure 1). The As K edge EXAFS spectrum is dominated by back scattering from an O first shell (labeled as I), with additional contributions from two smaller shells (II and III in Figure 2). The fitted interatomic distance of the arsenic species in synthetic newberyite at 1.68 Å is in agreement with those of typical As5+ [18-21]. The fitted results for the outer single scattering As-Mg and As-O paths are also consistent with the extended P site, suggesting As5+ substituting for P5+ in the newberyite lattice.

Single-crystal EPR spectra

Single-crystal EPR spectra of gamma-ray-irradiated newberyite reveal two S=1/2 arsenic-associated oxyradicals: [AsO3]

2- and [AsO2]

2- (Figure 3) [22-24]. The orientations of the principal g2 and A1 axes of [AsO3]

2- are approximately along the P-O2 bond direction in the newberyite lattice. The close matches of these orientations suggest that the [AsO3]

2- radical formed from the diamagnetic [AsO4]

3- group substituting for [PO4]

3-, via a reaction involving an electron trapped on the central As5+ ion after removal of an O atom during gamma-ray irradiation: [AsO4]

3-+e [AsO3]2-+O2-

(Figure 3). Similarly, the directions of the g1 and g3 axes of the [AsO2]

2- radical are approximately perpendicular to the P-O1-O2 and P-O2-O4 planes, respectively; while the unique A1 axis is almost along the P-O2 bond direction. These close matches suggest that the [AsO2]

2- radical in newberyite is related to a substitutional As3+ ion at the P site via the reaction [AsO3]

3-+e [AsO2]2-

+O2- (Figure 3).

Implications for the fate of arsenic in green fertilizers

Guano deposits from the excrements of birds and cave-dwelling bats have been used as fertilizers since antiquity and are increasingly favoured by organic farmers. The As contents in newberyite from Skipton Caves are similar to those in bats' guano elsewhere [25], suggesting that As was retained during the transformation from struvite to newberyite. This finding is

Figure 1. (a) as K edge XaneS spectra of model compounds and newberyite from Synthesis #1; and (b) corresponding first-derivative XaneS spectra.

consistent with our experimental results that both struvite and newberyite are capable of sequestering significant amounts of As. The elevated level of As in newberyite from Paoha Island relative to its counterpart from Skipton Caves is undoubtedly related to the accumulation of this metalloid in the food chain [26-28], because birds in the region are known to feed on brine shrimps in the As-rich Mono Lake [17]. These results show that guano deposits, while natural, cannot be taken for granted when it comes to arsenic and other heavy metals and metalloids.

Our synthesis experiments at pH=6.4 are particularly relevant to understanding the fate of arsenic in struvite-based green fertilizers, which have been shown to be the most effective for moderately acidic soils [14-16]. Under such conditions, newberyite is a common decomposition product of struvite, involving the release of ammonia and water [14]. The apparent accommodation and retention of arsenic in both synthetic and natural newberyite suggest that decomposition of struvite to newberyite possesses no negative impact on the fate of arsenic in soils. Of course, complete dissolution of struvite (and its decomposition product newberyite) from green fertilizers, if containing arsenic, will contaminate soils over time. Therefore, processes for removal of arsenic (other heavy metals and metalloids as well) from wastewaters must be developed before phosphate recovery for manufacturing green fertilizers [11].

Conclusion Newberyite is an important decomposition product of struvite that is an increasingly popular green fertilizer recovered from wastewaters. Two samples of newberyite containing 1099 and 25 ppm As have been obtained at pH=6.4, by using Na2HAsO4·7H2O and NaAsO2 as the dopant, respectively (i.e. Synthesis #1 and #2). Synchrotron arsenic K-edge X-ray absorption spectroscopic data of newberyite from Synthesis #1 show that As5+ is dominant and has a local environment typical of the arsenate species. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated newberyite from Synthesis #1 contain two arsenic-associated oxyradicals: [AsO3]

2- and [AsO2]2-

derived from As5+ and As3+, respectively, at the P site. Quantitative analyses of powder EPR spectra allow determinations of the As5+ and As3+ contents in newberyite from Synthesis #1 and #2. Elevated concentrations of arsenic also occur in natural newberyite transformed from struvite in guano deposits and record the accumulation of this metalloid in the food chain. Therefore, newberyite, which sequesters As during crystallization and retains this metalloid during the transformation from struvite, can attenuate arsenic contamination from green fertilizers in moderately acidic soils. Also, the capacity for accommodating both As5+ and As3+ in the crystal lattice coupled with simple chemistry and easy crystallization at ambient conditions makes newberyite an attractive material for remediation of arsenic contamination in aqueous environments.


references [1] Smil, v. (2000). Phosphorus in the environment: natural flows and human interferences. Annual review of energy and the environment, 25(1), 53-88.

[2] valsami-Jones, e. (ed.). (2004). Phosphorus in environmental technologies: Principles and applications. iWa Publishing.

[3] Cordell, d., drangert, J. o., & White, S. (2009). the story of phosphorus: global food security and food for thought. Global environmental change, 19(2), 292-305.

[4] Jaffer, Y., Clark, t. a., Pearce, P., & Parsons, S. a. (2002). Potential phosphorus recovery by struvite formation. Water Research, 36(7), 1834-1842.

[5] rahman, M. M., Salleh, M. a. M., rashid, u., ahsan, a., hossain, M. M., & ra, C. S. (2014). Production of slow release crystal fertilizer from wastewaters through struvite crystallization–a review. Arabian Journal of Chemistry, 7(1), 139-155.

[6] ronteltap, M., Maurer, M., & gujer, W. (2007). the behaviour of pharmaceuticals and heavy metals during struvite precipitation in urine. Water research, 41(9), 1859-1868.

[7] torras, J., Buj, i., rovira, M., & de Pablo, J. (2011). Semi-dynamic leaching tests of nickel containing wastes stabilized/solidified with magnesium potassium phosphate cements. Journal of hazardous materials, 186(2), 1954-1960.

[8] Mohan, d.; Pittman Jr, C. u. (2007). arsenic removal from water/wastewater using adsorbents—a critical review. J. Hazard. Mater. 142 (1–2), 1-53.

[9] Liu, r., Xu, W., Wu, K., gong, W., Liu, h., & Qu, J. (2013). Species distribution of arsenic in sediments after an unexpected emergent discharge of high-arsenic wastewater into a river. Frontiers of Environmental Science & Engineering, 7(4), 568-578.

[10] Church, C. d.; Kleinman, P.; Bryant, r. S., LS; allen, a., (2010). occurrence of arsenic and phosphorus in ditch flow from litter-amended soils and barn areas. J. Environ. Qual. 39 (6), 2080-2088.

[11] güney, K., Weidelener, a., & Krampe, J. (2008). Phosphorus recovery from digested sewage sludge as MaP by the help of metal ion separation. Water research, 42(18), 4692-4698.

Figure 3. representative single-crystal ePr spectrum of gamma-ray-irradiated newberyite from Synthesis #1, measured with the magnetic field B parallel to the crystallographic c-axis, illustrating the well-resolved [aso3]2− and [aso2]2− radicals. Sticks mark the characteristic 75as hyperfine structures.

Figure 2. r-space curve fittings for as K edge eXaFS spectra of newberyite from Synthesis #1. The Fourier transforms of k3•χ(k) spectra were performed over the k ranges of 2.89-13.08 Å-1 and r-space fitting windows of 0.83-3.38 Å. Both the magnitude (positive envelopes) and the imaginary (oscillating parts) of the Fourier transforms are shown. Also included in inserts are the k3•χ(k) spectra in comparison with those from r-space fittings.

[12] Lin, J., Chen, n., & Pan, Y. (2013). arsenic incorporation in Synthetic Struvite (nh4MgPo4· 6h2o): a Synchrotron XaS and Single-Crystal ePr Study.Environmental science & technology, 47(22), 12728-12735.

[13] Whitaker, a. (1968). the decomposition of struvite. Mineral. Mag. 36 (282), 820-824.

[14] Lindsay, W. L., Frazier, a. W., & Stephenson, h. F. (1962). identification of reaction products from phosphate fertilizers in soils. Soil Science Society of America Journal, 26(5), 446-452.

[15] Johnston, a. e.; richards, i. r. (2003). effectiveness of different precipitated phosphates as phosphorus sources for plants. Soil Use Manag. 19, 45-49.

[16] gell, K.; de ruijter, F. J.; Kuntke P.; de graaff M.; Smit, a. L. (2011) Safety and effectiveness of struvite from black water and urine as a phosphorus fertilizer. J. Agr. Sci. 3, 67-80.

[17] Kulp, t. r., hoeft, S. e., asao, M., Madigan, M. t., hollibaugh, J. t., Fisher, J. C., ... & oremland, r. S. (2008). arsenic (iii) fuels anoxygenic photosynthesis in hot spring biofilms from Mono Lake, California. Science, 321(5891), 967-970.

[18] Lin, J., Chen, n., nilges, M. J., & Pan, Y. (2013). arsenic speciation in synthetic gypsum (CaSo 4· 2h 2 o): a synchrotron XaS, single-crystal ePr, and pulsed endor study. Geochimica et Cosmochimica Acta, 106, 524-540.

[19] Foster, a. L.; Brown, g. e.; tingle, t. n.; Parks, g. a. (1998). Quantitative arsenic speciation in mine tailings using X-ray absorption spectroscopy. Am. Mineral. 83, (553-568).

[20] Moldovan, B. J., Jiang, d. t., & hendry, M. J. (2003). Mineralogical characterization of arsenic in uranium mine tailings precipitated from iron-rich hydrometallurgical solutions. Environmental science & technology, 37(5), 873-879.

[21] Li, r., Lin, J., nilges, M. J., Chen, n., & Pan, Y. (2014). arsenic speciation in danburite (CaB2Si2o8): a synchrotron XaS and single-crystal ePr study. European Journal of Mineralogy, 26(1), 113-125.

[22] Pan, Y. arsenic speciation in rock-forming minerals determined by ePr spectroscopy. (2013). Arsenic: sources, environmental impacts, toxicity and human health: A medical geology perspective, Masotti, a., ed. nova Science Publishers inc. 39-52.

[23] Mao, M., Lin, J., & Pan, Y. (2010). hemimorphite as a natural sink for arsenic in zinc deposits and related mine tailings: evidence from single-crystal ePr spectroscopy and hydrothermal synthesis. Geochimica et Cosmochimica Acta,74(10), 2943-2956.

[24] Pan, Y., & nilges, M. J. (2014). electron paramagnetic resonance spectroscopy: Basic principles, experimental techniques and applications to earth and planetary sciences. Reviews in Mineralogy and Geochemistry, 78(1), 655-690.

[25] o'Shea, t. J., everette, a. L., & ellison, L. e. (2001). Cyclodiene insecticide, dde, ddt, arsenic, and mercury contamination of big brown bats (eptesicus fuscus) foraging at a Colorado Superfund site. Archives of Environmental Contamination and Toxicology, 40(1), 112-120.

[26] Bou-olayan, a. h.; al-Yakoob, S.; al-hossaini, M. (1995). arsenic in shrimp from Kuwait. Bull. Environ. Contam. Toxicol. 54 (4), 584-590.

[27] Larsen, e. h.; Quétel, C. r.; Munoz, r.; Fiala-Medioni, a.; donard, o. F. X. (1997). arsenic speciation in shrimp and mussel from the Mid-atlantic hydrothermal vents. Mar. Chem. 57 (3–4), 341-346.

[28] raissy, M., rahimi, e., nadeali, v., ansari, M., & Shakerian, a. (2014). Mercury and arsenic in green tiger shrimp from the Persian gulf. Toxicology and industrial health, 30(3), 206-210.

acknowledgements We thank the Canadian Light Source and the Saskatchewan Structural Sciences Centre for access to synchrotron XaS and ePr experiments, respectively, and nSerC for financial support.

Beamline information arsenic K edge (11,867 ev) spectra were collected at the hXMa beamline of the Canadian Light Source. Monochromatic beam was produced using a pair of Si(111) monochromator crystals with the second crystal detuned by 50% of fully tuned beam intensity for the reduction of harmonic; and rh mirrors were introduced in this experiment. the sample of newberyite from Synthesis #1 was mounted in an aluminum holder covered with Kapton at 45° to the incident X-ray beam and measured in the fluorescence mode using a 32-element solid state ge detector positioned at 90° to the X-ray beam. the sample was held at 8 K using an oxford instruments liquid helium flow cryostats to reduce the beam damage, and straight ion chamber detectors filled with standard >99.99% nitrogen gas.


2 0 1 4 r e s e a r c h r e p o r t 35

PRINCIPAL CONTACT:

Dr. adam Gillespie, soil chemistry Research associate canadian Light source [email protected] 306-657-3651


Biogeochemistry, 2014, Volume 117, Issue 2-3, pp. 337–350. DoI:10.1007/s10533-013-9871-z

AuThORS:

Gillespie, a.W. Regier, t.Z., chevrier, D., Dynes, J.J. canadian Light source

Diochon, a. Department of Geology Lakehead University

Kellman, L. Department of earth sciences st. Francis Xavier University

Walley, F.L. Department of soil science University of saskatchewan

Ma, B.L., Morrison, M.J., Gregorich, e.G. agriculture and agri-Food canada

Nitrogen input quality changes the biochemical composition of soil organic matter stabilized in the fine fraction: a long-term study

introductionSoil organic matter (SOM) underpins the ecosystem services provided by soil, which include fertility, resistance to erosion and the capacity to absorb environmental changes. Nitrogen plays an important role in decomposition of plant residues and SOM turnover, but assessments of how additions of specific forms of supplemental N affect the chemical composition of stabilized SOM are lacking.

In agricultural systems, synthetic fertilizers, livestock manure and N-fixing legumes are the most common sources of supplemental N that are introduced into agricultural soils [1]. Different mechanisms and decomposition kinetics are promoted by adding different N-sources to agricultural soils. Therefore different types of compounds may be preferentially degraded and/or enriched, changing the chemical composition of the remaining stabilized soil organic matter (SOM) [2,3].

We tested the hypothesis that the chemical composition of the SOM would be different if the supplemental N was from a synthetic, animal manure, or legume source. The specific questions we wished to address were whether long-term application of N had an effect on the chemical structure of SOM and how the microbial community responded to long-term additions of different N-sources. We focused on the fine (< 5µm) fraction to understand the microbial products of SOM degradation. In addition to synchrotron techniques, we used amino sugar analysis [4] to evaluate the microbial contributions to the SOM and linked this information with that obtained with XANES spectroscopy.

ScienceSoils used in this study were obtained from the long-term field trial involving crop rotations and fertilization using organic and synthetic N amendments that was initiated in 1992 and is located at the Agriculture and Agri-Food Canada Central Experimental Farm in Ottawa, Ontario [5]. The five treatments were: continuous monoculture maize treatments receiving three

different N amendments (no fertilization; N as ammonium nitrate (NH4NO3); N as composted dairy manure); a two-year rotation of maize and soybeans which did not receive any further N fertilization; and soil kept fallow, receiving no fertilization. All plots were fertilized with adequate P and K fertilizer (except fallow) according to soil test recommendations prior to planting. Isolation of soil particles <5 µm in size was carried out by sedimentation in water by applying Stoke’s Law at room temperature [6]. Amino sugars were recovered from soil by hydrolysis and analysed using gas chromatography [7]. Amino sugar analysis allows differentiation between bacterial and fungal residues in SOM. Bacterial peptidoglycan is a polymer of 1:1 acetylglucosamine:muramic acid, whereas fungal chitin is a polymer of acetylglucosamine. Therefore, increases in glucosamine:muramic acid (gluN:mur) indicates a shift from bacterial to fungal predominance [4].

For XANES analysis, subsamples were slurried in water, deposited onto Au-coated Si wafers and air-dried at room temperature, affixed to sample holders for insertion into the absorption chamber. Spectra were acquired using the slew-scanning mode of the SGM beamline, which continuously scans the energy of the monochromator while acquiring data in order to minimize X-ray exposure. Total Fluorescence Yield (TFY) was recorded using a two-stage microchannel plate detector. Differences between soils were explored using non-metric multidimensional scaling (NMS) ordination as described by Gillespie et al. [7], where XANES spectra were deconvoluted and spectral features were assigned to specific functional groups. This technique allows multivariate comparisons between spectra; no attempt was made toward quantitative analysis, or toward comparison between features within single spectra.

discussion The addition of N to soils (i.e., synthetic fertilizer, manure, and maize/soybean treatments) resulted in the enrichment of proteinaceous compounds (Figures 1 and 3). Soils that did not receive supplemental N (i.e., fallow and maize with no N additions) were enriched in plant-

2 Earth & EnvironmEntal


derived compounds (e.g., aromatics, phenolics, carboxylic acids and aliphatic compounds, Figures 2 and 3), suggesting that decomposition of plant residues was constrained by N-limitation. Microbial populations assessed by amino sugar biomarker ratios showed that the highest contributions to SOM by bacteria occurred in the manure treatment (high N input), and by fungi in the fallow treatment (low N input). The SOM in the synthetic fertilizer and maize/soybean treatments was enriched in N-bonded aromatics (Figure 1); we attribute this enrichment to the abiotic reaction of inorganic N with organic C structures [7,8]. The SOM in the manure treatment was enriched in pyridinic-N, likely as a result of intense microbial processing and high SOM turnover [9]. The presence of signals for ketone and pyrrole compounds in XANES spectra suggest their use as biomarkers for microbially transformed and stabilized SOM. The SOM in the manure treatment was enriched in ketones, which are likely microbial by-products of fatty acid catabolism. Pyrrole compounds, which may accumulate over the long term as by-products of protein transformations by an N-limited microbial community [10], were dominant in the fallow soil.

The ketone and pyrrole signals observed with XANES deserve attention because they may be indicators of the microbial community's ability to metabolize specific SOM components as a function of N availability. The ketone signal is strongest in the manure treatment and is also apparent in the synthetic fertilizer treatment. XANES spectra of bacterial material often show the presence of ketones and aldehydes [11,12], which are catabolic by-products of fatty acid metabolism. This suggests that the microbial population in soils receiving supplemental N are able to effectively metabolize fatty acids, leaving behind ketone by-products and this observation is confirmed by the strong positive correlation between total amino sugar and ketone compounds as well as the strong negative correlation with carboxylic acids (Figure 3).

Conclusion Analysis by XANES combined with measurement of amino sugar biomarkers showed that composition of SOM in the fine fraction of soil is influenced by the source of supplemental N. Nitrogen additions to soil resulted in the enrichment of N-containing organic compounds, mainly

Figure 1. normalized absorbance (fluorescence) of n K-edge XaneS spectra of soils under different n supplementations. nitrogen features identified as: (1) aromatic n in 6-membered rings (pyridines, pyrazines) at 398.8 ev, (2) amide (protein) at 401.2 ev, (3) n with unpaired electrons in 5-membered rings (pyrrolic) at 402.5 ev, (4) n-bonded aromatic at 403.5-403.8 ev, and (5) alkyl-n at 406 ev.

Figure 2. normalized absorbance (fluorescence yield) of C K-edge XaneS spectra of soils under different n supplementation. Carbon features have been identified as: (1) aromatic C at 285 ev; (2) pyridinic n at 285.5 ev; (3) ketone at 286.8 ev; (4) phenolic at 287.1 ev; (5) aliphatic at 287.5 ev; (6) carboxylic at 288.6 ev; and (7) carbohydrate hydroxyl at 289.6 ev.


2 0 1 4 r e s e a r c h r e p o r t 37

protein-containing amides and amino groups. Plant-derived compounds (such as aromatics, phenolics, carboxylic acids, and aliphatic compounds) were enriched in the continuous maize without fertilizer treatment, and their persistence in this treatment was probably because limitations in N restricted decomposition. Fertilizer and legume sources of N added to soil appeared to promote development of N-bonded aromatics. Pyridinic-N was observed in all treatments receiving supplemental N, but was strongest in the manure treatment, suggesting that its accumulation was the result of extensive microbial turnover of organic N. Amino sugar analyses indicated that the microbial populations shifted towards fungal populations in the fallow soil, but towards bacterial populations in the manure-amended soil. The appearance of two compound signals in XANES spectra, for ketone and pyrrole, suggest their use as possible biomarkers. Ketone signals were greatest in the soils receiving manure and attributed to microbial by-products of fatty acid metabolism. Pyrrole signals appeared concomitant with the depletion of amides in the fallow treatment suggesting these compounds resulted from the degradation

of proteins. This study showed that an increase in N availability allows the microbial community to transform plant material into microbial by-products, which occur as stable SOM compounds in the fine soil fraction.

references [1] Smil, v. enriching the earth: Fritz haber, Carl Bosch, and the transformation of world food production. The MIT Press (2001).

[2] Wallenstein, M. d., haddix, M. L., Lee, d. d., Conant, r. t. & Paul, e. a. a litter-slurry technique elucidates the key role of enzyme production and microbial dynamics in temperature sensitivity of organic matter decomposition. Soil Biol. Biochem. 47, 18–26 (2012).

[3] Wickings, K., grandy, a. S., reed, S. C. & Cleveland, C. C. the origin of litter chemical complexity during decomposition. Ecol. Lett. 15, 1180–1188 (2012).

[4] amelung, W. in assessment methods for soil carbon (eds. Lal, r., Kimble, J. M., Follett, r. F. & Stewart, B. a.) 233–272. Lewis Publishers (2001).

[5] Ma, B. L., Ying, J., dwyer, L. M., gregorich, e. g. & Morrison, M. J. Crop rotation and soil n amendment effects on maize production in eastern Canada. Can. J. Soil Sci. 83, 483–495 (2003).

[6] Kroetsch, d. & Wang, C. Soil sampling and methods of analysis (eds. Carter, M. r. & gregorich, e. g.) 2nd, 713–725 (CrC Press, 2008).

[7] gillespie, a. W. et al. XaneS and pyrolysis-FiMS evidence of organic matter composition in a hummocky landscape. Soil Sci. Soc. Am. J. 75, 1741–1755 (2011).

Figure 3. non-metric multidimensional (nMS) scaling analysis of C and n K-edge XaneS features from soils under different cropping and n fertilizer management. Multidimensional analysis performed using peak heights from deconvoluted XaneS spectra. Blue vectors show correlation between source variables and the final ordination, where the direction and relative length of the vector indicates the strength of correlation. red vectors are ratios of amino sugar concentrations, which are indicators of increasing fungal:bacterial dominance.

1: glucosamine:muramic acid; 2: galactosamine:muramic acid; 3: mannosamine:muramic acid.

[8] davidson, e. a., Chorover, J. & dail, d. B. a mechanism of abiotic immobilization of nitrate in forest ecosystems: the ferrous wheel hypothesis. Glob. Change Biol. 9, 228–236 (2003).

[9] Mengel, K. turnover of organic nitrogen in soils and its availability to crops. Plant Soil 181, 83–93 (1996).

[10] Corpe, W. a. extracellular accumulation of pyrroles in bacterial cultures. Appl. Microbiol. 11, 145–150 (1963).

[11] hitchcock, a. P. et al. Soft X-ray spectromicroscopy of nickel sorption in a natural river biofilm. Geobiology 7, 432–453 (2009).

[12] Chan, C. S., Fakra, S. C., edwards, d. C., emerson, d. & Banfield, J. F. iron oxyhydroxide mineralization on microbial extracellular polysaccharides. Geochim. Cosmochim. acta 73, 3807–3818 (2009).

acknowledgementsamino sugar analysis at agriculture and agri-Food Canada was conducted by a. Spasojevic, S.S. Wu and a. Fok. a.W. gillespie, B.L. Ma, M.J. Morrison and e.g. gregorich acknowledge financial support for this research through agriculture and agri-Food Canada’s Science and technology Branch and the SageS program.

Beamline informationSgM beamline, bulk X-ray absorption Spectroscopy (XaneS or neXaFS) at the carbon and nitrogen K-edges.


Industrial Science update Jeffrey Cutler, Chief industrial Science officer

2014 was a good year for industrial engagement at the CLS. We completed more than 30 projects for 17 clients, with approximately 70% returning clients across a number of industry sectors (Figure 1), and average beamtime use of ~8% across the facility.

pharmaceuticals - Crystallography

We have been actively involved in the pharmaceutical sector for the last several years and we are currently supporting a number of service companies operating as contract research organizations (Cros) for the pharmaceutical and biotechnology sectors. By working with these Cros we have served a greater number of multinational, small- and medium-sized enterprises, than would have been able to use our macromolecular facilities directly. our expanded reach has increased our support of the private sector as well as our impact on health and life science research.

mining - oil and gas - environment

Working with Western university, the university of Manitoba and several industry

partners, the CLS industrial Science team developed important research projects in mineral exploration, including work on gold and uranium ore. this work focuses on applying synchrotron techniques like Micro X-ray Fluorescence (µ-XrF) mapping to identify indicator minerals, their oxidation states and co-location, which will increase our understanding of gold and uranium deposits, their formation, and how to better predict their location.

We continue to work with areva resources to increase their understanding of forms of arsenic found in the JeB tailings Management Facility (tMF), an existing repository for waste products (tailings) resulting from processing of uranium at the McClean Lake JeB mill in northern Saskatchewan, and how those

figure 1. Distribution of CLS clients by industry sector for 2014.

Sector Foci PHARMA 23%

MATERIALS 12%

OTHER 18%

AUTO 6%

OIL/GAS 12%

MINING 17%

ENERGY 12%

PHARMA 23%

MATERIALS 12%

OTHER 18%

AUTO 6%

OIL/GAS 12%

MINING 17%

ENERGY 12%

CLS InnovatIonS


2 0 1 4 r e s e a r c h r e p o r t 39

Battery research on the ideaS beamline at the CLS with industrial staff scientists Jigang Zhou and toby Bond.

CLS director of industrial Science Jeff Cutler (right) and Mitacs vice President, Strategic enterprises, duncan Phillips sign an Mou that will increase innovation and commercialization projects across Canada.

materials alter during aging of the tailings. the project represents one of the most comprehensive sets of samples collected from a tailings impoundment and has afforded new insight into the aging mechanisms of mining waste.

We have also developed an on-going project with SrK Consulting in vancouver to examine the consolidation of oil sands fine tailings using comuted tomography (Ct) techniques on BMit. this work was recently presented at the international oil Sands tailings Conference (ioStC). By using the tomography capabilities on BMit, SrK has proposed a characterization framework to enhance our understanding of the chemical and physical mechanisms affecting ultimate material dewatering.

Batteries

in terms of battery research, we focus on performing in-situ experiments of lithium-ion batteries using common commercial form factors in order to improve battery safety. other synchrotrons working in this area have focused on basic materials synthesis, using purpose-built, specialized batteries that do not always reflect real-world operating conditions. We hope to differentiate ourselves by focusing on specific problems that occur in actual commercial batteries, arising from implemented electrode geometries (such as non-uniform thermal distribution, degradation, and mechanical stress). Proof-of-concept work has been carried out on in-situ Xrd and XaneS experiments

on an unmodified commercial pouch cell and we were able to observe the change in electrode chemistry as a function of charging and discharging.

aerospace

Several projects have been developed on composite characterization, including a new venture exploring the interface between carbon fibre and resin, and its correlation with material strength. an ongoing initiative focuses on gas transport during the curing process of out-of-

autoclave composites. in collaboration with the Composite research network at the university of British Columbia, we have used BMit to track gas diffusion and debulking processes at room temperature. the next phase of the project will examine debulking at curing temperatures.

overview

the CLS is determined to become an integral part of Canadian industry’s research and development toolbox. Whether helping business create new products, assisting with sustainability issues, thanks to its unique capability to examine and illuminate environmental challenges, or providing solutions for major health concerns, and increasing understanding of composites and biomaterials, our impact will be both tangible and impactful.

Canada’s synchrotron is a space for brilliant ideas that will help Canada build a more sustainable environment, productive businesses, and healthy people. increased scientific output will lead to more revenue generation for the facility and great economic impact for Canada. the sky is not the limit. Stay tuned!


CLS InnovatIonS

Saving LiveS With Light:

The Medical Isotopes Project

in november, the Canadian Light Source proudly made its first shipment of molybdenum-99 (Mo-99) medical isotopes, the culmination of years of work on the Medical isotope Project.

Mo-99 decays into technetium-99m (tc-99m), which hospitals use regularly in medical scans. in fact, tc-99m is by far the most used medical isotope in Canada with about 5,500 medical scans daily.

today, most medical tc-99m is derived from weapons-grade uranium. Because of both the danger and waste associated with such highly-enriched uranium, the international community has been searching for alternative sources.

the CLS Medical isotope Project is developing and putting into action one of the most promising alternatives for

“We are excited to be producing medical

isotopes at this critical time in history. To be

part of a project that will meet the health

needs of so many Canadians, that is the most

gratifying element.”

– CLS CEO Rob Lamb

creating invaluable medical isotopes for diagnostic tests: photo-neuron reaction using the facility’s linear accelerator (see next page).

in 2015, the facility will aim to ship medical isotopes to Winnipeg weekly, where key health Canada tests for medical approval will be completed. Chief Medical isotopes officer Mark de Jong hopes that approvals will be finished by the end of the year.

once approved, the facility is projected to supply enough isotopes for all of Saskatchewan and Manitoba. Looking further ahead, de Jong hopes to develop two or three accelerator systems like the one operating at the CLS, which could produce enough medical isotopes to supply all of Canada.

2 0 1 4 r e s e a r c h r e p o r t 41


how does mip work?

the MiP facility produces Mo-99 using a process called photo-neutron reaction. an electron accelerator bombards a target made of molybdenum 100 (Mo-100) metal, producing high-energy X-rays. the X-rays then convert Mo-100 atoms into Mo-99 isotopes by knocking out one neutron from the atom. the Mo-99 decays into tc-99m that is used for tagging radiopharmaceuticals for medical diagnostic tests. after the Mo-99 has decayed, the remaining Mo-100 is recovered and recycled into new targets (See right).

diagram of the proposed process. an electron beam from a linear accelerator is used to produce high-energy X-rays. X-rays shine on a target consisting of molybdenum-100 (Mo-100) discs. an X-ray strikes the nucleus of a Mo-100 atom, knocking away a neutron to create Mo-99, which decays to become tc-99m. a radionuclide separator separates the tc-99m from the Mo-100 so that it can be injected into patients undergoing medical tests. the Mo-100 can then be recycled into new targets.

Mark de Jong in the Medical isotope Project (MiP) facility.David Stobbe / Stobbe Photographyisotope Project (MiP) facility.


Students on the BeamlineSpecial thanks for the support of the following CLS staff: HSE, USO, Robert Blyth, Ferenc Borondics, Jay Dynes, Adam Gillespie, Michael Greschner, Michelle Hogan, Chithra Karunakaran, Gosia Korbas, Rachid Lahlali, Xia Liu, Joyce McBeth, David Muir, Joel Reid, Samira Sumaila, Nicole Sylvain, Kim Tan & Julie Thompson and to the following from the University of Saskatchewan staff: Jordan Hamilton, Tim Molnar, Derek Peak, Courtney Phillips, Rick Retzlaff, Sakeena Akhtar, and Rameez Virji.

1 shad valley 2014 – studying Compost samples from across Canada

Students from across Canada participating in Shad at the university of Saskatchewan campus investigated compost samples from three sources (vegetation, food waste, and a combination) to see which could best resist the leaching effects of acid rain. their work had a special focus on Manganese, an essential nutrient and involved in the stability of metals in plants and soils.

2 elements in the sediments – notre dame high school, Calgary, aB aum sotB poster prize winner

Motivated by flooding in spring 2013 and resulting concerns regarding sanitary conditions of water systems in southern alberta and Saskatchewan. they wondered if there was potential for hazardous bioavailable materials to be introduced to these water systems and could be detected in riverbank sediments.

While traces of contaminants were found, concentrations were very low and there was no indication that they were a result of flooding.

3 the effects of Water treatments on manganese – evan hardy Collegiate institute, saskatoon, sK

Literature suggests high Mn concentrations could cause neurological disorders and have been connecting to Parkinson’s-like symptoms. Students wanted to investigate if the application of commonly used water treatment methods would change Mn speciation to a less bioavailable species. the only method found to oxidize Mn was the addition of potassium permanganate, KMno4, a disinfectant.

4 space tomatoes – lloydminster Comprehensive high school, lloydminster, sK

Students obtained tomato seeds that had been exposed to cosmic radiation on the international Space Station

from tomatoSphere© and investigated differences in growth and chemistry from seeds from the same source without exposure. differences were observed in growth rates, concentrations of several elements (Fe, Ca, Z, & Mn) as well as polysaccharide, carbohydrate and protein levels. their work was performed on ideaS and Mid ir beamlines, and the project continues on Mid ir in 2015.

5 an ongoing exploration of the effect of acid rain on Boreal forest and arctic soils – Centennial Collegiate institute, saskatoon, sK

this multi-year Centennial Collegiate research project, begun in 2008, investigates the possible effects of acid rain on boreal forest soils. Previously, students found that soil exhibits horizon-dependent effects as a result of treatment with simulated acid rain. each soil horizon or layer behaved differently when treated independently with nitric acid. this year they explored effects on Mn, finding several horizon-dependent chemical changes. the project continues on SgM in 2015.

1 2

3 4

2 0 1 4 r e s e a r c h r e p o r t 43

6 lentil resistance to saline Conditions – appleby College integrated science Club, oakville, on

the un Food and agriculture organization reports that Canada is the largest exporter of red lentils in the world. however, lentils, like many other crops, are threatened by rising sea levels. Students investigated the effects exposure to salty conditions might have on the growth of lentils and chick peas, and whether a boost of abscisic acid might mitigate negative effects. the abscisic acid, a natural plant growth hormone, benefitted each plant differently.

7 airborne peanut allergens and selenium in nuts – Bishop Carroll high school, Calgary, aB

this group completed two projects on the ideaS beamline. First, they attempted to detect a peanut allergen in simulated mucus present during ‘aggressive consumption’ of peanuts to investigate the possibility of airborne allergens and learned the value of a ‘null’ result.

Second, they investigated natural speciation of Se in several different kinds

of nuts for comparison to the speciation detected in dietary supplements and to the information on the packaging label.

8 Comparison & Contrast of elemental Components of urban vs. rural honey Bees in saskatchewan – stem teacher Candidates from the university of saskatchewan College of education Winner of the aum graduate student poster competition—life sciences

the health of honey bees has been of concern lately because of the rapid decline of honey bee populations due to Colony Collapse disorder. u of S teacher candidates investigated the presence of common pesticides and other environmental stressors using ideaS. they found that urban bees have higher levels of K and Cu while rural bees have elevated concentrations of Cr, ni, and Zn. however, Mn and Fe were roughly equal for both populations. elevated concentrations of Cr, ni and Zn in rural bees may be attributed to the differentiated elemental components of urban and rural pollens.

9 the fracking study of the frac’cing Water – school division 60, fort st. John, BC

the goal of the project was to look at the chemistry of fluids used in the hydraulic fracturing process and possible effects on the formation, environment, and the hydraulic fracturing process itself. Specifically, students considered the differences in fluids in added to the well before and after fracturing. there were indications of possible chemical reactions occurring between the hydraulic fracturing fluid and the formation.

10 exploring how Xrf measurements Contribute to graduate student soil science research – university of saskatchewan

Students taking Soil Science 803 submitted proposals based on their graduate studies projects, the best of which were granted time on the ideaS beamline so students could learn first-hand how their research might benefit from these techniques. they investigated the chemistry of environmental contaminants of soils from around the world.


5

6

7 8 10

9


g. MiChaeL BanCroFt Phd theSiS aWard:

Riccardo Comin’s high-Tc Superconductivity Insight

in 2013, that student was riccardo Comin, a condensed-matter physicist whose work focuses on understanding the secrets of high-temperature superconductors. excellent candidates in the search for room-temperature superconductivity, copper-oxide-based ceramics, known as cuprates, become superconducting at temperatures as high as -100˚C.

Since their discovery in 1986, copper-oxide materials have intrigued and challenged condensed matter experimentalists and theorists alike. electrons in cuprates exhibit an intimate competition: some of them

every year the Canadian Light Source presents the g. Michael Bancroft Phd thesis award to a graduate student with the strongest published work using data collected at the synchrotron.


reiXS scientists ronny Sutarto (left) and Feizhou he (right) with university of toronto researcher riccardo Comin (middle).

flow in a coherent and cooperative stream known as the superconducting state, while other electrons aggregate into static and periodic patterns known as charge-density-waves.

Comin, who recently graduated with a Phd in Physics from andrea damascelli’s group at the university of British Columbia, conducts experiments on the soft X-ray reiXS beamline to understand the nature of these static electronic waves, which are believed to be key for the ultimate understanding of the so-far elusive nature of superconductivity.

Experts hope that a more

comprehensive understanding

of charge-density-waves in

cuprates will be instrumental

to one day achieving room-

temperature superconductivity.

2 0 1 4 r e s e a r c h r e p o r t 45

a look at the reiXS preparation vacuum chamber. arPeS momentum-energy map along the nodal direction Γà(π ,π).

on the reiXS beamline

experts hope that a more comprehensive understanding of charge-density-waves in cuprates will be instrumental to one day achieving room-temperature superconductivity.

“the wealth of experimental information that our work at the CLS has brought to light will be fundamental for the understanding and design of better superconducting materials which are poised for tremendous technological applications,” says Comin, who was presented the Bancroft award and a $3,000 cash prize at the 2014 CLS annual users’ Meeting.

riccardo Comin's Phd work at uBC led to the publication of several papers on the topic, including one Nature Communications and three Science papers.

"The wealth of experimental information that our work

at the CLS has brought to light will be fundamental for

the understanding and design of better superconducting

materials which are poised for tremendous technological

applications." – Riccardo Comin

in March, he published new research in Science, which demonstrates for the first time the full nanoscale symmetry of charge-density-waves in one of the purest cuprate superconductors, YBa2Cu3o6+y.

Comin has recently joined the Sargent group at the university of toronto as a post-doctoral fellow.


46

BeamlinesCLS has developed a unique suite of beamlines to meet the needs of the Canadian synchrotron research community, with capabilities and design characteristics that make many of them globally unique, providing academic researchers and industrial customers with an array of techniques for research on materials, earth and the environment, and life sciences.

this diagram shows the current layout of the experimental floor, including facilities in all phases of development.

operational

Beamlines with general user beamtime available through the peer review or letter of intent process.

under ConstruCtion

Beamlines in a detailed design or construction phase.

availaBle ports

Ports available for construction of new beamlines.

Quatum MaterialsSpectroscopy Centre (QMSC)

Soft X-ray Spectromicroscopy (SM)

variable Line Spacing Plane grating Monochromator

(vLS-PgM)

Spherical grating Monochromator (SgM)

Mid infrared Spectromicroscopy (Mid-ir)

Far infrared high resolution gas Phase Spectroscopy (Far-ir)

optical Synchrotron radiationFacility diagnostic Beamline(oSr)

X-ray Synchrotron radiationFacility diagnostic Beamline (XSr)

resonant elastic andinelastic X-ray Scattering (reiXS)

10B2

10B1

9B2

11B1

Acceleratorslinear aCCelerator (linaC)

Booster ring – Booster to storage

storage ring

shielding

F a c i l i t y U p d a t e


Canadian Macromolecular Crystallography Facility

Beamline (CMCF-BM)

Biomedical imaging and therapy id (BMit-id)Biomedical imaging and

therapy BM (BMit-BM)

Synchrotron Laboratory for Micro- and nano-devices (SyLMand)

Soft X-ray MicrocharacterizationBeamline (SXrMB)

hard X-ray Microanalysis (hXMa)

Canadian MacromolecularCrystallography Facility Beamline (CMCF-id)

Biological X-ray absorption Spectroscopy (BioXaS)

very Sensitive Probe employingradiation from a Synchrotron (veSPerS)

4B2

3B2

Brockhouse X-ray diffraction and Scattering Sector (BXdS)

3B13id

6B2

FirSt BuiLding eXPanSion

BXdS eXPanSion

ideaS

2 0 1 4 r e s e a r c h r e p o r t 472 0 1 4 r e s e a r c h r e p o r t 47

Port Beamline energy technique Beamline StatuS

01B1-1 Mid infrared Spectromicroscopy (Mid-ir) 560 - 6000 cm-1

• Spectromicroscopy at diffraction-limited spatial resolution

• Photoacoustic Spectroscopy

accepting proposals

02B1-1 high resolution Far ir Spectroscopy (Far-ir) 5 - 1000 cm-1 • Fourier Transform Absorption Spectroscopy accepting

proposals

04id-1 Brockhouse X-ray diffraction Sector 3000 - 15 000 ev

• Inelastic X-ray scattering• Resonant X-ray scattering• Grazing incidence diffraction• Reflectivity• Small and Wide Angle X-ray scattering

Construction

04id-2 Brockhouse X-ray diffraction Sector 7000 - 60 000 ev

• Powder diffraction• Single Crystal Crystallography• High pressure diamond anvil cell• High Q-space PDF

Construction

05id-2 Biomedical imaging and therapy (BMit) 20 000 - 100 000 ev

• Imaging – conventional absorption imaging, DEI / MIR, Ct, K-edge Subtraction (KeS)

• Therapy – Microbeam Radiation Therapy, CT Therapy

accepting proposals

05B1-1 Biomedical imaging and therapy (BMit) 8000 - 40 000 ev

• Conventional absorption imaging • Phase contrast or in-line holography • Ultra-small, small, wide angle scattering imaging • Computer Tomography (CT) • Diffraction Enhanced Imaging (DEI) / Multiple Image

radiography (Mir)

accepting proposals

05B2-1Synchrotron Laboratory for Micro and nano devices (SyLMand)

1000 - 15 000 ev• Deep X-ray lithography• LIGA process lithography steps

accepting Lois

06id hard X-ray Microanalysis (hXMa) 5000 - 40 000 ev

• X-ray Absorption Fine Structure (XAFS)• Microprobe• Powder Diffraction • X-ray Scattering

accepting proposals

06B1-1Soft X-ray Microcharacterization Beamline (SXrMB)

1700 - 10 000 ev

• X-ray Absorption Spectroscopy (XAS)• X-ray Excited Optical Luminescence (XEOL)• X-ray Magnetic Linear Dichroism (XMLD) • Photoemission Electron Microscopy (PEEM)• X-ray Magnetic Circular Dichroism (XMCD) • Resonant spectroscopies • Photo and Auger Electron Spectroscopy

accepting proposals

07id-1 BioXaS 4000 - 21 000 ev• X-ray Absorption Fine Structure (XAFS)• Macro-, Micro- and Nanoprobe Imaging and XAFS• Confocal Imaging and XAFS

Construction

07id-2 BioXaS 5000 - 28 000 ev• X-ray Absorption Fine Structure (XAFS)• Dilute Sample XAFS• Very High Resolution XAFS

Construction

table 1:

Photon Port Allocation


48 C a n a d i a n L i g h t S o u r C e


Port Beamline energy technique Beamline StatuS

07B2-1very Sensitive Probe employing radiation from a Synchrotron (veSPerS)

6000 - 30 000 ev

• X-ray Laue Diffraction• X-ray Fluorescence Spectroscopy • X-ray Absorption Near Edge Structure (XANES)• Differential Aperture X-ray Microscopy• Multi-bandpass and pink beam capability• Microprobe

accepting proposals

08id-1 CMCF – Macromolecular Crystallography 6500 - 18 000 ev

• Single crystal X-ray diffraction • Multiwavelength Anomalous Dispersion (MAD) • XANES on crystals

accepting proposals

08B1-1 CMCF – high throughput Crystallography 4000 - 18 000 ev

• High throughput X-ray diffraction • Multiwavelength Anomalous Dispersion (MAD) • Powder diffraction• EXAFS on crystals• Small molecule crystallography

accepting proposals

09id Quantum Materials Spectroscopy Centre 10 - 1000 ev

• Spin and Angle Resolved Photoemission Spectroscopy• Molecular Beam Epitaxy and Characterization for

organics and inorganicsConstruction

10id-1 Soft X-ray Spectromicroscopy 100 - 2500 ev

• Photoemission Electron Microscopy (PEEM)• Scanning transmission X-ray Microscopy (STXM) • Circular and linear polarization

accepting proposals

10id-2resonant elastic and inelastic X-ray Scattering (reiXS)

80 - 2000 ev

• X-ray Absorption Spectroscopy (XAS)• X-ray Emission Spectroscopy • Resonant Inelastic X-ray Scattering • Resonant Elastic X-ray Scattering • Coherent X-ray Scattering (Speckle) • Magnetic X-ray Dichroism • Molecular Beam Epitaxy

accepting proposals

11id-1high resolution Spherical grating Monochromator (SgM)

240 - 2000 ev

• X-ray Absorption Spectroscopy (XAS) • Photo and Auger Electron Spectroscopy• XEOL• Gas Phase Photoelectron and Coincidence

Spectroscopy• TOF measurements

accepting proposals

11id-2variable Line Spacing Plane grating Monochromator (vLS-PgM)

5.5 - 250 ev

• X-ray Absorption Spectroscopy (XAS)• Photo and Auger Electron Spectroscopy

• XEOL

• Gas Phase Photoelectron and Coincidence Spectroscopy

accepting proposals

08B2-1industry, development, education, applications, Students (ideaS)

2000 - 20 000 ev • X-ray Absorption Spectroscopy (XAS) Commissioning


2 0 1 4 r e s e a r c h r e p o r t 49


Facts and Figuresthe CLS has hosted 2500 researchers from academic institutions, government, and industry from 28 countries and 12 provinces

and territories; delivered over 29,000 experimental shifts; received over 10,000 user visits; and provided a scientific service critical

in over 1,000 scientific publications, since beginning operations in 2005.

Storage Ring User Beam Reliability Annual Hours of Operation

Users and Proposals

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014

Mean time between trips (hours)

User shifts with no trips (percentage)

2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014

Machine Studies (annual)

SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed

Material & Chemical Sciences

Life Sciences

Environmental & Earth Sciences

Macromolecular Chrystallography

900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty

Research Associate Other

1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK

Canada, Other Provinces

International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329

BBEAM TEAM MEMBER 585

PURCHASED ACCESS 465

SPECIAL REQUESTS 281

BEAMLINE SCIENTIST 364

BL MAINTENANCE & UPGRADEDEVELOPMENT 1524

2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014


2 0 1 4 r e s e a r c h r e p o r t 51

F a c i l i t y u p d a t e

Oversubscription2009 2010 2011 2012 2013 2014

number of shifts requested 1768 2675 3456 4538 4788 4921

number of shifts allocated 1252 1816 2203 3305 3077 3082

oversubscription 41% 47% 57% 37% 56% 60%

no. of beamlines participating 5.5 8 10 10 10 10

Discipline of Users

Classification of Users Geographical Distribution of Shifts

Shifts delivered per Category per Year

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

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750

883

850

450

900

896

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2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

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800

600

400

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757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

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02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014

90

80

70

60

50

40

30

20

10

020092008 2010 2011 2012 2013 2014



2000

1800

1600

1400

1200

1000

800

600

400

200

020092008

757

2007

566

2006

386

2010

1236

2011 2012 2013 2014

7000

6000

5000

4000

3000

2000

1000

02007 20082004 2005 2006 2009 2010 2011 2012 2013 2014


SR1 Fill (annual)

SR1 Stored (annual)

1000

800

600

400

200

02007 20082005 2006 2009 2010 2011 2012 2013 2014

Unclassi�ed


Life Sciences



900

800

700

600

500

400

300

200

100

02007 20082006 2009 2010 2011 2012 2013 2014

Student

PDF

Scientist

Faculty


1800

1600

1400

1200

1000

800

600

400

200

02009 2010 2011 2012 2013 2014

Canada, SK


International

User Visits

Users

Proposals Received

Proposal Target

Publications

User Visits Target

Users Target

911 1100

1295

1300 1431

1621

1835

18001700

1500

447393

208

300

311350 400

390469

506 531

190

282195

22 5162 93 134

197 223 258 224

577

2010

650

2011

755

750

883

850

450

900

896

500

GENERAL USER 3329






2014

C a n a d i a n L i g h t S o u r C e52 C a n a d i a n L i g h t S o u r C e52

REFEREED JOURnALFrandoloso, r.; Martinez-Martinez, S.; Calmettes, C.; Fegan, J.; Costa, e.; Curran, d.; Yu, r.-h.; gutierrez-Martin, C. B.; rodriguez Ferri, e. F.; Moraes, t. F.; Schryvers, a. B. (2014). Nonbinding site-directed mutants of transferrin binding protein B enhances their immunogenicity and protective capabilities. Infection and Immunity. 10.1128/iai.02572-14

CMCF-BM, CMCF-id

anzar, Muhammad; grochulski, Pawel; Bonnet, Brennan (2014). Synchrotron X-ray Diffraction to Detect Glass or Ice Formation in the Vitrified Bovine Cumulus-Oocyte Complexes and Morulae. PLoS one 9(12), e114801. 10.1371/journal.pone.0114801.

CMCF

rené, olivier; Fauber, Benjamin P.; Boenig, gladys de Leon; Burton, Brenda; eidenschenk, Céline; everett, Christine; gobbi, alberto; hymowitz, Sarah g.; Johnson, adam r.; Kiefer, James r.; Liimatta, Marya; Lockey, Peter; norman, Maxine; ouyang, Wenjun; Wallweber, heidi a.; Wong, harvey (2014). Minor Structural Change to Tertiary Sulfonamide RORc Ligands Led to Opposite Mechanisms of Action. aCS Medicinal Chemistry Letters, 141223070836000. 10.1021/ml500420y.

CMCF-id

Lahlali, rachid; Jiang, Yunfei; Kumar, Saroj; Karunakaran, Chithra; Liu, Xia; Borondics, Ferenc; hallin, emil; Bueckert, rosalind (2014). ATRâ€“FTIR spectroscopy reveals involvement of lipids and proteins of intact pea pollen grains to heat stress tolerance. Frontiers in Plant Science 5. 10.3389/fpls.2014.00747.

Far-ir

Yachnin, Brahm J.; Mcevoy, Michelle B.; MacCuish, roderick J. d.; Morley, Krista L.; Lau, Peter C. K.; Berghuis, albert M. (2014). Lactone-Bound Structures of Cyclohexanone Monooxygenase Provide Insight into the Stereochemistry of Catalysis. aCS Chemical Biology 9(12), 2843-2851. 10.1021/cb500442e.

CMCF-id

Chan, anson C. K.; Blair, Kris M.; Liu, Yanjie; Frirdich, emilisa; gaynor, erin C.; tanner, Martin e.; Salama, nina r.; Murphy, Michael e. P. (2014). Helical Shape of Helicobacter pylori Requires an Atypical Glutamine as a Zinc Ligand in the Carboxypeptidase Csd4. Journal of Biological Chemistry, jbc.M114.624734. 10.1074/jbc.M114.624734.

CMCF-BM, CMCF-id

vadlamani, grishma; thomas, Misty d.; Patel, trushar r.; donald, Lynda J.; reeve, thomas M.; Stetefeld, Jörg; Standing, Kenneth g.; vocadlo, david J.; Mark, Brian L. (2014). the β-Lactamase gene regulator ampr is a tetramer that Recognizes and Binds the d-Ala-d-Ala Motif of Its Repressor UDP- N -acetylmuramic Acid (MurNAc)-pentapeptide. Journal of Biological Chemistry 290(5), 2630-2643. 10.1074/jbc.m114.618199.

Leedahl, B.; Zatsepin, d. a.; Boukhvalov, d. W.; Kurmaev, e. Z.; green, r. J.; Zhidkov, i. S.; Kim, S. S.; Cui, L.; gavrilov, n. v.; Cholakh, S. o.; Moewes, a. (2014). Study of the Structural Characteristics of 3d Metals Cr, Mn, Fe, Co, Ni, and Cu Implanted in ZnO and TiO 2 —Experiment and Theory. the Journal of Physical Chemistry C 118(48), 28143-28151. 10.1021/jp509761c.

SgM

Lee, Kee eun; Liu, Lijia; Kelly, timothy L. (2014). Effect of Molybdenum Oxide Electronic Structure on Organic Photovoltaic Device Performance: An X-ray Absorption Spectroscopy Study. the Journal of Physical Chemistry C 118(48), 27735-27741. 10.1021/jp508972v.

SXrMB

Conly, Cuylar J. t.; Skovpen, Yulia v.; Li, Shuo; Palmer, david r. J.; Sanders, david a. r. (2014). Tyrosine 110 Plays a Critical Role in Regulating the Allosteric Inhibition of Campylobacter jejuni Dihydrodipicolinate Synthase by Lysine. Biochemistry 53(47), 7396-7406. 10.1021/bi5012157.

CMCF-BM, CMCF-id

Liu, Jian; Xiao, Biwei; Banis, Mohammad n.; Li, ruying; Sham, tsun-Kong; Sun, Xueliang (2014). Atomic layer deposition of amorphous iron phosphates on carbon nanotubes as cathode materials for lithium-ion batteries. electrochimica acta. 10.1016/j.electacta.2014.12.158.

hXMa

Yue, Caixia; Wang, Jiancheng; han, Lina; Chang, Liping; hu, Yongfeng; Wang, hui (2014). Effects of pretreatment of Pd/AC sorbents on the removal of Hg0 from coal derived fuel gas. Fuel Processing technology. 10.1016/j.fuproc.2014.11.038.

SXrMB

duan, James J. -W.; Lu, Zhonghui; Jiang, Bin; Yang, Bingwei v.; doweyko, Lidia M.; nirschl, david S.; haque, Lauren e.; Lin, Shuqun; Brown, gregory; hynes, John; tokarski, John S.; Sack, John S.; Khan, Javed; Lippy, Jonathan S.; Zhang, rosemary F.; Pitt, Sidney; Shen, guoxiang; Pitts, William J.; Carter, Percy h.; Barrish, Joel C.; nadler, Steven g.; Salter-Cid, Luisa M.; McKinnon, Murray; Fura, aberra; Schieven, gary L.; Wrobleski, Stephen t. (2014). Discovery of pyrrolo [1,2-b] pyridazine-3-carboxamides as Janus kinase (JAK) inhibitors. Bioorganic & Medicinal Chemistry Letters 24(24), 5721-5726. 10.1016/j.bmcl.2014.10.061.

CMCF-id

aluri, esther rani; grosvenor, andrew P. (2014). An investigation of the electronic structure and structural stability of RE2Ti2O7 by glancing angle and total electron yield XANES. Journal of alloys and Compounds 616, 516-526. 10.1016/j.jallcom.2014.07.151.

aCCeSS-PnC/XSd

niakan, h.; Zhang, C.; Yang, L.; Yang, Q.; Szpunar, J.a. (2014). Structure and properties of DLC-MoS2 thin films synthesized by BTIBD method. Journal of Physics and Chemistry of Solids 75(12), 1289-1294. 10.1016/j.jpcs.2014.07.002.

SXrMB

Javed, Muhammad Babar; Kachanoski, gary; Siddique, tariq (2014). Arsenic fractionation and mineralogical characterization of sediments in the Cold Lake area of Alberta, Canada. the Science of the total environment 500-501, 181-190. 10.1016/j.scitotenv.2014.08.083.

veSPerS

doores, Katie J.; Kong, Leopold; Krumm, Stefanie a.; Le, Khoa M.; Sok, devin; Laserson, uri; garces, Fernando; Poignard, Pascal; Wilson, ian a.; Burton, dennis r. (2014). Two Classes of Broadly Neutralizing Antibodies within a Single Lineage Directed to the High-Mannose Patch of HIV Envelope. Journal of virology 89(2), 1105-1118. 10.1128/jvi.02905-14.

May, timothy; duffy, alan (2014). Modeling infrared beam lines with Shadow and Zemax. vibrational Spectroscopy 75, 123-126. 10.1016/j.vibspec.2014.08.009.

Far-ir

Catalano, S.; gibert, M.; Bisogni, v.; Peil, o. e.; he, F.; Sutarto, r.; viret, M.; Zubko, P.; Scherwitzl, r.; georges, a.; Sawatzky, g. a.; Schmitt, t.; triscone, J. -M. (2014). Electronic transitions in strained SmNiO3 thin films. aPL Materials 2(11), 116110. 10.1063/1.4902138.

reiXS

Sharma, rajesh v.; Baroi, Chinmoy; dalai, ajay K. (2014). Production of biodiesel from unrefined canola oil using mesoporous sulfated Ti-SBA-15 catalyst. Catalysis today 237, 3-12. 10.1016/j.cattod.2014.07.005.

hXMa

Banerjee, abhinandan; theron, robin; Scott, robert W.J. (2014). Design, synthesis, catalytic application, and strategic redispersion of plasmonic silver nanoparticles in ionic liquid media. Journal of Molecular Catalysis a Chemical 393, 105-111. 10.1016/j.molcata.2014.05.036.

SXrMB

Leon, Y.; Saheb, M.; drouet, e.; neff, d.; Foy, e.; Leroy, e.; dynes, J.J.; dillmann, P. (2014). Interfacial layer on archaeological mild steel corroded in carbonated anoxic environments studied with coupled micro and nano probes. Corrosion Science 88, 23-35. 10.1016/j.corsci.2014.07.005.

SM

hitchcock, adam P.; Berejnov, viatcheslav; Lee, vincent; West, Marcia; Colbow, vesna; dutta, Monica; Wessel, Silvia (2014). Carbon corrosion of proton exchange membrane fuel cell catalyst layers studied by scanning transmission X-ray microscopy. Journal of Power Sources 266, 66-78. 10.1016/j.jpowsour.2014.04.119.

SM

Bailey-elkin, B. a.; Knaap, r. C. M.; Johnson, g. g.; dalebout, t. J.; ninaber, d. K.; van Kasteren, P. B.; Bredenbeek, P. J.; Snijder, e. J.; Kikkert, M.; Mark, B. L. (2014). Crystal Structure of the Middle East Respiratory Syndrome Coronavirus (MERS-CoV) Papain-like Protease Bound to Ubiquitin Facilitates Targeted Disruption of Deubiquitinating Activity to Demonstrate Its Role in Innate Immune Suppression. Journal of Biological Chemistry 289(50), 34667-34682. 10.1074/jbc.m114.609644.

CMCF-BM

ootsuki, d.; takubo, K.; Kudo, K.; ishii, h.; nohara, M.; Saini, n. L.; Sutarto, r.; he, F.; regier, t. Z.; Zonno, M.; Schneider, M.; Levy, g.; Sawatzky, g. a.; damascelli, a.; Mizokawa, t. (2014). Effect of Pt substitution on the electronic structure of AuTe2. Physical review B 90(14). 10.1103/physrevb.90.144515.

SgM

gobeil, Sophie M.C.; Clouthier, Christopher M.; Park, Jaeok; gagné, donald; Berghuis, albert M.; doucet, nicolas; Pelletier, Joelle n. (2014). Maintenance of Native-like Protein Dynamics May Not Be Required for Engineering Functional Proteins. Chemistry & Biology 21(10), 1330-1340. 10.1016/j.chembiol.2014.07.016.

CMCF-id

ritchie, andrew; eger, Shaylin; Wright, Chelsey; Chelladurai, daniel; Borrowman, Cuyler; olovsson, Weine; Magnuson, Martin; verma, Jai; Jena, debdeep; Xing, huili grace; dubuc, Christian; urquhart, Stephen (2014). Strain sensitivity in the nitrogen 1s NEXAFS spectra of gallium nitride. applied Surface Science 316, 232-236. 10.1016/j.apsusc.2014.07.070.

SM

Lee, vincent; Berejnov, viatcheslav; West, Marcia; Kundu, Sumit; Susac, darija; Stumper, Jürgen; atanasoski, radoslav t.; debe, Mark; hitchcock, adam P. (2014). Scanning transmission X-ray microscopy of nano structured thin film catalysts for proton-exchange-membrane fuel cells. Journal of Power Sources 263, 163-174. 10.1016/j.jpowsour.2014.04.020.

SM

Yao, Yali; hu, Yongfeng; Scott, robert W. J. (2014). Watching Iron Nanoparticles Rust: An in Situ X-ray Absorption Spectroscopic Study. the Journal of Physical Chemistry C 118(38), 22317-22324. 10.1021/jp506281d.

SgM, SXrMB

Pichaandi, Jothirmayanantham; das, gautom Kumar; Johnson, noah J. J.; regier, tom; van veggel, Frank C. J. M. (2014). Probing the Structure of NaYF 4 Nanocrystals using Synchrotron-Based Energy-Dependent X-ray Photoelectron Spectroscopy. the Journal of Physical Chemistry C 118(37), 21639-21646. 10.1021/jp505646j.

Singh, anirudh K.; Pluvinage, Benjamin; higgins, Melanie a.; dalia, ankur B.; Woodiga, Shireen a.; Flynn, Matthew; Lloyd, audrey r.; Weiser, Jeffrey n.; Stubbs, Keith a.; Boraston, alisdair B.; King, Samantha J. (2014). Unravelling the Multiple Functions of the Architecturally Intricate Streptococcus pneumoniae β-galactosidase, BgaA. PLoS Pathogens 10(9), e1004364. 10.1371/journal.ppat.1004364.

CMCF-BM, CMCF-id

2014 Publications

2 0 1 4 r e s e a r c h r e p o r t 53

P u b l i c a t i o n s

Michaelian, K.h.; oladepo, S.a.; Shaw, J.M.; Liu, X.; Bégué, d.; Baraille, i. (2014). Raman and photoacoustic infrared spectra of fluorene derivatives: Experiment and calculations. vibrational Spectroscopy 74, 33-46. 10.1016/j.vibspec.2014.07.003.

Mid-ir

Baroi, Chinmoy; dalai, ajay K. (2014). Esterification of free fatty acids (FFA) of Green Seed Canola (GSC) oil using H-Y zeolite supported 12-Tungstophosphoric acid (TPA). applied Catalysis a general 485, 99-107. 10.1016/j.apcata.2014.07.033.

hXMa

groves, Michael n.; Malardier-Jugroot, Cecile; Jugroot, Manish (2014). Environmentally friendly synthesis of supportless Pt based nanoreactors in aqueous solution. Chemical Physics Letters 612, 309-312. 10.1016/j.cplett.2014.08.017.

CMCF-BM

Li, Y.S.; Ma, h.t.; Yang, L.Z.; Zhang, C.Z.; Feng, r.F.; Yang, Q.; hirose, a. (2014). Competitive graphitization and diamond growth on hot-dip aluminized carbon steel substrate. applied Surface Science 314, 1041-1046. 10.1016/j.apsusc.2014.06.051.

veSPerS

Moazed, Banafsheh; hashemi, Manouchehr; achenbach, Sven (2014). Novel PMMA Polymer-Based Nanopores Capable of Detection and Discrimination Between Structurally Different Biomolecules. ieee Sensors Journal 14(9), 3292-3309. 10.1109/jsen.2014.2326426.

SYLMand

Kim, Chang-Yong; Kim, Seok hwan; Kim, Seong Jun; an, Ki-Seok (2014). VO2 (110) film formation on TiO2 (110) through post-reduction of ALD grown vanadium oxide. applied Surface Science 313, 368-371. 10.1016/j.apsusc.2014.05.216.

hXMa, SgM

Lieverse, a.r.; Pratt, i.v.; Schulting, r.J.; Cooper, d.M.L.; Bazaliiskii, v.i.; Weber, a.W. (2014). Point taken: An unusual case of incisor agenesis and mandibular trauma in Early Bronze Age Siberia. international Journal of Paleopathology 6, 53-59. 10.1016/j.ijpp.2014.04.004.

BMit-BM

hong, Seongjin; Khim, Jong Seong; Park, Jinsoon; Son, hee-Sik; Choi, Sung-deuk; Choi, Kyungho; ryu, Jongseong; Kim, Chang-Yong; Chang, gap Soo; giesy, John P. (2014). Species- and tissue-specific bioaccumulation of arsenicals in various aquatic organisms from a highly industrialized area in the Pohang City, Korea. environmental Pollution 192, 27-35. 10.1016/j.envpol.2014.05.004.

hXMa

Basnayaka, upekha; Chapman, dean; adams, gregg; Wysokinski, tomasz; Belev, george; Baerwald, angela (2014). Diffraction-enhanced Synchrotron Imaging of Bovine Ovaries Ex Vivo. Journal of Medical imaging and radiation Sciences 45(3), 307-315. 10.1016/j.jmir.2014.01.004.

BMit-BM

nearing, Michelle M.; Koch, iris; reimer, Kenneth J. (2014). Complementary arsenic speciation methods: A review. Spectrochimica acta Part B atomic Spectroscopy 99, 150-162. 10.1016/j.sab.2014.07.001.

aCCeSS-PnC/XSd

achkar, a. J.; Mao, X.; McMahon, Christopher; Sutarto, r.; he, F.; Liang, ruixing; Bonn, d. a.; hardy, W. n.; hawthorn, d. g. (2014). Impact of Quenched Oxygen Disorder on Charge Density Wave Order in YBa2Cu3O6+x. Physical review Letters 113(10). 10.1103/physrevlett.113.107002.

reiXS

Schroeder, Kristen L.; Sylvain, nicole J.; Kirkpatrick, Lisa J.; rosser, Benjamin W. C. (2014). Fibre types in primary ‘flight’ muscles of the African Penguin (Spheniscus demersus). acta Zoologica, n/a-n/a. 10.1111/azo.12097.

Patel, Mihir; aswath, Pranesh B. (2014). Structure and chemistry of crankcase and cylinder soot and tribofilms on piston rings from a Mack T-12 dynamometer engine test. tribology international 77, 111-121. 10.1016/j.triboint.2014.04.004.

SgM, SXrMB, vLS-PgM

eickhoff, Merle; obst, Martin; Schröder, Christian; hitchcock, adam P.; tyliszczak, tolek; Martinez, raul e.; robbins, Leslie J.; Konhauser, Kurt o.; Kappler, andreas (2014). Nickel partitioning in biogenic and abiogenic ferrihydrite: The influence of silica and implications for ancient environments. geochimica et Cosmochimica acta 140, 65-79. 10.1016/j.gca.2014.05.021.

SM

hosseini, M.; Klymyshyn, d.M. (2014). Properties of small gap-loaded patch antenna with fast-wave behaviours. electronics Letters 50(18), 1268-1269. 10.1049/el.2014.1887.

SYLMand

Chang, hyun-shik; Buettner, Shea W.; Seaman, John. C.; Jaffé, Peter r.; Koster van groos, Paul. g.; Li, dien; Peacock, aaron d.; Scheckel, Kirk g.; Kaplan, daniel i. (2014). Uranium Immobilization in an Iron-Rich Rhizosphere of a Native Wetland Plant from the Savannah River Site under Reducing Conditions. environmental Science & technology 48(16), 9270-9278. 10.1021/es5015136.

hXMa

Luan, X.; Campanucci, v. a.; nair, M.; Yilmaz, o.; Belev, g.; Machen, t. e.; Chapman, d.; ianowski, J. P. (2014). Pseudomonas aeruginosa triggers CFTR-mediated airway surface liquid secretion in swine trachea. Proceedings of the national academy of Sciences 111(35), 12930-12935. 10.1073/pnas.1406414111.

BMit

Chamberlain, Philip P; Lopez-girona, antonia; Miller, Karen; Carmel, gilles; Pagarigan, Barbra; Chie-Leon, Barbara; rychak, emily; Corral, Laura g; ren, Yan J; Wang, Maria; riley, Mariko; delker, Silvia L; ito, takumi; ando, hideki; Mori, tomoyuki; hirano, Yoshinori; handa, hiroshi; hakoshima, toshio; daniel, thomas o; Cathers, Brian e (2014). Structure of the human Cereblon-DDB1-lenalidomide complex reveals basis for responsiveness to thalidomide analogs. nature Structural & Molecular Biology 21(9), 803-809. 10.1038/nsmb.2874.

CMCF-id

Macke, Sebastian; radi, abdullah; hamann-Borrero, Jorge e.; verna, adriano; Bluschke, Martin; Brück, Sebastian; goering, eberhard; Sutarto, ronny; he, Feizhou; Cristiani, georg; Wu, Meng; Benckiser, eva; habermeier, hanns-ulrich; Logvenov, gennady; gauquelin, nicolas; Botton, gianluigi a.; Kajdos, adam P.; Stemmer, Susanne; Sawatzky, george a.; haverkort, Maurits W.; Keimer, Bernhard; hinkov, vladimir (2014). Element Specific Monolayer Depth Profiling. advanced Materials 26(38), 6554-6559. 10.1002/adma.201402028.

reiXS

rafiuddin, Mohamed ruwaid; Mueller, eric; grosvenor, andrew P. (2014). X-ray Spectroscopic Study of the Electronic Structure of Monazite- and Xenotime-Type Rare-Earth Phosphates. the Journal of Physical Chemistry C 118(31), 18000-18009. 10.1021/jp5051996.

SgM, SXrMB, vLS-PgM

Suits, M. d. L.; Pluvinage, B.; Law, a.; Liu, Y.; Palma, a. S.; Chai, W.; Feizi, t.; Boraston, a. B. (2014). Conformational Analysis of the Streptococcus pneumoniae Hyaluronate Lyase and Characterization of Its Hyaluronan-specific Carbohydrate-binding Module. Journal of Biological Chemistry 289(39), 27264-27277. 10.1074/jbc.m114.578435.

CMCF-BM

de gregorio, Bradley t.; Stroud, rhonda M.; nittler, Larry r.; Cody, george; david Kilcoyne, a. L. (2014). Coordinated Electron and X-ray Microscopy of Cometary Organic Matter Collected by the NASA Stardust Mission. Microscopy and Microanalysis 20(S3), 1694-1695. 10.1017/s1431927614010204.

SM

Sandilands, L. J.; reijnders, a. a.; Su, a. h.; Baydina, v.; Xu, Z.; Yang, a.; gu, g.; Pedersen, t.; Borondics, F.; Burch, K. S. (2014). Origin of the insulating state in exfoliated high-Tc two-dimensional atomic crystals. Physical review B 90(8). 10.1103/physrevb.90.081402.

Mid-ir

takubo, K.; Comin, r.; ootsuki, d.; Mizokawa, t.; Wadati, h.; takahashi, Y.; Shibata, g.; Fujimori, a.; Sutarto, r.; he, F.; Pyon, S.; Kudo, K.; nohara, M.; Levy, g.; elfimov, i. S.; Sawatzky, g. a.; damascelli, a. (2014). Bond order and the role of ligand states in stripe-modulated IrTe2. Physical review B 90(8). 10.1103/physrevb.90.081104.

reiXS

diaz, B.; gomez, a.; Meyer, B.; duffy, a.; hallin, e.; Kycia, S. (2014). Undulator beamline of the Brockhouse sector at the Canadian Light Source. review of Scientific instruments 85(8), 085104. 10.1063/1.4890815.

Zhang, X.h.; han, J.C; Zhou, J.g.; Xin, C.; Zhang, Z.h.; Song, B. (2014). Ferromagnetism in homogeneous (Al,Co)-codoped 4H-silicon carbides. Journal of Magnetism and Magnetic Materials 363, 34-42. 10.1016/j.jmmm.2014.03.062.

vLS-PgM

Li, Jinhua; Bernard, Sylvain; Benzerara, Karim; Beyssac, olivier; allard, thierry; Cosmidis, Julie; Moussou, Julien (2014). Impact of biomineralization on the preservation of microorganisms during fossilization: An experimental perspective. earth and Planetary Science Letters 400, 113-122. 10.1016/j.epsl.2014.05.031.

SM

Miot, Jennyfer; Li, Jinhua; Benzerara, Karim; Sougrati, Moulay tahar; ona-nguema, georges; Bernard, Sylvain; Jumas, Jean-Claude; guyot, François (2014). Formation of single domain magnetite by green rust oxidation promoted by microbial anaerobic nitrate-dependent iron oxidation. geochimica et Cosmochimica acta 139, 327-343. 10.1016/j.gca.2014.04.047.

SM

Walker, James d.S.; hayes, John r.; grosvenor, andrew P. (2014). Examination of the site preference of metals in NiAl2−xGaxO4 spinel-type oxides by X-ray absorption near-edge spectroscopy. Journal of electron Spectroscopy and related Phenomena 195, 139-144. 10.1016/j.elspec.2014.06.013.

vLS-PgM, aCCeSS-PnC/XSd

Khatir, S.; hirose, a.; Xiao, C. (2014). Coating diamond-like carbon films on polymer substrates by inductively coupled plasma assisted sputtering. Surface and Coatings technology 253, 96-99. 10.1016/j.surfcoat.2014.05.020.

reiXS

hunt, a.; Kurmaev, e.Z.; Moewes, a. (2014). Band gap engineering of graphene oxide by chemical modification. Carbon 75, 366-371. 10.1016/j.carbon.2014.04.015.

SgM

hehemann, Jan-hendrik; Law, adrienne; redecke, Lars; Boraston, alisdair B. (2014). The Structure of RdDddP from Roseobacter denitrificans Reveals That DMSP Lyases in the DddP-Family Are Metalloenzymes. PLoS one 9(7), e103128. 10.1371/journal.pone.0103128.

CMCF-id

Bondici, v.F.; Khan, n.h.; Swerhone, g.d.W.; dynes, J.J.; Lawrence, J.r.; Yergeau, e.; Wolfaardt, g.M.; Warner, J.; Korber, d.r. (2014). Biogeochemical activity of microbial biofilms in the water column overlying uranium mine tailings. Journal of applied Microbiology 117(4), 1079-1094. 10.1111/jam.12593.

SM

Penfield, J. S.; Worrall, L. J.; Strynadka, n. C.; eltis, L. d. (2014). Substrate Specificities and Conformational Flexibility of 3-Ketosteroid 9 -Hydroxylases. Journal of Biological Chemistry 289(37), 25523-25536. 10.1074/jbc.m114.575886.

CMCF-BM

rema, t.; Lawrence, J. r.; dynes, J. J.; hitchcock, a. P.; Korber, d. r. (2014). Microscopic and Spectroscopic Analyses of Chlorhexidine Tolerance in Delftia acidovorans Biofilms. antimicrobial agents and Chemotherapy 58(10), 5673-5686. 10.1128/aac.02984-14.

Mid-ir, SM

Liu, Jian; Banis, Mohammad n.; Sun, Qian; Lushington, andrew; Li, ruying; Sham, tsun-Kong; Sun, Xueliang (2014). Rational Design of Atomic-Layer-Deposited LiFePO 4 as a High-Performance Cathode for Lithium-Ion Batteries. advanced Materials 26(37), 6472-6477. 10.1002/adma.201401805.

SgM, SM, vLS-PgM


roach, e. J.; Kimber, M. S.; Khursigara, C. M. (2014). Crystal Structure and Site-directed Mutational analysis reveals Key residues involved in escherichia coli Zapa Function. Journal of Biological Chemistry 289(34), 23276-23286. 10.1074/jbc.m114.561928.

CMCF-id

Lobacheva, o.; Chavarha, M.; Yiu, Y. M.; Sham, t. K.; goncharova, L. v. (2014). The local structure and ferromagnetism in Fe-implanted SrTiO3 single crystals. Journal of applied Physics 116(1), 013901. 10.1063/1.4886875.

SgM, aCCeSS-PnC/XSd

Little, d. J.; Li, g.; ing, C.; diFrancesco, B. r.; Bamford, n. C.; robinson, h.; nitz, M.; Pomes, r.; howell, P. L. (2014). Modification and periplasmic translocation of the biofilm exopolysaccharide poly- -1,6-N-acetyl-D-glucosamine. Proceedings of the national academy of Sciences 111(30), 11013-11018. 10.1073/pnas.1406388111.

CMCF-id

Zhang, Xuewei; Yu, Peiqiang (2014). Using a Non-invasive Technique in Nutrition: Synchrotron Radiation Infrared Microspectroscopy Spectroscopic Characterization of Oil Seeds Treated with Different Processing Conditions on Molecular Spectral Factors Influencing Nutrient Delivery. Journal of agricultural and Food Chemistry 62(26), 6199-6205. 10.1021/jf501553g.

Mid-ir

Li, Y. S.; Yang, L. Z.; Ma, h. t.; Feng, r. F.; Yang, Q.; hirose, a. (2014). Enhanced diamond deposition on Kovar alloy substrate with Al interlayer. Materials research innovations 18(S4), S4-979-S4-982. 10.1179/1432891714z.000000000818.

veSPerS

Badoga, Sandeep; Sharma, rajesh v.; dalai, ajay K.; adjaye, John (2014). Hydrotreating of heavy gas oil on mesoporous zirconia supported NiMo catalyst with EDTA. Fuel 128, 30-38. 10.1016/j.fuel.2014.02.056.

hXMa

Lezcano-gonzalez, i.; deka, u.; van der Bij, h.e.; Paalanen, P.; arstad, B.; Weckhuysen, B.M.; Beale, a.M. (2014). Chemical deactivation of Cu-SSZ-13 ammonia selective catalytic reduction (NH3-SCR) systems. applied Catalysis B environmental 154-155, 339-349. 10.1016/j.apcatb.2014.02.037.

SM

Plumb, K. W.; Clancy, J. P.; Sandilands, L. J.; Shankar, v. vijay; hu, Y. F.; Burch, K. S.; Kee, hae-Young; Kim, Young-June (2014). α−RuCl3: A spin-orbit assisted Mott insulator on a honeycomb lattice. Physical review B 90(4). 10.1103/physrevb.90.041112.

SXrMB

Bassey, Bassey; abueidda, abdallah; Cubbon, grant; Street, darin; Sabbir ahmed, asm; Wysokinski, tomasz W.; Belev, george; Chapman, dean (2014). Supplemental shielding of BMIT SOE-1 at the Canadian Light Source. radiation Physics and Chemistry 100, 8-12. 10.1016/j.radphyschem.2014.02.023.

niakan, h.; Zhang, C.; hu, Y.; Szpunar, J.a.; Yang, Q. (2014). Thermal stability of diamond-like carbon–MoS2 thin films in different environments. thin Solid Films 562, 244-249. 10.1016/j.tsf.2014.04.068.

SXrMB

Predoi-Cross, adriana; rosario, hoimonti; di Lonardo, gianfranco; Fusina, Luciano; tamassia, Filippo (2014). Far-infrared spectra and ground state spectroscopic parameters of 15NH2D. Journal of Molecular Spectroscopy 301, 13-14. 10.1016/j.jms.2014.05.002.

Far-ir

engel, annette Summers; Bovenkamp, gudrun Lisa; Prange, alexander; hormes, Josef (2014). In situ speciation of sulfur vapors by X-ray absorption near edge structure spectroscopy. Chemical geology 380, 1-6. 10.1016/j.chemgeo.2014.04.019.

das, Soumya; essilfie-dughan, Joseph; hendry, M. Jim (2014). Arsenate adsorption onto hematite nanoparticles under alkaline conditions: effects of aging. Journal of nanoparticle research 16(7). 10.1007/s11051-014-2490-3.

hXMa

Zhang, Linjuan; Zhou, Jing; Li, Jiong; Liu, gang; Lin, Xiao; Mao, Baohua; Liu, renduo; Zhang, Shuo; Wang, Jian-Qiang (2014). Surface Structural Reconstruction for Optical Response in Iodine-Modified TiO 2 Photocatalyst System. the Journal of Physical Chemistry C 118(25), 13726-13732. 10.1021/jp503966r.

hXMa

Balestrieri, M.; gallart, M.; Ziegler, M.; Bazylewski, P.; Ferblantier, g.; Schmerber, g.; Chang, g. S.; gilliot, P.; Muller, d.; Slaoui, a.; Colis, S.; dinia, a. (2014). Luminescent Properties and Energy Transfer in Pr 3+ Doped and Pr 3+ -Yb 3+ Co-doped ZnO Thin Films. the Journal of Physical Chemistry C 118(25), 13775-13780. 10.1021/jp502311z.

reiXS

iyer, ganjigunte r. Swathi; Wang, Jian; Wells, garth; guruvenket, Srinivasan; Payne, Scott; Bradley, Michael; Borondics, Ferenc (2014). Large-Area, Freestanding, Single-Layer Graphene–Gold: A Hybrid Plasmonic Nanostructure. aCS nano 8(6), 6353-6362. 10.1021/nn501864h.

Mid-ir, SM, SYLMand

Khozeimeh Sarbisheh, elaheh; green, Jennifer C.; Müller, Jens (2014). Isomerization of an Enantiomerically Pure Phosphorus-Bridged [1] Ferrocenophane. organometallics, 140623081557009. 10.1021/om500424m.

CMCF-BM

Bertwistle, drew; vogt, Linda; aamudalapalli, hari Babu; Palmer, david r. J.; Sanders, david a. r. (2014). Purification, crystallization and room-temperature X-ray diffraction of inositol dehydrogenase LcIDH2 from Lactobacillus casei BL23. acta Crystallographica Section F Structural Biology and Crystallization Communications 70(7), 979-983. 10.1107/s2053230x14011595.

CMCF-id

Metzler, rebecca a.; rez, Peter (2014). Polarization Dependence of Aragonite Calcium L-Edge XANES Spectrum Indicates c and b Axes Orientation. the Journal of Physical Chemistry B 118(24), 6758-6766. 10.1021/jp503565e.

SM

Zhang, huaihao; Jiang, Yuanyuan; hu, Yongfeng; Maclennan, aimee; Wang, hui; Wang, Chengyin (2014). Effect of Pyrite in Precursor on Capacitance Behavior of Prepared Activated Carbon. industrial & engineering Chemistry research 53(24), 10125-10132. 10.1021/ie501944r.

SXrMB

Liu, Jinyin; Bai, Lili; Wang, Jian; Zhao, guanqi; Sun, Xuhui; Zhong, Jun (2014). Measuring inside damage of individual multi-walled carbon nanotubes using scanning transmission X-ray microscopy. applied Physics Letters 104(24), 241602. 10.1063/1.4883919.

SM

tempel, W.; grabovec, i.; MacKenzie, F.; dichenko, Y. v.; usanov, S. a.; gilep, a. a.; Park, h.-W.; Strushkevich, n. (2014). Structural characterization of human cholesterol 7 -hydroxylase. the Journal of Lipid research 55(9), 1925-1932. 10.1194/jlr.m050765.

CMCF-id

Boyko, t. d.; green, r. J.; Moewes, a.; regier, t. Z. (2014). Measuring partial fluorescence yield using filtered detectors. Journal of Synchrotron radiation 21(4), 716-721. 10.1107/s160057751401073x.

SgM

Johnson, ted W.; richardson, Paul F.; Bailey, Simon; Brooun, alexei; Burke, Benjamin J.; Collins, Michael r.; Cui, J. Jean; deal, Judith g.; deng, Ya-Li; dinh, dac; engstrom, Lars d.; he, Mingying; hoffman, Jacqui; hoffman, robert L.; huang, Qinhua; Kania, robert S.; Kath, John C.; Lam, hieu; Lam, Justine L.; Le, Phuong t.; Lingardo, Laura; Liu, Wei; Mctigue, Michele; Palmer, Cynthia L.; Sach, neal W.; Smeal, tod; Smith, graham L.; Stewart, albert e.; timofeevski, Sergei; Zhu, huichun; Zhu, Jinjiang; Zou, helen Y.; edwards, Martin P. (2014). Discovery of (10 R)-7-Amino-12-fluoro-2, 10,16-trimethyl-15-oxo-10, 15,16,17-tetrahydro- 2H -8,4-(metheno) pyrazolo [4,3- h][2,5,11]-benzoxadiazacyclotetradecine-3-carbonitrile (PF-06463922), a Macrocyclic Inhibitor of Anaplastic Lymphoma Kinase (ALK) and c-ros Oncogene 1

(ROS1) with Preclinical Brain Exposure and Broad-Spectrum Potency against ALK-Resistant Mutations. Journal of Medicinal Chemistry 57(11), 4720-4744. 10.1021/jm500261q.

CMCF-id

Johnson, neil W.; vogt, Patrick; resta, andrea; de Padova, Paola; Perez, israel; Muir, david; Kurmaev, ernst Z.; Le Lay, guy; Moewes, alexander (2014). The Metallic Nature of Epitaxial Silicene Monolayers on Ag(111). advanced Functional Materials 24(33), 5253-5259. 10.1002/adfm.201400769.

reiXS

Lin, Jinru; Chen, ning; Pan, Yuanming (2014). arsenic Speciation in newberyite (MghPo 4 ·3h 2 o) determined by Synchrotron X-ray Absorption and Electron Paramagnetic Resonance Spectroscopies: Implications for the Fate of Arsenic in Green Fertilizers. environmental Science & technology, 140606080250001. 10.1021/es405735p.

hXMa

hunt, adrian; Kurmaev, ernst Z.; Moewes, alex (2014). A Re-evaluation of How Functional Groups Modify the Electronic Structure of Graphene Oxide. advanced Materials 26(28), 4870-4874. 10.1002/adma.201401300.

SgM, reiXS

Lan, Yaqi; Corradini, Maria g.; Liu, Xia; May, tim e.; Borondics, Ferenc; Weiss, richard g.; rogers, Michael a. (2014). Comparing and Correlating Solubility Parameters Governing the Self-Assembly of Molecular Gels Using 1,3:2,4-Dibenzylidene Sorbitol as the Gelator. Langmuir, 140605080104002. 10.1021/la5008389.

Mid-ir

Kirmani, ahmad r.; Carey, graham h.; abdelsamie, Maged; Yan, Buyi; Cha, dongkyu; rollny, Lisa r.; Cui, Xiaoyu; Sargent, edward h.; amassian, aram (2014). Effect of Solvent Environment on Colloidal-Quantum-Dot Solar-Cell Manufacturability and Performance. advanced Materials 26(27), 4717-4723. 10.1002/adma.201400577.

vLS-PgM

Chen, Chunmei; dynes, James J.; Wang, Jian; Karunakaran, Chithra; Sparks, donald L. (2014). Soft X-ray Spectromicroscopy Study of Mineral-Organic Matter Associations in Pasture Soil Clay Fractions. environmental Science & technology, 140604083949004. 10.1021/es405485a.

SM

Lekin, Kristina; Phan, hoa; Winter, Stephen M.; Wong, Joanne W. L.; Leitch, alicea a.; Laniel, dominique; Yong, Wenjun; Secco, richard a.; tse, John S.; desgreniers, Serge; dube, Paul a.; Shatruk, Michael; oakley, richard t. (2014). Heat, Pressure and Light-Induced Interconversion of Bisdithiazolyl Radicals and Dimers. Journal of the american Chemical Society 136(22), 8050-8062. 10.1021/ja502753t.

hXMa

grishin, andrey M.; Condos, tara e.C.; Barber, Kathryn r.; Campbell-valois, François-Xavier; Parsot, Claude; Shaw, gary S.; Cygler, Miroslaw (2014). Structural Basis for the Inhibition of Host Protein Ubiquitination by Shigella Effector Kinase OspG. Structure 22(6), 878-888. 10.1016/j.str.2014.04.010.

CMCF-id

azargohar, ramin; nanda, Sonil; Kozinski, Janusz a.; dalai, ajay K.; Sutarto, ronny (2014). Effects of temperature on the physicochemical characteristics of fast pyrolysis bio-chars derived from Canadian waste biomass. Fuel 125, 90-100. 10.1016/j.fuel.2014.01.083.

reiXS

Farvid, Shokouh S.; Sabergharesou, tahereh; hutfluss, Lisa n.; hegde, Manu; Prouzet, eric; radovanovic, Pavle v. (2014). Evidence of Charge-Transfer Ferromagnetism in Transparent Diluted Magnetic Oxide Nanocrystals: Switching the Mechanism of Magnetic Interactions. Journal of the american Chemical Society 136(21), 7669-7679. 10.1021/ja501888a.

SM

2 0 1 4 r e s e a r c h r e p o r t 55


Prince, L.; Korbas, M.; davidson, P.; Broberg, K.; rand, M. d. (2014). Target Organ Specific Activity of Drosophila MRP (ABCC1) Moderates Developmental Toxicity of Methylmercury. toxicological Sciences 140(2), 425-435. 10.1093/toxsci/kfu095.

aCCeSS-PnC/XSd

Pravica, Michael; Sneed, daniel; Wang, Yonggang; Smith, Quinlan; Subrahmanyam, garimella (2014). Carbon tetrachloride under extreme conditions. the Journal of Chemical Physics 140(19), 194503. 10.1063/1.4876220.

Mid-ir

Loewen, Peter C.; Carpena, Xavi; vidossich, Pietro; Fita, ignacio; rovira, Carme (2014). An Ionizable Active-Site Tryptophan Imparts Catalase Activity to a Peroxidase Core. Journal of the american Chemical Society 136(20), 7249-7252. 10.1021/ja502794e.

CMCF-id

tonkin, M. L.; Beck, J. r.; Bradley, P. J.; Boulanger, M. J. (2014). The Inner Membrane Complex Sub-compartment Proteins Critical for Replication of the Apicomplexan Parasite Toxoplasma gondii Adopt a Pleckstrin Homology Fold. Journal of Biological Chemistry 289(20), 13962-13973. 10.1074/jbc.m114.548891.

CMCF-id

Schmid, g.; Zeitvogel, F.; hao, L.; ingino, P.; Floetenmeyer, M.; Stierhof, Y.-d.; Schroeppel, B.; Burkhardt, C. J.; Kappler, a.; obst, M. (2014). 3-D analysis of bacterial cell-(iron)mineral aggregates formed during Fe(II) oxidation by the nitrate-reducing Acidovorax sp. strain BoFeN1 using complementary microscopy tomography approaches. geobiology 12(4), 340-361. 10.1111/gbi.12088.

SM

Laniel, dominique; Sebastiao, elena; Cook, Cyril; Murugesu, Muralee; hu, anguang; Zhang, Fan; desgreniers, Serge (2014). Dense nitrogen-rich energetic materials: A study of 5,5'-bis(1H-tetrazolyl)amine. the Journal of Chemical Physics 140(18), 184701. 10.1063/1.4870830.

hXMa

Singh, Sudhir P.; vogel-Mikuš, Katarina; vavpetič, Primož; Jeromel, Luka; Pelicon, Primož; Kumar, Jitendra; tuli, rakesh (2014). Spatial X-ray fluorescence micro-imaging of minerals in grain tissues of wheat and related genotypes. Planta 240(2), 277-289. 10.1007/s00425-014-2084-4.

veSPerS

King, d. t.; Lameignere, e.; Strynadka, n. C. J. (2014). Structural Insights into the Lipoprotein Outer Membrane Regulator of Penicillin-binding Protein 1B. Journal of Biological Chemistry 289(27), 19245-19253. 10.1074/jbc.m114.565879.

CMCF-BM

oh, angela; ho, Yen-Ching; Zak, Mark; Liu, Yongbo; Chen, Xukun; Yuen, Po-wai; Zheng, Xiaozhang; Liu, Yichin; dragovich, Peter S.; Wang, Weiru (2014). Structural and Biochemical Analyses of the Catalysis and Potency Impact of Inhibitor Phosphoribosylation by Human Nicotinamide Phosphoribosyltransferase. ChemBioChem 15(8), 1121-1130. 10.1002/cbic.201402023.

CMCF-id

Zhao, Fuyan; Kasrai, Masoud; Sham, tsun-Kong; Bai, Zhimin; Zhao, dong (2014). Characterization of tribofilms derived from zinc dialkyl dithiophosphate and serpentine by X-ray absorption spectroscopy. tribology international 73, 167-176. 10.1016/j.triboint.2014.01.015.

SgM, SXrMB, vLS-PgM

Li, dien; Seaman, John C.; Chang, hyun-Shik; Jaffe, Peter r.; Koster van groos, Paul; Jiang, de-tong; Chen, ning; Lin, Jinru; arthur, Zachary; Pan, Yuanming; Scheckel, Kirk g.; newville, Matthew; Lanzirotti, antonio; Kaplan, daniel i. (2014). Retention and chemical speciation of uranium in an oxidized wetland sediment from the Savannah River Site. Journal of environmental radioactivity 131, 40-46. 10.1016/j.jenvrad.2013.10.017.

hXMa

Liu, Lijuan; Fei, Jinxia; Cui, Mingqi; hu, Yongfeng; Wang, Jie (2014). XANES spectroscopic study of sulfur transformations during co-pyrolysis of a calcium-rich lignite and a high-sulfur bituminous coal. Fuel Processing technology 121, 56-62. 10.1016/j.fuproc.2013.12.008.

SXrMB

Li, X.J.; Li, Y.S.; Pan, t.J.; Yang, L.Z.; he, L.L.; Yang, Q.; hirose, a. (2014). Adhesion enhancement of diamond coating on minor Al-modified copper substrate. diamond and related Materials 45, 1-6. 10.1016/j.diamond.2014.03.001.

SXrMB, veSPerS

nyrow, a.; Sternemann, C.; Wilke, M.; gordon, r. a.; Mende, K.; Yavaş, h.; Simonelli, L.; hiraoka, n.; Sahle, Ch. J.; huotari, S.; andreozzi, g. B.; Woodland, a. B.; tolan, M.; tse, J. S. (2014). Iron speciation in minerals and glasses probed by M2/3-edge X-ray Raman scattering spectroscopy. Contributions to Mineralogy and Petrology 167(5). 10.1007/s00410-014-1012-8.

aCCeSS-PnC/XSd

Bassey, Bassey; Moreno, Beatriz; gomez, ariel; ahmed, asm Sabbir; ullrich, doug; Chapman, dean (2014). Synchrotron radiation shielding design for the Brockhouse sector at the Canadian light source. radiation Physics and Chemistry 98, 109-112. 10.1016/j.radphyschem.2014.01.011.

Shen, Shaohua; Chen, Jie; Koodali, ranjit t.; hu, Yongfeng; Xiao, Qunfeng; Zhou, Jigang; Wang, Xixi; guo, Liejin (2014). Activation of MCM-41 mesoporous silica by transition-metal incorporation for photocatalytic hydrogen production. applied Catalysis B environmental 150-151, 138-146. 10.1016/j.apcatb.2013.12.014.

SXrMB

Blattner, Claudia; Lee, Jeong hyun; Sliepen, Kwinten; derking, ronald; Falkowska, emilia; de la Peña, alba torrents; Cupo, albert; Julien, Jean-Philippe; van gils, Marit; Lee, Peter S.; Peng, Wenjie; Paulson, James C.; Poignard, Pascal; Burton, dennis r.; Moore, John P.; Sanders, rogier W.; Wilson, ian a.; Ward, andrew B. (2014). Structural Delineation of a Quaternary, Cleavage-Dependent Epitope at the gp41-gp120 Interface on Intact HIV-1 Env Trimers. immunity 40(5), 669-680. 10.1016/j.immuni.2014.04.008.

CMCF-id

elliott, J.Michael; ultsch, Mark; Lee, Joshua; tong, raymond; takeda, Kentaro; Spiess, Christoph; eigenbrot, Charles; Scheer, Justin M. (2014). Antiparallel Conformation of Knob and Hole Aglycosylated Half-Antibody Homodimers Is Mediated by a CH2–CH3 Hydrophobic Interaction. Journal of Molecular Biology 426(9), 1947-1957. 10.1016/j.jmb.2014.02.015.

CMCF-id

Saikia, Binoy K.; Khound, Kakoli; Baruah, Bimala P. (2014). Extractive de-sulfurization and de-ashing of high sulfur coals by oxidation with ionic liquids. energy Conversion and Management 81, 298-305. 10.1016/j.enconman.2014.02.043.

SXrMB

Persch, elke; Bryson, Steve; todoroff, nickolay K.; eberle, Christian; thelemann, Jonas; dirdjaja, natalie; Kaiser, Marcel; Weber, Maria; derbani, hassan; Brun, reto; Schneider, gisbert; Pai, emil F.; Krauth-Siegel, r. Luise; diederich, François (2014). Binding to Large Enzyme Pockets: Small-Molecule Inhibitors of Trypanothione Reductase. ChemMedChem, n/a-n/a. 10.1002/cmdc.201402032.

CMCF-BM

Zhu, Y; Samadi, n; Martinson, M; Bassey, B; Wei, Z; Belev, g; Chapman, d (2014). Spectral K -edge subtraction imaging. Physics in Medicine and Biology 59(10), 2485-2503. 10.1088/0031-9155/59/10/2485.

BMit-BM

aluri, esther rani; hayes, John r.; Walker, James d. S.; grosvenor, andrew P. (2014). Investigation of the Structural Stability of Ion-Implanted Gd 2 Ti 2– x Sn x O 7 Pyrochlore-Type Oxides by Glancing Angle X-ray Absorption Spectroscopy. the Journal of Physical Chemistry C 118(15), 7910-7922. 10.1021/jp4095497.

SXrMB, aCCeSS-PnC/XSd

okada, go; ueda, Jumpei; tanabe, Setsuhisa; Belev, george; Wysokinski, tomasz; Chapman, dean; tonchev, dancho; Kasap, Safa (2014). Samarium-Doped Oxyfluoride Glass-Ceramic as a New Fast Erasable Dosimetric Detector Material for Microbeam Radiation Cancer Therapy Applications at the Canadian Synchrotron. Journal of the american Ceramic Society 97(7), 2147-2153. 10.1111/jace.12938.

BMit-BM

hayes, John r.; grosvenor, andrew P.; rowson, John; hughes, Kebbi; Frey, ryan a.; reid, Joel (2014). Analysis of the Mo Speciation in the JEB Tailings Management Facility at McClean Lake, Saskatchewan. environmental Science & technology 48(8), 4460-4467. 10.1021/es404980x.

hXMa, veSPerS

gruninger, robert J.; thibault, John; Capeness, Michael J.; till, robert; Mosimann, Steven C.; Sockett, r. elizabeth; Selinger, Brent L.; Lovering, andrew L. (2014). Structural and Biochemical Analysis of a Unique Phosphatase from Bdellovibrio bacteriovorus Reveals Its Structural and Functional Relationship with the Protein Tyrosine Phosphatase Class of Phytase. PLoS one 9(4), e94403. 10.1371/journal.pone.0094403.

CMCF-id

Wyrzucki, a.; dreyfus, C.; Kohler, i.; Steck, M.; Wilson, i. a.; hangartner, L. (2014). Alternative Recognition of the Conserved Stem Epitope in Influenza A Virus Hemagglutinin by a VH3-30-Encoded Heterosubtypic Antibody. Journal of virology 88(12), 7083-7092. 10.1128/jvi.00178-14.

CMCF-id

Fodje, Michel; grochulski, Pawel; Janzen, Kathryn; Labiuk, Shaunivan; gorin, James; Berg, russ (2014). 08B1-1: an automated beamline for macromolecular crystallography experiments at the Canadian Light Source. Journal of Synchrotron radiation 21(3), 633-637. 10.1107/s1600577514005578.

CMCF-BM

tafti, F. F.; Clancy, J. P.; Lapointe-Major, M.; Collignon, C.; Faucher, S.; Sears, J. a.; Juneau-Fecteau, a.; doiron-Leyraud, n.; Wang, a. F.; Luo, X.-g.; Chen, X. h.; desgreniers, S.; Kim, Young-June; taillefer, Louis (2014). Sudden reversal in the pressure dependence of Tc in the iron-based superconductor CsFe2As2: A possible link between inelastic scattering and pairing symmetry. Physical review B 89(13). 10.1103/physrevb.89.134502.

hXMa

higgins, Melanie a.; Suits, Michael d.; Marsters, Candace; Boraston, alisdair B. (2014). Structural and Functional Analysis of Fucose-Processing Enzymes from Streptococcus pneumoniae. Journal of Molecular Biology 426(7), 1469-1482. 10.1016/j.jmb.2013.12.006.

CMCF-BM

akhter, Mst. Fardausi; omelon, Christopher r.; gordon, robert a.; Moser, desmond; Macfie, Sheila M. (2014). Localization and chemical speciation of cadmium in the roots of barley and lettuce. environmental and experimental Botany 100, 10-19. 10.1016/j.envexpbot.2013.12.005.

aCCeSS-PnC/XSd

Fox-rabinovich, g.; Kovalev, a.; aguirre, M.h.; Yamamoto, K.; veldhuis, S.; gershman, i.; rashkovskiy, a.; endrino, J.L.; Beake, B.; dosbaeva, g.; Wainstein, d.; Yuan, Junifeng; Bunting, J.W. (2014). Evolution of self-organization in nano-structured PVD coatings under extreme tribological conditions. applied Surface Science 297, 22-32. 10.1016/j.apsusc.2014.01.052.

SgM

das, S.; essilfie-dughan, J.; hendry, M. J. (2014). Arsenate partitioning from ferrihydrite to hematite: Spectroscopic evidence. american Mineralogist 99(4), 749-754. 10.2138/am.2014.4657.

hXMa

rezaei, ebrahim; Soltan, Jafar (2014). EXAFS and kinetic study of MnOx/γ-alumina in gas phase catalytic oxidation of toluene by ozone. applied Catalysis B environmental 148-149, 70-79. 10.1016/j.apcatb.2013.10.041.

hXMa

Sun, Cheng-Jun; Zhang, Bangmin; Brewe, dale L.; Chen, Jing-Sheng; Chow, g. M.; venkatesan, t.; heald, Steve M. (2014). Note: Application of a pixel-array area detector to simultaneous single crystal X-ray diffraction and X-ray absorption spectroscopy measurements. review of Scientific instruments 85(4), 046109. 10.1063/1.4871055.

aCCeSS-PnC/XSd


Woll, arthur r; agyeman-Budu, david; Choudhury, Sanjukta; Coulthard, ian; Finnefrock, adam C; gordon, robert; hallin, emil; Mass, Jennifer (2014). Lithographically-fabricated channel arrays for confocal X-ray fluorescence microscopy and XAFS. Journal of Physics: Conference Series 493, 012028. 10.1088/1742-6596/493/1/012028.

aCCeSS-PnC/XSd

haji-ghassemi, o.; Muller-Loennies, S.; Saldova, r.; Muniyappa, M.; Brade, L.; rudd, P. M.; harvey, d. J.; Kosma, P.; Brade, h.; evans, S. v. (2014). Groove-type Recognition of Chlamydiaceae-specific Lipopolysaccharide Antigen by a Family of Antibodies Possessing an Unusual Variable Heavy Chain N-Linked Glycan. Journal of Biological Chemistry 289(24), 16644-16661. 10.1074/jbc.m113.528224.

CMCF-id

Wang, Ziwei; Yao, Yansun; Zhu, Li; Liu, hanyu; iitaka, toshiaki; Wang, hui; Ma, Yanming (2014). Metallization and superconductivity of BeH2 under high pressure. the Journal of Chemical Physics 140(12), 124707. 10.1063/1.4869145.

thi, nhung nguyen; offen, Wendy a.; Shareck, François; davies, gideon J.; doucet, nicolas (2014). Structure and Activity of the Streptomyces coelicolor A3(2) β- N -Acetylhexosaminidase Provides Further Insight into GH20 Family Catalysis and Inhibition. Biochemistry 53(11), 1789-1800. 10.1021/bi401697j.

CMCF-id

Yuan, Mingjian; Kemp, Kyle W.; thon, Susanna M.; Kim, Jin Young; Chou, Kang Wei; amassian, aram; Sargent, edward h. (2014). High-Performance Quantum-Dot Solids via Elemental Sulfur Synthesis. advanced Materials 26(21), 3513-3519. 10.1002/adma.201305912.

hXMa

Siddique, tariq; Kuznetsov, Petr; Kuznetsova, alsu; Li, Carmen; Young, rozlyn; arocena, Joselito M.; Foght, Julia M. (2014). Microbially-accelerated consolidation of oil sands tailings. Pathway II: solid phase biogeochemistry. Frontiers in Microbiology 5. 10.3389/fmicb.2014.00107.

veSPerS

vidossich, Pietro; Loewen, Peter C.; Carpena, Xavi; Fiorin, giacomo; Fita, ignacio; rovira, Carme (2014). Binding of the Antitubercular Pro-Drug Isoniazid in the Heme Access Channel of Catalase-Peroxidase (KatG). A Combined Structural and Metadynamics Investigation. the Journal of Physical Chemistry B 118(11), 2924-2931. 10.1021/jp4123425.

CMCF-id

arrua, r. dario; hitchcock, adam P.; hon, Wei Boon; West, Marcia; hilder, emily F. (2014). Characterization of Polymer Monoliths Containing Embedded Nanoparticles by Scanning Transmission X-ray Microscopy (STXM). analytical Chemistry 86(6), 2876-2881. 10.1021/ac403166u.

SM

green, r. J.; Zatsepin, d. a.; St. onge, d. J.; Kurmaev, e. Z.; gavrilov, n. v.; Zatsepin, a. F.; Moewes, a. (2014). Electronic band gap reduction and intense luminescence in Co and Mn ion-implanted SiO2. Journal of applied Physics 115(10), 103708. 10.1063/1.4868297.

SgM

Maynard, andrew; Crosby, renae M.; ellis, Byron; hamatake, robert; hong, Zhi; Johns, Brian a.; Kahler, Kirsten M.; Koble, Cecilia; Leivers, anna; Leivers, Martin r.; Mathis, amanda; Peat, andrew J.; Pouliot, Jeffrey J.; roberts, Christopher d.; Samano, vicente; Schmidt, rachel M.; Smith, gary K.; Spaltenstein, andrew; Stewart, eugene L.; thommes, Pia; turner, elizabeth M.; voitenleitner, Christian; Walker, Jill t.; Waitt, greg; Weatherhead, Jason; Weaver, Kurt; Williams, Shawn; Wright, Lois; Xiong, Zhiping Z.; haigh, david; Shotwell, J. Brad (2014). Discovery of a Potent Boronic Acid Derived Inhibitor of the HCV RNA-Dependent RNA Polymerase. Journal of Medicinal Chemistry 57(5), 1902-1913. 10.1021/jm400317w.

CMCF-id

McLeod, J. a.; Boukhvalov, d. W.; Zatsepin, d. a.; green, r. J.; Leedahl, B.; Cui, L.; Kurmaev, e. Z.; Zhidkov, i. S.; Finkelstein, L. d.; gavrilov, n. v.; Cholakh, S. o.; Moewes,

a. (2014). Local Structure of Fe Impurity Atoms in ZnO: Bulk versus Surface. the Journal of Physical Chemistry C 118(10), 5336-5345. 10.1021/jp411219z.

SgM

Martinson, Mercedes; Samadi, nazanin; Belev, george; Bassey, Bassey; Lewis, rob; aulakh, gurpreet; Chapman, dean (2014). Development of a bent Laue beam-expanding double-crystal monochromator for biomedical X-ray imaging. Journal of Synchrotron radiation 21(3), 479-483. 10.1107/s1600577514003014.

BMit-BM

Wang, Jiajun; Yang, Jinli; tang, Yongji; Liu, Jian; Zhang, Yong; Liang, guoxian; gauthier, Michel; Karen Chen-Wiegart, Yu-chen; norouzi Banis, Mohammad; Li, Xifei; Li, ruying; Wang, Jun; Sham, t. K.; Sun, Xueliang (2014). Size-dependent surface phase change of lithium iron phosphate during carbon coating. nature Communications 5. 10.1038/ncomms4415.

vLS-PgM

Wadati, h; geck, J; Schierle, e; Sutarto, r; he, F; hawthorn, d g; nakamura, M; Kawasaki, M; tokura, Y; Sawatzky, g a (2014). Revealing orbital and magnetic phase transitions in Pr 0.5 Ca 0.5 MnO 3 epitaxial thin films by resonant soft X-ray scattering. new Journal of Physics 16(3), 033006. 10.1088/1367-2630/16/3/033006.

reiXS

abad, Manuel d.; veldhuis, Stephen C.; endrino, Jose L.; Beake, Ben d.; garcía-Luis, alberto; Brizuela, Marta; Sánchez-López, Juan C. (2014). Mechanical and phase stability of TiBC coatings up to 1000 °C. Journal of vacuum Science & technology a vacuum Surfaces and Films 32(2), 021508. 10.1116/1.4861365.

vLS-PgM

Yannikos, nils; Leinweber, Peter; helgason, Bobbi L.; Baum, Christel; Walley, Fran L.; van rees, Ken C.J. (2014). Impact of Populus trees on the composition of organic matter and the soil microbial community in Orthic Gray Luvisols in Saskatchewan (Canada). Soil Biology and Biochemistry 70, 5-11. 10.1016/j.soilbio.2013.11.025.

SgM

normandeau, J.; van Kessel, C.; nicholson, d.; rahusaar routledge, B.; Fawcett, a.; Lim-Cole, L.; Condy, C.; Sylvain, n.; Walker, t.; Borondics, F. (2014). Spider silk protein structure analysis by FTIR and STXM spectromicroscopy techniques. Canadian Young Scientist Journal 2014(1), 35-42. 10.13034/cysj-2014-006.

Mid-ir, SM

Sahle, Ch J; Sternemann, C; Sternemann, h; tse, J S; gordon, r a; desgreniers, S; Maekawa, S; Yamanaka, S; Lehmkühler, F; Wieland, d C F; Mende, K; huotari, S; tolan, M (2014). The Ba 4d–4f giant dipole resonance in complex Ba/Si compounds. Journal of Physics B atomic Molecular and optical Physics 47(4), 045102. 10.1088/0953-4075/47/4/045102.

aCCeSS-PnC/XSd

Park, Jaeok; Lin, Yih-Shyan; tsantrizos, Youla S.; Berghuis, albert M. (2014). Structure of human farnesyl pyrophosphate synthase in complex with an aminopyridine bisphosphonate and two molecules of inorganic phosphate. acta Crystallographica Section F Structural Biology and Crystallization Communications 70(3), 299-304. 10.1107/s2053230x14002106.

CMCF-id

Schmid, gregor; Zeitvogel, Fabian; hao, Likai; ingino, Pablo; Kuerner, Wolfgang; dynes, James J.; Karunakaran, Chithra; Wang, Jian; Lu, Yingshen; ayers, travis; Schietinger, Chuck; hitchcock, adam P.; obst, Martin (2014). Synchrotron-Based Chemical Nano-Tomography of Microbial Cell-Mineral Aggregates in their Natural, Hydrated State. Microscopy and Microanalysis 20(02), 531-536. 10.1017/s1431927613014104.

SM

Morrell, B.; okada, g.; vahedi, S.; Koughia, C.; edgar, a.; varoy, C.; Belev, g.; Wysokinski, t.; Chapman, d.; Sammynaiken, r.; Kasap, S. o. (2014). Optically erasable samarium-doped fluorophosphate glasses for high-dose measurements in microbeam radiation therapy. Journal of applied Physics 115(6), 063107. 10.1063/1.4864424.

BMit-BM

Badoga, Sandeep; dalai, ajay K.; adjaye, John; hu, Yongfeng (2014). Combined Effects of EDTA and Heteroatoms (Ti, Zr, and Al) on Catalytic Activity of SBA-15 Supported NiMo Catalyst for Hydrotreating of Heavy Gas Oil. industrial & engineering Chemistry research 53(6), 2137-2156. 10.1021/ie400695m.

SXrMB

Leedahl, B.; Zatsepin, d. a.; Boukhvalov, d. W.; green, r. J.; McLeod, J. a.; Kim, S. S.; Kurmaev, e. Z.; Zhidkov, i. S.; gavrilov, n. v.; Cholakh, S. o.; Moewes, a. (2014). Structural defects induced by Fe-ion implantation in TiO2. Journal of applied Physics 115(5), 053711. 10.1063/1.4864748.

SgM

Keeling, thomas J.; Samborska, Bożena; demers, ryan W.; Kimber, Matthew S. (2014). Interactions and structural variability of β-carboxysomal shell protein CcmL. Photosynthesis research 121(2-3), 125-133. 10.1007/s11120-014-9973-z.

CMCF-id

izadifar, Zohreh; Chapman, Leroy dean; Chen, Xiongbiao (2014). Computed Tomography Diffraction-Enhanced Imaging for In Situ Visualization of Tissue Scaffolds Implanted in Cartilage. tissue engineering Part C Methods 20(2), 140-148. 10.1089/ten.tec.2013.0138.

BMit-BM

grishin, andrey M.; Cherney, Maia; anderson, deborah h.; Phanse, Sadhna; Babu, Mohan; Cygler, Miroslaw (2014). NleH Defines a New Family of Bacterial Effector Kinases. Structure 22(2), 250-259. 10.1016/j.str.2013.11.006.

CMCF-id

ding, Yang; Chen, Cheng-Chien; Zeng, Qiaoshi; Kim, heung-Sik; han, Myung Joon; Balasubramanian, Mahalingam; gordon, robert; Li, Fangfei; Bai, Ligang; Popov, dimitry; heald, Steve M.; gog, thomas; Mao, ho-kwang; van veenendaal, Michel (2014). Novel High-Pressure Monoclinic Metallic Phase of V2O3. Physical review Letters 112(5). 10.1103/physrevlett.112.056401.

aCCeSS-PnC/XSd

Li, rong; Lin, Jinru; nilges, Mark J.; Chen, ning; Pan, Yuanming (2014). Arsenic speciation in danburite (CaB2Si2O8): a synchrotron XAS and single-crystal EPR study. european Journal of Mineralogy 26(1), 113-125. 10.1127/0935-1221/2014/0026-2358.

hXMa

Clancy, J. P.; Lupascu, a.; gretarsson, h.; islam, Z.; hu, Y. F.; Casa, d.; nelson, C. S.; LaMarra, S. C.; Cao, g.; Kim, Young-June (2014). Dilute magnetism and spin-orbital percolation effects in Sr2Ir1−xRhxO4. Physical review B 89(5). 10.1103/physrevb.89.054409.

SXrMB

Karimi, elham; teixeira, ivo Freitas; gomez, ariel; de resende, eliane; gissane, Christopher; Leitch, Jay; Jollet, véronique; aigner, isabella; Berruti, Franco; Briens, Cedric; Fransham, Peter; hoff, Brent; Schrier, nick; Lago, rochel M.; Kycia, Stefan W.; heck, richard; Schlaf, Marcel (2014). Synergistic co-processing of an acidic hardwood derived pyrolysis bio-oil with alkaline Red Mud bauxite mining waste as a sacrificial upgrading catalyst. applied Catalysis B environmental 145, 187-196. 10.1016/j.apcatb.2013.02.007.

rudyk, Brent W.; Stoyko, Stanislav S.; oliynyk, anton o.; Mar, arthur (2014). Rare-earth transition-metal gallium chalcogenides RE3MGaCh7 (M=Fe, Co, Ni; Ch=S, Se). Journal of Solid State Chemistry 210(1), 79-88. 10.1016/j.jssc.2013.11.003.

SgM

Yao, deqiang; Cherney, Maia; Cygler, Miroslaw (2014). Structure of the N-terminal domain of the effector protein LegC3 from Legionella pneumophila. acta Crystallographica Section d Biological Crystallography 70(2), 436-441. 10.1107/s139900471302991x.

CMCF-id

Yu, Yong; Luo, Zhentao; Chevrier, daniel M.; Leong, david tai; Zhang, Peng; Jiang, de-en; Xie, Jianping (2014). Identification of a Highly Luminescent Au 22 (SG) 18 Nanocluster. Journal of the american Chemical Society 136(4), 1246-1249. 10.1021/ja411643u.

aCCeSS-PnC/XSd

2 0 1 4 r e s e a r c h r e p o r t 57


Wang, hui; LeBlanc, K. a.; gao, Bo; Yao, Yansun (2014). Thermodynamic ground state of MgB6 predicted from first principles structure search methods. the Journal of Chemical Physics 140(4), 044710. 10.1063/1.4862831.

Liu, Yijin; Wang, Junyue; azuma, Masaki; Mao, Wendy L.; Yang, Wenge (2014). Five-dimensional visualization of phase transition in BiNiO3 under high pressure. applied Physics Letters 104(4), 043108. 10.1063/1.4863229.

aCCeSS-PnC/XSd

Lewis, Steven M; Wu, Xiufeng; Pustilnik, anna; Sereno, arlene; huang, Flora; rick, heather L; guntas, gurkan; Leaver-Fay, andrew; Smith, eric M; ho, Carolyn; hansen-estruch, Christophe; Chamberlain, aaron K; truhlar, Stephanie M; Conner, elaine M; atwell, Shane; Kuhlman, Brian; demarest, Stephen J (2014). Generation of bispecific IgG antibodies by structure-based design of an orthogonal Fab interface. nature Biotechnology 32(2), 191-198. 10.1038/nbt.2797.

CMCF-id

Boyko, teak d.; gross, toni; Schwarz, Marcus; Fuess, hartmut; Moewes, alexander (2014). The local crystal structure and electronic band gap of β-sialons. Journal of Materials Science 49(8), 3242-3252. 10.1007/s10853-014-8030-9.

SgM, vLS-PgM

Wong, Joanne W. L.; Mailman, aaron; Lekin, Kristina; Winter, Stephen M.; Yong, Wenjun; Zhao, Jianbao; garimella, Subrahmanyam v.; tse, John S.; Secco, richard a.; desgreniers, Serge; ohishi, Yasuo; Borondics, Ferenc; oakley, richard t. (2014). Pressure Induced Phase Transitions and Metallization of a Neutral Radical Conductor. Journal of the american Chemical Society 136(3), 1070-1081. 10.1021/ja411057x.

Mid-ir

Kiefer, Susan e.; Chang, ChiehYing J.; Kimura, S. roy; gao, Mian; Xie, dianlin; Zhang, Yaqun; Zhang, guifen; gill, Martin B.; Mastalerz, harold; thompson, Lorin a.; Cacace, angela M.; Sheriff, Steven (2014). The structure of human tau-tubulin kinase 1 both in the apo form and in complex with an inhibitor. acta Crystallographica Section F Structural Biology and Crystallization Communications 70(2), 173-181. 10.1107/s2053230x14000144.

CMCF-id

Wang, Junlei; Santana, Juan a Colón; Wu, ning; Karunakaran, Chithra; Wang, Jian; dowben, Peter a; Binek, Christian (2014). Magnetoelectric Fe 2 TeO 6 thin films. Journal of Physics Condensed Matter 26(5), 055012. 10.1088/0953-8984/26/5/055012.

SM

Feng, Shanglei; Li, Li; Yang, Xinmei; Zhou, Xingtai; Bai, Shuo; Sham, tsun Kong (2014). Effect of Defects Induced by 12 C + Ion Irradiation on the Fluorination of Pyrolytic Carbon Coating in Flinak Salt. advanced engineering Materials 16(7), 897-904. 10.1002/adem.201300479.

SgM

van veggel, Frank C. J. M. (2014). Near-Infrared Quantum Dots and Their Delicate Synthesis, Challenging Characterization, and Exciting Potential Applications. Chemistry of Materials 26(1), 111-122. 10.1021/cm4021436.

SgM

Wang, hui; Yao, Yansun; Si, Yanling; Wu, Zhijian; vaitheeswaran, g. (2014). Hidden Thermodynamic Ground State of Calcium Diazenide. the Journal of Physical Chemistry C 118(1), 650-656. 10.1021/jp410281q.

van der Bij, hendrik e.; aramburo, Luis r.; arstad, Bjørnar; dynes, James J.; Wang, Jian; Weckhuysen, Bert M. (2014). Phosphatation of Zeolite H-ZSM-5: A Combined Microscopy and Spectroscopy Study. ChemPhysChem 15(2), 283-292. 10.1002/cphc.201300910.

SM

Yadegari, hossein; Li, Yongliang; Banis, Mohammad norouzi; Li, Xifei; Wang, Biqiong; Sun, Qian; Li, ruying; Sham, tsun-Kong; Cui, Xiaoyu; Sun, Xueliang (2014). on rechargeability and reaction kinetics of sodium–air batteries. energy & environmental Science 7(11), 3747-3757. 10.1039/c4ee01654h.

vLS-PgM

gomez, Mario a.; hendry, M. Jim; elouatik, Samir; essilfie-dughan, Joseph; Paikaray, Susanta (2014). Fe(ii) (aq) uptake of Mg(ii)–Al(iii)/Fe(iii)–SO 4 /CO 3 HTLCs under alkaline conditions: adsorption and solid-state transformation mechanisms. rSC advances 4(98), 54973-54988. 10.1039/c4ra08802f.

SgM

Chen, Yi; guo, Xiaoxuan; tse, Wai hei; Sham, tsun-Kong; Zhang, Jin (2014). Magnetic anisotropy induced in NiCo granular nanostructures by ZnO nanorods deposited on a polymer substrate. rSC advances 4(89), 47987-47991. 10.1039/c4ra07210c.

SXrMB

Wang, Zhijiang; Wu, Lina; Zhou, Jigang; Jiang, Zhaohua; Shen, Baozhong (2014). Chemoselectivity-induced multiple interfaces in MWCNT/Fe 3 O 4 @ZnO heterotrimers for whole X-band microwave absorption. nanoscale. 10.1039/c4nr03040k.

Moriarty, Maeve M.; Lai, vivian W.-M.; Koch, iris; Cui, Longpeng; Combs, Chris; Krupp, eva M.; Feldmann, Jörg; Cullen, William r.; reimer, Kenneth J. (2014). Speciation and toxicity of arsenic in mining-affected lake sediments in the Quinsam watershed, British Columbia. the Science of the total environment 466-467, 90-99. 10.1016/j.scitotenv.2013.07.005.

aCCeSS-PnC/XSd

Piao, Ying; Qin, Yan; ren, Yang; heald, Steve M.; Sun, Chengjun; Zhou, dehua; Polzin, Bryant J.; trask, Steve e.; amine, Khalil; Wei, Yinjin; Chen, gang; Bloom, ira; Chen, Zonghai (2014). A XANES study of LiVPO4F: a factor analysis approach. Physical Chemistry Chemical Physics 16(7), 3254. 10.1039/c3cp54588a.

aCCeSS-PnC/XSd

Liu, Jin; Yang, Jianjun; Liang, Xinqiang; Zhao, Yue; Cade-Menun, Barbara J.; hu, Yongfeng (2014). Molecular Speciation of Phosphorus Present in Readily Dispersible Colloids from Agricultural Soils. Soil Science Society of america Journal 78(1), 47. 10.2136/sssaj2013.05.0159.

SXrMB

Xu, Ben; Poduska, Kristin M. (2014). Linking crystal structure with temperature-sensitive vibrational modes in calcium carbonate minerals. Physical Chemistry Chemical Physics 16(33), 17634. 10.1039/c4cp01772b.

Mid-ir

Li, Chenge; Kumar, Saroj; Montigny, Cédric; le Maire, Marc; Barth, andreas (2014). Quality assessment of recombinant proteins by infrared spectroscopy. Characterisation of a protein aggregation related band of the Ca 2+ -ATPase. the analyst 139(17), 4231. 10.1039/c4an00483c.

Wang, Zhiqiang; Wang, Jian; Sham, tsun-Kong; Yang, Shaoguang (2014). Origin of luminescence from ZnO/CdS core/shell nanowire arrays. nanoscale 6(16), 9783. 10.1039/c4nr02231a.

SgM, SXrMB, SM, vLS-PgM

gillespie, a.W.; Sanei, h.; diochon, a.; ellert, B.h.; regier, t.Z.; Chevrier, d.; dynes, J.J.; tarnocai, C.; gregorich, e.g. (2014). Perennially and annually frozen soil carbon differ in their susceptibility to decomposition: Analysis of Subarctic earth hummocks by bioassay, XANES and pyrolysis. Soil Biology and Biochemistry 68, 106-116. 10.1016/j.soilbio.2013.09.021.

SgM

Patzig, Christian; höche, thomas; hu, Yongfeng; ikeno, hidekazu; Krause, Michael; dittmer, Marc; gawronski, antje; rüssel, Christian; tanaka, isao; henderson, grant S. (2014). Zr coordination change during crystallization of MgO–Al2O3–SiO2–ZrO2 glass ceramics. Journal of non-Crystalline Solids 384, 47-54. 10.1016/j.jnoncrysol.2013.04.014.

SXrMB

Wang, Wenhui; Zhang, Jiaolong; Jia, Zheng; dai, Changsong; hu, Yongfeng; Zhou, Jigang; Xiao, Qunfeng (2014). Enhancement of the cycling performance of Li3V2(PO4)3/C by stabilizing the crystal structure through Zn2+ doping. Physical Chemistry Chemical Physics 16(27) , 13858. 10.1039/c3cp55495c.

SXrMB

hunt, a.; dikin, d.a.; Kurmaev, e.Z.; Lee, Y.h.; Luan, n.v.; Chang, g.S.; Moewes, a. (2014). Modulation of the band gap of graphene oxide: The role of AA-stacking. Carbon 66, 539-546. 10.1016/j.carbon.2013.09.036.

SgM

hosseini, Mehdi; Klymyshyn, david M.; Wells, garth (2014). A Circuit Model for the Design of Self-Excited EBG Resonator Antennas With Miniaturized Unit Cells. ieee antennas and Wireless Propagation Letters 13, 1279-1283. 10.1109/lawp.2014.2333752.

SYLMand

Zhou, Chunyu; Wang, Jian; Szpunar, Jerzy a. (2014). X-ray chemical imaging and the electronic structure of a single nanoplatelet Ni/graphene composite. Chemical Communications 50(18), 2282. 10.1039/c3cc47008c.

SM

Baroi, Chinmoy; Mahto, Saloni; niu, Catherine; dalai, ajay K. (2014). Biofuel production from green seed canola oil using zeolites. applied Catalysis a general 469, 18-32. 10.1016/j.apcata.2013.09.034.

hXMa

Zhou, Jigang; duchesne, Paul n.; hu, Yongfeng; Wang, Jian; Zhang, Peng; Li, Yanguang; regier, tom; dai, hongjie (2014). Fe–N bonding in a carbon nanotube–graphene complex for oxygen reduction: an XAS study. Physical Chemistry Chemical Physics 16(30), 15787. 10.1039/c4cp01455c.

SXrMB

Zhao, ronghua; hallin, emil; ghosh, Subrata; Feng, renfei; Jones, Jennifer (2014). Intestinal Microparticles and Inflammatory Bowel Diseases. inflammatory Bowel diseases 20(4), 771-775. 10.1097/01.mib.0000441202.18078.d5.

veSPerS

Zhou, Jigang; hong, da; Wang, Jian; hu, Yongfeng; Xie, Xiaohua; Fang, haitao (2014). Electronic structure variation of the surface and bulk of a LiNi0.5Mn1.5O4 cathode as a function of state of charge: X-ray absorption spectroscopic study. Physical Chemistry Chemical Physics 16(27), 13838. 10.1039/c4cp01436g.

SgM

Yin, Ying; han, Jiecai; Zhang, Xinghong; Zhang, Yumin; Zhou, Jigang; Muir, david; Sutarto, ronny; Zhang, Zhihua; Liu, Shengwei; Song, Bo (2014). Facile synthesis of few-layer-thick carbon nitride nanosheets by liquid ammonia-assisted lithiation method and their photocatalytic redox properties. rSC advances 4(62), 32690. 10.1039/c4ra06036a.

reiXS

Farahi, nader; vanZant, Mathew; Zhao, Jianbao; tse, John S.; Prabhudev, Sagar; Botton, gianluigi a.; Salvador, James r.; Borondics, Ferenc; Liu, Zhenxian; Kleinke, holger (2014). Sb- and Bi-doped Mg 2 Si: location of the dopants, micro- and nanostructures, electronic structures and thermoelectric properties. dalton transactions 43(40), 14983-14991. 10.1039/c4dt01177e.

Mid-ir

Sun, Ke; Shen, Shaohua; Cheung, Justin S.; Pang, Xiaolu; Park, namseok; Zhou, Jigang; hu, Yongfeng; Sun, Zhelin; noh, Sun Young; riley, Conor t.; Yu, Paul K. L.; Jin, Sungho; Wang, deli (2014). Si photoanode protected by a metal modified ITO layer with ultrathin NiOx for solar water oxidation. Physical Chemistry Chemical Physics 16(10), 4612. 10.1039/c4cp00033a.

SgM

Wang, dongniu; Yang, Jinli; Liu, Jian; Li, Xifei; Li, ruying; Cai, Mei; Sham, tsun-Kong; Sun, Xueliang (2014). Atomic layer deposited coatings to significantly stabilize anodes for Li ion batteries: effects of coating thickness and the size of anode particles. Journal of Materials Chemistry 2(7), 2306. 10.1039/c3ta13677a.

SgM, vLS-PgM


Singh, Shashi B.; Wang, Yu-Fu; Shao, Yu-Cheng; Lai, hsuan-Yu; hsieh, Shang-hsien; Limaye, Mukta v.; Chuang, Chen-hao; hsueh, hung-Chung; Wang, hsaiotsu; Chiou, Jau-Wern; tsai, hung-Ming; Pao, Chih-Wen; Chen, Chia-hao; Lin, hong-Ji; Lee, Jyh-Fu; Wu, Chun-te; Wu, Jih-Jen; Pong, Way-Faung; ohigashi, takuji; Kosugi, nobuhiro; Wang, Jian; Zhou, Jigang; regier, tom; Sham, tsun-Kong (2014). Observation of the origin of d 0 magnetism in ZnO nanostructures using X-ray-based microscopic and spectroscopic techniques. nanoscale 6(15), 9166. 10.1039/c4nr01961j.

SM

Li, Xifei; Liu, Jian; Banis, Mohammad norouzi; Lushington, andrew; Li, ruying; Cai, Mei; Sun, Xueliang (2014). Atomic layer deposition of solid-state electrolyte coated cathode materials with superior high-voltage cycling behavior for lithium ion battery application. energy & environmental Science 7(2), 768. 10.1039/c3ee42704h.

hXMa

van der Bij, hendrik e.; Weckhuysen, Bert M. (2014). Local silico-aluminophosphate interfaces within phosphated H-ZSM-5 zeolites. Physical Chemistry Chemical Physics 16(21), 9892. 10.1039/c3cp54791d.

SM

heredia, e.; diaz, B.; Malachias, a.; rappl, P.h.o.; iikawa, F.; Brasil, M.J.S.P; Motisuke, P. (2014). Anomalous strain behavior on EuTe self-assembled islands. Journal of Crystal growth 386, 139-145. 10.1016/j.jcrysgro.2013.10.002.

Behyan, Shirin; hu, Yongfeng; urquhart, Stephen g. (2014). Chemical sensitivity of sulfur 1s NEXAFS spectroscopy I: Speciation of sulfoxides and sulfones. Chemical Physics Letters 592, 69-74. 10.1016/j.cplett.2013.10.026.

SXrMB

Zheng, Xiaozhang; Baumeister, timm; Buckmelter, alexandre J.; Caligiuri, Maureen; Clodfelter, Karl h.; han, Bingsong; ho, Yen-Ching; Kley, nikolai; Lin, Jian; reynolds, dominic J.; Sharma, geeta; Smith, Chase C.; Wang, Zhongguo; dragovich, Peter S.; oh, angela; Wang, Weiru; Zak, Mark; Wang, Yunli; Yuen, Po-wai; Bair, Kenneth W. (2014). Discovery of potent and efficacious cyanoguanidine-containing nicotinamide phosphoribosyltransferase (Nampt) inhibitors. Bioorganic & Medicinal Chemistry Letters 24(1), 337-343. 10.1016/j.bmcl.2013.11.006.

CMCF-id

Balestrieri, Matteo; Colis, Silviu; gallart, Mathieu; Ferblantier, gérald; Muller, dominique; gilliot, Pierre; Bazylewski, Paul; Chang, gap Soo; Slaoui, abdelillah; dinia, aziz (2014). Efficient energy transfer from ZnO to Nd 3+ ions in Nd-doped ZnO films deposited by magnetron reactive sputtering. Journal of Materials Chemistry. 10.1039/c4tc00980k.

reiXS

Li, Xia; Li, Xifei; Banis, Mohammad n.; Wang, Biqiong; Lushington, andrew; Cui, Xiaoyu; Li, ruying; Sham, tsun-Kong; Sun, Xueliang (2014). Tailoring interactions of carbon and sulfur in Li–S battery cathodes: significant effects of carbon–heteroatom bonds. Journal of Materials Chemistry 2(32), 12866. 10.1039/c4ta02007c.

vLS-PgM

Behyan, Shirin; hu, Yongfeng; urquhart, Stephen g. (2014). Chemical sensitivity of sulfur 1s NEXAFS spectroscopy II: Speciation of disulfide functional groups. Chemical Physics Letters 592, 109-113. 10.1016/j.cplett.2013.10.027.

SXrMB

MAGAzInE ARTICLE Cutler, Jeffrey (2014). Industrial Science at the Canadian Light Source: Access, Services, and Strategies. Synchrotron radiation news 27(3), 3-6. 10.1080/08940886.2014.908697.

MASTERS THESISKeeling, t.J. (2014). Characterization of the Interactions Mediated by the Key Structural Protein CcmL: Cornerpiece of the Beta-Carboxysome. Canada, on: university of guelph.

CMCF-id

rajendran, J. (2014). XANES and FTIR on dried and calcinied bones. uSa, tX: university of texas at arlington

SgM, SXrMB, vLS-PgM

Zuhaib, a. (2014). Methods to induce a preferred molecular alignment in the epitaxial growth of n-Alkane thin films. Canada, SK: university of Saskatchewan.

SM

goff, K.L. (2014). Toxicity, Morphological Changes and Dissipation of Oil Sands Naphthenic Acids in Chlamydomonas Reinhardtii. Canada, SK: university of Saskatchewan.

Mid-ir

dobosz, a.n. (2014). Characterization of Carlin-type Auriferous Arsaenian pyrite from the Goldstrike Property using EMP, SIMS and VESPERS Synchrotron u-XRF: Constraints to ore deposition mechanisms. Canada, on: Queens university.

veSPerS

guan, Y. (2014). Characterization of Alginate Scaffolds using X-ray imaging techniques. Canada, SK: university of Saskatchewan.

BMit-BM

ukpabi, g.n. (2014). Structural Basis for Heme Degradation in Staphylococcus Aureus. Canada, BC: university of British Columbia.

CMCF-id

Franz, e.d. (2014). Selenium Bioaccumulation and speciation in Chironomus Dilutus: An Assessment of exposure pathways and bioavailability. Canada, SK: university of Saskatchewan.

hXMa

rahman, K.M.M. (2014). In-Situ 3d Imaging Of Structure And Failure Of Materials Using Synchrotron Radiation Tomography. Canada, SK: university of Saskatchewan.

BMit-BM

erik B. durnburg (2014). Load Transfer In An Isolated Particle Embedded Within An Epoxy Matrix. Fl, usa: university of Central Florida.

veSPerS

Bluemel, B. (2014). Biogeochemical Expressions of buried REE Mineralization at the Norra Kärr Alkaline Complex, southern Sweden. Canada, BC: university of victoria.

hXMa

Wilson, S.C. (2014). Osseous skull development of Ambystoma macrodactylum krausei from post-hatching through metamorphosis. Canada, aB: university of Calgary.

BMit-BM

Krska, d. (2014). Larvin: The characterization of a novel mono-ADP-ribosyltransferase toxin. Canada, on: the university of guelph.

CMCF-id

PATEnTKikkert, M.; Mark, B.L.; van Kasteren, P.B.; James, t.W.; Snijder, e.J. (2014). Arterivirus. Patent number: uS20140154265a1.

CMCF-id

PDB DEPOSITIOnPark, J.; de Schutter, J.W.; tsantrizos, Y.S.; Berghuis, a.M. (2014). Crystal Structure Of Human Fpps In Complex With Nickel, Jds05120, And Sulfate. Protein data Bank: 4nfk, 4nfi.

CMCF-id

Cappadocia, L.; Mascle, X.h.; Bourdeau, v.; tremblay-Belzile, S.; Chaker-Margot, M.; Lussier-Price, M.; Wada, J.; Sakaguchi, K.; aubry, M.; Ferbeyre, g.; omichinski, J.g. (2014). Crystal Structure Of Sumo1 In Complex With Phosphorylated Pml. Protein data Bank: 4wjn.

CMCF-id

Chan, a.C.; Blair, K.M.; Liu, Y.; Frirdich, e.; gaynor, e.C.; tanner, M.e.; Salama, n.r.; Murphy, M.e. (2014). Crystal Structure Of Cell Shape Determinant Protein Csd4 Gln46His Variant From Helicobacter Pylori. Protein data Bank: 4wcm, 4wcl, 2wcn, 2wck.

CMCF-BM, CMFC-id

duan, J.J.; Lu, Z.; Jiang, B.; Yang, B.v.; doweyko, L.M.; nirschl, d.S.; haque, L.e.; Lin, S.; Brown, g.; hynes, J.; tokarski, J.S.; Sack, J.S.; Khan, J.; Lippy, J.S.; Zhang, r.F.; Pitt, S.; Shen, g.; Pitts, W.J.; Carter, P.h.; Barrish, J.C.; nadler, S.g.; Salter-Cid, L.M.; McKinnon, M.; Fura, a.; Schieven, g.L.; Wrobleski, S.t. (2014). Crystal Structure Of Jak3 Kinase Domain In Complex With A Pyrrolopyridazine Carboxamide Inhibitor. Protein data Bank: 4rio.

CMCF-id

Krska, d.; ravulapalli, r.; Fieldhouse, r.J.; Lugo, M.r.; Merrill, a.r. (2014). C3Larvin Toxin, An Adp-Ribosyltransferase From Paenibacillus Larvae. Protein data Bank: 4tr5.

CMCF-id

vadlamani, g.; thomas, M.d.; Patel, t.r.; donald, L.J.; reeve, t.M.; Stetefeld, J.; Standing, K.g.; vocadlo, d.J.; Mark, B.L. (2014). Ampr Effector Binding Domain From Citrobacter Freundii Bound To Udp-Murnac-Pentapeptide. Protein data Bank: 4wkm.

CMCF-id

dong, a.; dombrovski, L.; Walker, J.r.; getlik, M.; Kuznetsova, e.; Smil, d.; Barsyte, d.; Li, F.; Poda, g.; Senisterra, g.; Marcellus, r.; al-awar, r.; Bountra, C.; arrowsmith, C.h.; edwards, a.M.; Brown, P.J.; Schapira, M.; vedadi, M.; Wu, h.; Structural Genomics Consortium (SGC) (2014). Crystal Structure Of Human Wdr5 In Complex With Compound Oicr-9429. Protein data Bank: 4ql1.

CMCF-id

Bergeron, J.r.C.; Worrall, L.J.; de, S.; Sgourakis, n.g.; Cheung, a.h.; Lameignere, e.; okon, M.; Baker, d.; Mcintosh, L.P.; Strynadka, n.C.J. (2014). Crystal Structure Of The Prgk Periplasmic Domain 2. Protein data Bank: 4oyc.

CMCF-BM

Kwan, d.h.; Constantinescu, i.; Chapanian, r.; higgins, M.a.; Samain, e.; Boraston, a.B.; Kizhakkedathu, J.n.; Withers, S.g. (2014). Crystal Structure Of A Family 98 Glycoside Hydrolase Catalytic Module (Sp3Gh98) In Complex With The Blood Group A-Trisaccharide (L19 Mutant). Protein data Bank: 4d6g, 4d6d, 4d6e, 4d6c.

CMCF-BM, CMCF-id

doores, K.J.; Kong, L.; Krumm, S.a.; Le, K.M.; Sok, d.; Laserson, u.; garces, F.; Poignard, P.; Wilson, i.a.; Burton, d.r. (2014). Crystal Structure Of Broadly Neutralizing Anti-Hiv Antibody Pgt130. Protein data Bank: 4rnr.

CMCF-id

Lau, K.; van Petegem, F. (2014). Crystal Structure Of Mouse Ryanodine Receptor 2 Spry2 Domain (1080-1253). Protein data Bank: 4p9i.

CMCF-id

Bergeron, J.r.C.; Worrall, L.J.; de, S.; Sgourakis, n.; Cheung, a.h.; Lameigneire, e.; okon, M.; Wasney, g.a.; Baker, d.; Mcintosh, L.P.; Strynadka, n.C.J. (2014). Crystal Structure Of Prgk 19-92. Protein data Bank: 4w4m.

CMCF-id

Bailey-elkin, B.a.; Knaap, r.C.; Johnson, g.g.; dalebout, t.J.; ninaber, d.K.; van Kasteren, P.B.; Bredenbeek, P.J.; Snijder, e.J.; Kikkert, M.; Mark, B.L. (2014). Crystal Structure Of The Middle-East Respiratory Syndrome Coronavirus Papain-Like Protease. Protein data Bank: 4rez, 4rfl, 4rf0.

CMCF-BM

2 0 1 4 r e s e a r c h r e p o r t 59


Yachnin, B.J.; Mcevoy, M.B.; MacCuish, r.J.; Morley, K.L.; Lau, P.C.; Berghuis, a.M. (2014). Epsilon-Caprolactone-Bound Crystal Structure Of Cyclohexanone Monooxygenase In The Tight Conformation. Protein data Bank: 4rg3.

CMCF-id

grishin, a.M.; ajamian, e.; tao, L.; Bostina, M.; Zhang, L.; trempe, J.; Menard, r.; rouiller, i.; Cygler, M. (2014). The Phenylacetyl-Coa Monooxygenase - Mutant Paaa E49Q K68Q - Paac Wild Type Subcomplex With Benzoyl-Coa. Protein data Bank: 4ii4.

CMCF-id

Singh, a.K.; Pluvinage, B.; higgins, M.a.; dalia, a.B.; Woodiga, S.a.; Flynn, M.; Lloyd, a.r.; Weiser, J.n.; Stubbs, K.a.; Boraston, a.B.; King, S.J. (2014). Unravelling The Multiple Functions Of The Architecturally Intricate Streptococcus Pneumoniae Beta-Galactosidase, Bgaa. Protein data Bank: 4cu9.

CMCF-BM

Suits, M.d.L.; Pluvinage, B.; Law, a.; Liu, Y.; Palma, a.S.; Chai, W.; Feizi, t.; Boraston, a.B. (2014). Hyaluronan Binding Module Of The Streptococcal Pneumoniae Hyaluronate Lyase. Protein data Bank: 4d0q.

CMCF-BM

Loewen, P.C.; Carpena, X.; vidossich, P.; Fita, i.; rovira, C. (2014). Crystal Structure Of B. Pseudomallei Katg Treated With Hydrogen Peroxide. Protein data Bank: 4mvp.

CMCF-id

Chamberlain, P.P.; Wang, M.; riley, M.; delker, S.; Carmel, g.; Miller, K.; Lopez-girona, a.; Pagarigan, B.; Leon, B.; rychak, e.; Corral, L.; Lopez-girona, a.; ren, Y.; Wang, M.; riley, M.; delker, S.; ito, t.; hideki, a.; Mori, t.; handa, h.; hakoshima, t.; daniel, t.o.; Miller, K.; Cathers, B.e.; Carmel, g.; Pagarigan, B.; Leon, B.; rychak, e.; Corral, L.; ren, Y. (2014). Crystal Structure Of Human Cereblon In Complex With Ddb1 And Lenalidomide. Protein data Bank: 4tz4.

CMCF-id

Penfield, J.S.; Worrall, L.J.; Strynadka, n.C.; eltis, L.d. (2014). Crystal Structure Of 3-Ketosteroid-9-Alpha-Hydroxylase 5 (Ksha5) From R. Rhodochrous In Complex With Fe2/S2 (Inorganic) Cluster. Protein data Bank: 4qdc.

CMCF-BM

Penfield, J.S.; Worrall, L.J.; Strynadka, n.C.; eltis, L.d. (2014). Crystal Structure Of Apo Ksha5 And Ksha1 In Complex With 1,4-30Q-Coa From R. Rhodochrous. Protein data Bank: 4qdf.

CMCF-BM

dombrovski, L.; dong, a.; Wernimont, a.; Smil, d.; getlik, M.; Senisterra, g.; Poda, g.; al-awar, r.; Bountra, C.; arrowsmith, C.h.; edwards, a.M.; Brown, P.J.; Schapira, M.; vedadi, M.; Wu, h. (2014). Crystal Structure Of Wdr5, Wd Repeat Domain 5 In Complex With Compound Sgc-Ds-Mt-0345. Protein data Bank: 4qqe.

CMCF-id

gruninger, r.J.; thibault, J.; Capeness, M.J.; till, r.; Mosimann, S.C.; Sockett, r.e.; Selinger, B.L.; Lovering, a.L. (2014). Structure Of A Ptp-Like Phytase From Bdellovibrio Bacteriovorus. Protein data Bank: 4nx8.

CMCF-id

Man, h.; Loderer, C.; ansorge-Schumacher, M.B.; grogan, g. (2014). Structure Of Carbonyl Reductase Cpcr2 From Candida Parapsilosis In Complex With Nadh. Protein data Bank: 4c4o.

CMCF-id

roach, e.J.; Kimber, M.S.; Khursigara, C.M. (2014). The Structure Of Escherichia Coli Zapa. Protein data Bank: 4p1m.

CMCF-id

Little, d.J.; Li, g.; ing, C.; diFrancesco, B.r.; Bamford, n.C.; robinson, h.; nitz, M.; Pomes, r.; howell, P.L. (2014). Structure Of Escherichia Coli Pgab C-Terminal Domain In Complex With A Poly-Beta-1,6-N-Acetyl-D-Glucosamine (Pnag) Hexamer. Protein data Bank: 4p7r.

CMCF-id

grishin, a.M.; Condos, t.e.; Barber, K.r.; Campbell-valois, F.X.; Parsot, C.; Shaw, g.S.; Cygler, M. (2014). Shigella Effector Kinase Ospg Bound To Amppnp And E2-Ub Ubch7-Ub Conjugate. Protein data Bank: 4q5h.

CMCF-id

King, d.t.; Lameignere, e.; Strynadka, n.C. (2014). Lpob C-Terminal Domain From Salmonella Enterica (Sel-Met). Protein data Bank: 4q6v.

CMCF-BM

Blattner, C.; Lee, J.h.; Sliepen, K.; derking, r.; Falkowska, e.; de la Pena, a.t.; Cupo, a.; Julien, J.P.; van gils, M.; Lee, P.S.; Peng, W.; Paulson, J.C.; Poignard, P.; Burton, d.r.; Moore, J.P.; Sanders, r.W.; Wilson, i.a.; Ward, a.B. (2014). Crystal Structure Of Hiv-1 Broadly Neutralizing Antibody Pgt151. Protein data Bank: 4nug.

CMCF-id

recht, M.i.; Sridhar, v.; Badger, J.; Bounaud, P.Y.; Logan, C.; Chie-Leon, B.; nienaber, v.; torres, F.e. (2014). Crystal Structure Of Pde10A2 With Fragment Zt1595 (2-[(Quinolin-7-Yloxy) Methyl] Quinoline). Protein data Bank: 4msc.

CMCF-id

Persch, e.; Bryson, S.; todoroff, n.K.; eberle, C.; thelemann, J.; dirdjaja, n.; Kaiser, M.; Weber, M.; derbani, h.; Brun, r.; Schneider, g.; Pai, e.F.; Krauth-Siegel, r.L.; diederich, F. (2014). Crystal Structure Of Trypanothione Reductase From Trypanosoma Brucei In Complex With Inhibitor Ep127 (5-{5-[1-(Pyrrolidin-1-Yl) Cyclohexyl]-1,3-Thiazol-2-Yl}-1H-Indole). Protein data Bank: 4nev.

CMCF-id

recht, M.i.; Sridhar, v.; Badger, J.; Bounaud, P.Y.; Logan, C.; Chie-Leon, B.; nienaber, v.; torres, F.e. (2014). Crystal Structure Of Pde10A2 With Fragment Zt0443 (6-Chloropyrimidine-2,4-Diamine). Protein data Bank: 4ms0, 4mrz.

CMCF-id

Xu, C.; tempel, W.; he, h.; Wu, X.; Bountra, C.; arrowsmith, C.h.; edwards, a.M.; Min, J. (2014). Crystal Structure Of Tbl1Xr1 Wd40 Repeats. Protein data Bank: 4lg9.

CMCF-id

haji-ghassemi, o.; Muller-Loennies, S.; Saldova, r.; Muniyappa, M.; Brade, L.; rudd, P.M.; harvey, d.J.; Kosma, P.; Brade, h.; evans, S.v. (2014). Unliganded 3 Crystal Structure Of S25-26 Fab. Protein data Bank: 4ma1.

CMCF-id

haji-ghassemi, o.; Muller-Loennies, S.; Saldova, r.; Muniyappa, M.; Brade, L.; rudd, P.M.; harvey, d.J.; Kosma, P.; Brade, h.; evans, S.v. (2014). Unliganded 1 Crystal Structure Of S25-26 Fab. Protein data Bank: 4m7z.

CMCF-id

haji-ghassemi, o.; Muller-Loennies, S.; Saldova, r.; Muniyappa, M.; Brade, L.; rudd, P.M.; harvey, d.J.; Kosma, P.; Brade, h.; evans, S.v. (2014). Crystal Structure Of S25-26 In Complex With Kdo(2.8)Kdo(2.4)Kdo Trisaccharide. Protein data Bank: 4m7j.

CMCF-id

haji-ghassemi, o.; Muller-Loennies, S.; Saldova, r.; Muniyappa, M.; Brade, L.; rudd, P.M.; harvey, d.J.; Kosma, P.; Brade, h.; evans, S.v. (2014). Unliganded 2 Crystal Structure Of S25-26 Fab. Protein data Bank: 4m93.

CMCF-id

Qiu, W.; harris-Brandts, M.; Feher, M.; awrey, d.e.; Chirgadze, n.Y. (2014). Crystal Structure Of Ttk Kinase Domain With An Inhibitor: 400740. Protein data Bank: 4jt3.

CMCF-BM

vidossich, P.; Loewen, P.C.; Carpena, X.; Fiorin, g.; Fita, i.; rovira, C. (2014). Structure Of D141A Variant Of B. Pseudomallei Katg Complexed With Inh. Protein data Bank: 4ka6.

CMCF-id

vidossich, P.; Loewen, P.C.; Carpena, X.; Fiorin, g.; Fita, i.; rovira, C. (2014). Structure Of D141A Variant Of B. Pseudomallei Katg. Protein data Bank: 4ka5.

CMCF-id

nguyen thi, n.; offen, W.a.; Shareck, F.; davies, g.J.; doucet, n. (2014). Structure And Activity Of The Gh20 Beta-N-Acetylhexosaminidase From Streptomyces Coelicolor A3(2). Protein data Bank: 4c7f.

CMCF-id

Park, J.; Lin, Y.S.; tsantrizos, Y.S.; Berghuis, a.M. (2014). Crystal Structure Of Human Fpps In Complex With Ys0470 And Two Molecules Of Inorganic Phosphate. Protein data Bank: 4lfv.

CMCF-id

Keeling, t.J.; Samborska, B.; demers, r.W.; Kimber, M.S. (2014). Ccml From Thermosynechococcus Elongatus Bp-1. Protein data Bank: 4n8f.

CMCF-id

Keeling, t.J.; Samborska, B.; demers, r.W.; Kimber, M.S. (2014). The Structure Of Nostoc Sp. Pcc 7120 Ccml. Protein data Bank: 4n8x.

CMCF-id

elliott, J.M.; ultsch, M.; Lee, J.; tong, r.; takeda, K.; Spiess, C.; eigenbrot, C.; Scheer, J.M. (2014). Anti-Parallel Fc-Hole(T366S/L368A/Y407V) Homodimer. Protein data Bank: 4nqt.

CMCF-id

Parker, M.J.; gomery, K.; richard, g.; Mackenzie, C.r.; Cox, a.d.; richards, J.C.; evans, S.v. (2014). Crystal Structure Of The Igg2A Lpt3 In Complex With An 8-Sugar Inner Core Analogue Of Neisseria Meningitidis. Protein data Bank: 4c83.

CMCF-id

J., Kwan J.; Smirnova, e.; Saridakis, v.; W., donaldson L. (2014). Crystal Structure Of The Caskin2 Sam Domain Tandem. Protein data Bank: 4is7.

CMCF-BM

Lewis, S.M.; Wu, X.; Pustilnik, a.; Sereno, a.; huang, F.; rick, h.L.; guntas, g.; Leaver-Fay, a.; Smith, e.M.; ho, C.; hansen-estruch, C.; Chamberlain, a.K.; truhlar, S.M.; Conner, e.M.; atwell, S.; Kuhlman, B.; demarest, S.J. (2014). Structure Of Wild-Type Igg1 Antibody Heavy Chain Constant Domain 1 And Light Chain Lambda Constant Domain (Igg1 Ch1:Clambda) At 1.19A. Protein data Bank: 4lld.

CMCF-id

grishin, a.M.; Cherney, M.; anderson, d.h.; Phanse, S.; Babu, M.; Cygler, M. (2014). Bacterial Effector Nleh2 Kinase Domain. Protein data Bank: 4lrk.

CMCF-id

grishin, a.M.; Cherney, M.; anderson, d.h.; Phanse, S.; Babu, M.; Cygler, M. (2014). Bacterial Effector Nleh1 Kinase Domain With Amppnp And Mg2+. Protein data Bank: 4lrj.

CMCF-id

Leung, C.Y.; Park, J.; de Schutter, J.W.; Sebag, M.; Berghuis, a.M.; tsantrizos, Y.S. (2014). Crystal Structure Of Human Fpps In Complex With Magnesium, Cl02134, And Inorganic Pyrophosphate. Protein data Bank: 4l2x.

CMCF-id

Bacik, J.P.; tavassoli, M.; Patel, t.r.; McKenna, S.a.; vocadlo, d.J.; Khajehpour, M.; Mark, B.L. (2014). Crystal Structure Of Anmk Bound To Amppcp And Anhmurnac. Protein data Bank: 4mo5.

CMCF-id

Bacik, J.P.; tavassoli, M.; Patel, t.r.; McKenna, S.a.; vocadlo, d.J.; Khajehpour, M.; Mark, B.L. (2014). Crystal Structure Of Anmk Bound To Amppcp. Protein data Bank: 4mo4.

CMCF-id

Poulin, M.B.; Shi, Y.; Protsko, C.; dalrymple, S.a.; Sanders, d.a.; Pinto, B.M.; Lowary, t.L. (2014). Crystal Structure Of Udp-N-Acetylgalactopyranose Mutase From Campylobacter Jejuni. Protein data Bank: 4mo2.

CMCF-id

Leung, C.Y.; Park, J.; de Schutter, J.W.; Sebag, M.; Berghuis, a.M.; tsantrizos, Y.S. (2014). Crystal Structure Of Human Fpps In Complex With Magnesium, Cl01131, And Sulfate. Protein data Bank: 4jvj.

CMCF-id


DOCTORAL THESISvisschedyk, d.d. (2014). Photox and Certhrax: The characterization of novel mono-ADP-ribosyltransferase toxins. Canada, on: university of guelph. . CMCF-id

Zhang, d. (2014). Data Transfer and Sharing within Web Service Workflows. australia, Sa: university of adelaide.

Wurtz, W.a. (2014). Photodisintegration of lithium isotopes. Canada, SK: university of Saskatchewan.

Loonchanta, a. (2014). Structural Studies of Gelsolin and Binding Partners. Canada, BC: university of British Columbia.

CMCF-BM, CMCF-id

gillespie, a.W. (2014). Characterizing soil organic nitrogen using advanced molecular analytical techniques. Canada, SK: university of Saskatchewan.

SgM

Burkhardt, M.h. (2014). Real Space and Momentum Space X-ray Spectroscopy of Phase Separated Manganites. uSa, Ca: Stanford university.

reiXS

Xiaolu Linda Zhang (2014). Structural Analysis of Human Cardiac Troponin C and Myosin Binding Protein C. Canada, BC: university of British Columbia.

CMCF-BM, CMCF-id

Lin, J. (2014). Arsenic uptake and speciation in selected sulfate and phosphate minerals. Canada, SK: university of Saskatchewan.

hXMa, veSPerS

Cheng, C. (2014). Materials Optimization and GHz Spin Dynamics of Metallic Ferromagnetic Thin Film Heterostructures. uSa, oh: Columbia university.

SM

COnFEREnCE PROCEEEDInGCanova, h; Fontoura, a; neuenschwander, r t; diaz, B; rodella, C B (2014). Upgrades to the XRD1 beamline optics and endstation at the LNLS. Journal of Physics: Conference Series 493, 012004. 10.1088/1742-6596/493/1/012004.

Khatami, Z.; Wilson, P. r. J.; taggart, o.; Frisina, d. r.; Wojcik, J.; Mascher, P. (2014). Structural and Optical Properties of Luminescent Silicon Carbonitride Thin Films. eCS transactions 61(5), 97-103. 10.1149/06105.0097ecst.

SgM, SXrMB

Sun, X.; hegde, M.; Wang, J.; Zhang, Y.; Liao, J.; radovanovic, P. v.; Cui, B. (2014). Structural Analysis and Electrochemical Studies of Carbon Coated Li4Ti5O12 Particles Used as Anode for Lithium-Ion Battery. eCS transactions 58(14), 79-88. 10.1149/05814.0079ecst.

SM

Sugimoto, t.; Kimura, K.; nakatsuji, S.; Mizokawa, t.; Wadati, h.; takubo, K.; damascelli, a.; regier, t.Z.; Sawatzky, g.a.; Katayama, n.; Sawa, h. (2014). X-ray Photoemission and X-ray Absorption Spectroscopy of Hexagonal Ba3CuSb2O9. in JPS Conf Proc.

SgM

Warnock, r.; Bergstrom, J.; Klein, M. (2014). Coherent Synchrotron Radiation in Whispering Gallery Modes: Theory and Evidence. in Beam dynamics newsletter. Far-ir

dallin, L.o.; Sigrist, M.J.; Summers, t. (2014). Canadian Light Source Update - (Russian). In RuPAC 2006. Joint accelerator Conferences Website (JaCoW). 9783954500383.

Yiu, Y. M.; Murphy, M. W.; Liu, L.; hu, Y.; Sham, t. K. (2014). Experimental and theoretical XANES of CdSxSe1−x nanostructures. aiP Conference Proceedings 1590(26-31), 26-31. 10.1063/1.4870191.

SgM, SXrMB, aCCeSS-PnC/XSd

Wurtz, W.a.; Bertwistle, d.; dallin, L.o.; Sigrist, M.J. (2014). Simulation of a Long-period EPU Operating in Universal Mode at the Canadian Light Source. in Proceedings of iPaC'14. international Particle accelerator Conference. 9783954501328.

Wurtz, W.a.; dallin, L.o.; Bertwistle, d.; Sigrist, M.J.; vogt, J.M.; de Jong, M.S. (2014). Preventing Superconducting Wiggler Quench during Beam Loss at the Canadian Light Source. In Proceedings of IPAC'14. international Particle accelerator Conference. 9783954501328.

dallin, L.o.; Wurtz, W.a. (2014). Low Emittance Lattice Design for the Canadian Light Source. In Proceedings of IPAC'14. international Particle accelerator Conference. 9783954501328.

Lobacheva, o.; goncharova, L.v.; Chavarha, M.; Sham, t.K. (2014). XANES study of Fe-implanted strontium titanate. aiP Conference Proceedings 1590, 82-86. 10.1063/1.4870200.

SgM, aCCeSS-PnC/XSd

When the construction of the linear accelerator was announced in the fall of 1961, it was considered the next logical step for the reputable university of Saskatchewan department of Physics.

the 80-foot electron accelerator tube and facility cost $1,750,000, with the u of S covering the cost of the building and the national research Council meeting the equipment costs. on november 6, 1964, the Saskatchewan accelerator Laboratory officially opened and positioned the province at the forefront of nuclear physics in Canada.

50 Years of Accelerator Science

snowy wavesthe roof of SaL, still a distinctive part of the CLS facility, was designed to look like an electromagnetic wave.

sal (and Cls) Beginnings Sir John Cockcroft, nobel laureate, turns the first sod for SaL. May 10th 1962. u of S President J.W.t. Spinks watches.

some things never change the same linear accelerator that was used for some of the earliest experi-ments in Canada is still used as the linear accelerator for the Canadian Light Source synchrotron. on the left is Leon Katz, the first director of SaL, and on the right is CLS execu-tive director rob Lamb.

plans for sal a 1962 artist drawing of the planned linear accelerator building, from the u of S archives.

technology thenSaL accelerator Control Console in 1964.

Canadian Light Source Inc.44 innovation Boulevard, Saskatoon, SK, Canada S7n 2v3Phone: (306) 657-3500 Fax: (306) 657-3535

www.lightsource.ca

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