MoF

Metal Organic Framework

Derek Nelson Brett MichalkAziz Daabash

Amanda Mogollon

Introduction Molecular Rotors Catalyst Nanofibers Drug carriers Questions

Outline

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What is a MOF?◦ Porous crystalline compounds forming 1,2 or 3

dimensional structures with the use of metal ions◦ Consist of a metal ion and a

an organic molecule, often called a ligand.

Metal Organic Framework (MOF)

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MOF’s were born from zeolites, porous crystalline structures both found in nature and man made◦ Zeolites are made from

aluminosilicate materials◦ Named from Greek when a Swedish

man observed water boiling out of the rock

◦ Used in Chem-E industry as catalyst and adsobant

MOF’s are the next generation◦ Sigma-Aldrich, with BASF, have

developed a MOF with the surface area of a football field in 1 gram

Background

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mf.mpg.de

MOF’s have been synthesized in 2 ways◦ solvothermal techniques,

crystals are grown from a hot solution of metal precursor, such as a metal nitrate solution

◦ mechanochemical methods, grinding, to produce, however these are none porous

◦ mechanochemical methods with the addition of isonicotinate (ISA) created porous 3D crystals

Synthesis

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MOF’s have limitless potential in many fields◦ Porous

MOF’s large surface area to volume makes them perfect to replace zeolites at every level when they are available for mass production

◦ Solid As solid structures produced by mechochemical

synthesis, MOF’s have very unique electrical properties being explored

To the Futurehttp://www.cat-litter-critic.com/images/fresh-step-cat-litter.jpg

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Currently at the University of Colorado, Boulder researchers are investigating the use of MOF’s to replace liquid crystals for optoelectronic applications

MOF as Molecular Rotors

• Rotating or twisting molecules under an electric field is the principle behind liquid crystals. MOF crystals could lead to sturdier materials to be used in the data communications industry

• Currently tested MOF’s do not yet reach the barrier to rotation to replace liquid crystals

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Catalyst PaperStructural and Catalytic Performance of a Polyoxometalate-Based Metal-Organic

Framework Having a Lanthanide Nanocage as a Secondary Building Block

Dongbin Dang,†,‡ Yan Bai,‡ Cheng He,† Jian Wang,† Chunying Duan,*,† and Jingyang Niu‡

MOF’s have characteristics that lend themselves to being excellent heterogeneous catalysts

Zeolites are currently holding the market for acidic catalysts

MOF’s require strong Lewis acid properties in order to replace zeolitesfor the cleaving of certain compounds

Purpose

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Strong Lewis acid◦ accepts a pair of electrons from another species◦ Used in the nano cleavage of different molecules

Polyoxometalates (POMs)◦ Inorganic oxo clusters that contain transition

metals◦ Have many properties that can be used to induce

Lewis acid properties into MOFs Heterogeneous Catalyst

◦ For the purpose of this experiment hetero catalyst has a higher conversion than homo

◦ Properties used to see if experiment was a success

Theory

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Compound {[Ho4(dpdo)8(H2O)16BW12O40] 3 2H2O}, compound 1, was thermally crystallized from the solution◦ HoCl3 36H2O, 4,40-bipyridine-N,N0-dioxide

hydrate (dpdo),HoH2BW12O403 nH2O, and hexahydropyrazine (pz)

Compound 1 crystallizes as shown below

Synthesis of MOF

Dongbin Dang,†,‡ Yan Bai,‡ Cheng He

Synthesize a MOF with Lewis acid properties, to create a very effective heterogeneous catalyst.

Use the synthesized cata-list to cleave a BNPP molecule as shown

Use P NMR to monitor the reaction kinetics

Experiment


UV absorbance was used to determine if the experiment was a success

The compound 1 MOF demonstrated heterogeneous catalyst properties with a high yield

Results


Life cycle◦ How long will the catalyst last◦ Can it be regenerated?

Other MOF’s◦ Can it be mechanochemically synthesized?◦ Are there more efficient compounds?

Future Research

Amino Acid Based Metal-Organic

NanofibersInhar Imaz, Marta Rubio-Martínez, Wojciech J.

Saletra, David B. Amabilino, and Daniel Maspoch

Creation of 1-dimensional infinite coordination polymer particles (ICP’s) via conventional coordination chemistry

ICP’s offer◦ Promising functionalities

Magnetism Porosity Ion exchange Optical properties

◦ Encapsulating matricies

Motivation

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Martin et al. (2004)◦ First discrete metal-organic nanotubes by layer-by-layer growth.

Lin et al. ◦ Created Gd(III) based nanorods used as contrast agents by water-

in-oil microemulsion based technique Oh et al.

◦ Porous In(III) based hexagonal nanorods by hydrothermal synthesis You and Loh’s research groups

◦ Creation of coordination polymer based gels and nanofibers. Efficient in light harvesting due to 1-D structure.

Synthesis History

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Purpose: Formation of long chiral coordination polymer nanofibers

Conditions:◦ Ambient conditions◦ Use of aqueous/organic interfacial coordinative polymerization

Technique based on previous work involving Aspartic acid reacted with transition metal ions to create biorelated coordination polymers.

Experiment Introduction

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz,† Marta Rubio-Martínez

1) Aspartic acid and NaOH dissolved in EtOH/H2O mixture (5:1)

2) Cu(NO3)2*6H2O dissolved in water.3) Careful transference of both mixtures to a test tube.4) After 3 days, fibers form at the interface of the layers.5) During the next 2 weeks, the ethanol layer diffuses

into the aqueous phase, and causes formation of the fibers oriented along the direction of diffusion.

Experiment


Photomicrograph image of fiber bundles shows:◦ Length◦ High orientation

Transmission electron microscopy (TEM) depicts◦ Homogeneity of fibers◦ Diameter

Field-emission scanning electron microscopy (FESEM) confirms the uniformity of the sample as well as the narrow diameter distribution.

Results


Confirmation of 1-D structure◦ Proposed formula [Cu(Asp)(H2O)x]n

◦ Energy dispersive x-ray confirmed presence of copper, oxygen, nitrogen, and carbon

◦ IR spectra showed bands at wavelengths that suggest the presence of carboxylate groups of aspartic acid functional groups, and they are coordinating to the Cu(II) ions.

◦ Elemental analysis confirms 1:1 ratio of Cu(II) ions and Aspartic acid

Results continued

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When the aqueous and organic layers are mixed after addition to the test tube, an opaque blue gel is created.

Upon further examination (FESEM) it is observed that the gel is made up of homogeneous short-length nanofibers.

This result indicates that the length of the nanofibers is dependent on the method of synthesis.

Nanofiber Gel


Long chiral nanofibers can be grown using traditional coordination chemistry and biologically derived components by utilizing diffusion controlled growth procedures.

Simple changes in the experimental procedure can have large effects on the end product (nanofiber length and orientation)

Highly flexible composition of coordination polymers can have a huge impact on future applications.

Summary

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Metal–organic Frameworks as Potential Drug CarriersRachel C Huxford, Joseph Della Rocca and

Wenbin Lin

Metal-organic frameworks (MOFs) present a new way to introduce drugs to the body.

Offer high drug loadings, biodegradability, and versatile functionality.

Reduction to nano-scale will increase viability of MOFs to act as drug delivery vehicles.

Introduction

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Lots of progress in the understanding of diseases, but not nearly as much progress in the treatment of those diseases.

MOFs can help to target specific distribution areas (tumors for example) and will:◦ Lower the required doses◦ Extend the time the medication is

in the body◦ Optimize pharmacokinetics◦ Reduce side-effects

Motivation

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Important properties for MOFs used as drug transporters:◦ Size◦ Drug loading◦ Surface properties◦ Drug release kinetics◦ Improved pharmacokinetics◦ Biocompatibility ◦ Tissue specificity◦ Multiple agent engineering

Key Properties

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Major goal is to design a carrier that both the ligand and transition metal used exhibit little toxicity to the human body.

Iron, copper, manganese, nickel, and zinc are all found in the human body, however little is known about possible biological downfalls to each of these metals.

Drug Release with MOFs

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Materials of Institut Lavoisier (MIL) Trivalent metal centers with carboxylic

bridging ligands Large pores (25-34 Å) Large surface area (3100-5900 m2/g) Functional group incorporation Two MOFs studied, MIL-100 and MIL-101

Option 1

Metal–organic frameworks as potential drug carriersRachel C Huxford, Joseph Della Rocca and Wenbin Lin

Both MIL-100 and MIL-101 are chromium based and are tested with the storage and release of ibuprofen.

Drug loading◦ MIL-100 0.347g ibuprofen/g MOF◦ MIL-101 1.376g ibuprofen/g MOF◦ Difference attributed to pore size of MIL-101 at 12700 and 20600 Å

(8200 and 12700 Å for MIL-100) Drug release

◦ Tested using simulated body fluid at 37 °C◦ MIL-100 Initial release within two hours with full release after three

days◦ MIL-101 Steady release for eight hours with full release after six days

Option 1 continued

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The chromium used is highly toxic in the human body, so an iron analog, MIL-101(Fe) should be used as a more suitable drug carrier.

MIL-53 is another MOF in the MIL family that has properties that make it desirable for long release (3 weeks) medications.

MIL family has the highest drug loading capabilities of any material previously studied.

Option 1 continued

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MIL family have hydrophobic pores, but what about MOFs that use hydrophilic pores?

The hydrophilic pores will hold a positive or negative charge, and the drug used will contain opposite charges to the MOFs.

The Rosi group created a MOF consisting of zinc(II) ions, adenine, and para-biphenyl-dicarboxylic acid.

This MOF can be cationically triggered to release the drug contained inside.

Option 2

Storage◦ 0.22 g drug/g MOF◦ Loaded with a hydrochloride salt of procainamide

Release◦ Previously this drug is generally limited by its

rapid exit from the body, and requires re-dosing every three to four hours

◦ Use of MOF extended release time to 72 hours.

Option 2 continued


Gaseous therapeutic carriers – Nitric Oxide◦ Antibacterial◦ Antithrombotic◦ Wound healing applications

MOF made from cobalt or nickel and 2,5-dihydroxyterephthalic acid. ◦ Can absorb seven times

amount of NO as any other MOF

◦ Has little background release

Option 3


NO loaded MOF tested on pig coronary arteries induced vessel relaxation

Nickel and Cobalt are too toxic for biological applications, but this work shows the ability of MOFs to carry and release gaseous cargo.

Option 3 continued

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Previously discussed MOFs cannot work because of large size.

A reduction to the nano scale (nMOFs) will allow systemic circulation through the body while retaining the properties of bulk MOFs

Big Picture: Pharmacokinetic improvements!

Nano-MOFs

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Lin group fabricated nMOF designated NCP-1◦ Tb3+ ions and disuccinatocisplatin (DSCP)◦ ~58.3 nm in diameter◦ Encapsulated in silica to enhance stability◦ Functionalized with c(RGDfk) to target an integrin over

expressed in many cancers Once the MOF reaches the cancer cell, the drug is

reduced to a more toxic form to kill the cancer cell.

NCP-1


Lin group also loaded a nano form of MIL-101 with a cancer prodrug and imaging agent.

Addition of imaging agent suggests possible future of real time monitoring of the therapeutic response to the drug.

nanoMIL-101(Fe)

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Drug carriers can be formed from a vast amount of metal centers and connecting ligands to find desirable characteristics for the specific application.

Many different drugs can be incorporated into the MOF.

Therapeutic drugs in conjunction with imaging agents offer new ways to study the real time effects of medications.

Summary


Investigate the toxic effects of metals already found in the body for use in nMOFs

Explore additional slow release mechanisms for prolonged exposure to the drug.

Design nMOFs for large surface area/volume ratio to maximize drug loading capabilities.

Research coatings that will increase the stability of the nMOFs and possibly help contain the drug inside until the desired location is reached.

Future Research

QUESTIONS?

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Rebuttal Group from U4

Oral Presentation and Slides• We agree that their should have been an introduction slide, instead of

just assuming the audience realized the entire front matter before the three papers were the introduction.

• We agree that the Catalyst Paper slide title was inappropriate and should have matched the other two papers by using the title of the paper for the title of the slided.

• We agree that we should have stuck on one naming convention for metal organic frameworks, either saying its full description the whole time, or by condensing it to MOF every time after defining it in the introduction. We apologize for any distraction that this may have caused.

• We agree that some slides should have contained larger pictures, but for the most part we think that we filled the slides in nicely with ample text/figures.

Technical• We agree that our introduction was lacking in technical

information to provide the audience with a complete background for the papers.

• We also agree that in the first paper the heterogeneous/homogeneous catalyst properties should have been better explained.

• We agree the second paper was very well structured and presented, however we also agree that we should have done more to explain how this research will further research in the field.

• The third paper was not very descriptive on how the drugs target certain areas of the body. We should have done more in depth research to inform the audience that the ligand can be an amino acid that helps the MOF move to a targeted area.

• Overall we agree that we should have had a technical summary and additional research and benefits of our presentation

U1 review of U4Metal Organic Framework

Definition; ◦ consisting of metal ions or

clusters coordinated to often rigid organic molecules to form one-, two-, or three-dimensional structures that can be porous

Importance;◦ Have potential to replace

zeolite◦ Have unique electrical

properties that will be very useful in future electronics and computing

http://medgadget.com/archives/2008/02/organic_metal_hybrids_promise_materials_of_

the_future.html

About the presentation Overall presentation

◦ Well presented, well organized, clear slides and great research work. Thank you for the superb presentation.

Time length◦ It was little off the time limit of 30 minutes

but it wasn’t a boring presentation. They did well to engage the audiences and it was a very good stuff to learn

Food ◦ Provided (thank you)

Impact◦ We have an opportunity about the MOF and

about the research going on this topic◦ It is very helpful for some of us who is

considering nano-research as their career Final thoughts

◦ Such presentation will help in developing the research and presentation skills for undergraduate students like us.

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By Group U2: -Kyle Demel

-Keaton Hamm

-Bryan Holekamp

-Rachael Houk

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Review of Group U4’s Presentation-

The presenters did really well at: Food – This group by far brought the best food to class. Ice cream

sandwiches, cookies, cupcakes… how could we not give you an ‘A’ just for that?

Figures – The graphics used throughout the presentation were pertinent to the topics being presented. The use of graphics was very important to help demonstrate the material being discussed. The group did a good job of incorporating graphics onto every slide.

Structure – The group followed a clear presentation and structure order. They provided an outline and stuck with it. The outline could have been done better. The topics in the outline were vague and did not properly summarize each section.

Articles – The presenters chose appropriate articles for this presentation. A total of three articles were used. This is very impressive considering that most groups chose to only report on one pertinent article during their presentation. The speakers discussed metal organic frameworks with respect to catalysts (very important considering the reaction engineering that many students have learned), amino acid nanofibers (incorporating biology with our nanotechnology discussion), and potential drug carriers (which builds off of previous groups’ presentations.

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The group could improve at: Timing – The group needs to do a better job coordinating the

speaking parts and for how long each group member will talk. Only two of the group members presented, which is fine, but of these two members, one spoke for five minutes, and the other spoke for twenty-five minutes. That is clearly malproportioned. The speakers should practice together ahead of time to smooth out transitions and even out the amount of speaking parts.

Background – The background was very brief, and predictably, not very informative. The speakers rushed through the introduction in about two or three minutes. More time should be committed to communicating the basic material.

Slide Format – The group clearly went with a template formatting and meshed all the sections together. This led to striking inconsistencies in formatting. The text and heading size varied between the slides. Most slides also had too many words on them. These should be short bullet points, not paragraphs! The figures also need to be bigger. There is too much blank space on the slides. Space the text out more if you have to, but do not leave half a slide blank without reason.

Stronger Beginning & End – The opening was kind of weak; the intro slide was bland and the outline was not very well done. Also, the conclusion was sort of abrupt. You need to summarize what was discussed during the presentation.

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Group U3: Krista Melish James

KancewickPhillip Keller Mike Jones

Undergrad 2nd Review for Group U4Metal Organic Frameworks

Presentation Review: Ugrad #4Presentation Review Introduction

The introduction contained good information to describe what MOF’s are, but we would have liked to see more information on their history.

The papers covered after the introduction should have been mentioned even if each paper has its own intro slides. This would help the audience to see where the presentation is going.

Paper 1: Catalyst Intro slide communicated all necessary

information to understand the problem and experiemnt.

The theory slide could have been more effective. The last bullet about heterogenous catalystdoesn’t seem to be correctly integrated. Heterogenous catalysts simply are ones that have reaction sites within them. Zeolites and MOF’s are both heterogenous catalyst types.

Explanation of the mechanism of using polyoxometalates to obtain the desired behavior in the MOF could have been done better.

Paper 2: Amino acid based metal organic nanofibers Effective introduction to the topic, and especially

liked the history which put it in perspective. The experiemnt and results where both explained

well, and in a way that was easy to understand. The only thing that should have been better

clarified are the specific positive properties this ICP yielded. The intro mentioned some areas where the might ne useful, but there wasn’t much on how this experiment might affect future things. It seemed like it didn’t have an end goal in mind in advancing the field.

Paper 3: MOF’s as potential drug carriers It is not apparent how MOF’s can help target

specific distribution areas in the body as mentioned in the intro. The rest of the information is correct, but MOFs can’t distinguish between different areas of the body.

Good job explaining how high surface area of MOF can lend istelf to storage and release of medications, as well as why this fact is important.

Experimental results were presented in an easy to understand way. The point was clear, and the limtations of the mofs due to their toxicity was also clearly presented. Would have liked a slide on the specific methods used to create the MOFs.

.

Review Of Group U4 by Group U5


Oral skills and preparation very good.

First speakers seemed to have practiced and knew their information but later speakers needed more work.

Great slide quality and sequence. A lot of pictures, figures, and graphics that were helpful for understanding

Oral and Quality of Slides


Very good introduction. Liked how they described what MOFs were, but would have liked to learn more about their history and past work more.

Choice of papers were relevant and interesting

Did not like how they nicknamed the first paper “Catalyst Paper.” Would have preferred for them to use the actual title of the paper

Technical Review



Metal Organic FrameworkReview of Team U4 by Team U5

Jaynesh Shah Greg Pudewell Edwin L. Youmsi Pete John Pack

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Oral and Quality of Slides Review

Both speakers were loud, clear, audible and maintained eye-contact

They were confident and sounded knowledgeable on the subject

The slides were visually appealing and consistent

All the graphics in the slides were appropriately cited and were relevant to the topic

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Technical Review

Speakers made good use of technical jargon

The papers discussed were relevant and interesting

Could and should have discussed further research a little bit more


Presented by: Group U4Critiqued by: Group U6

Pavitra Timbalia + Michael Trevathan


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Critique: Oral Presentation & SlidesSlide Background made the font easy to read and the pictures easy

to seeThe “Overview” slide did a good job summarizing the topics aheadShould have had a slide which said “Introduction” Instead of saying “Catalyst Paper” could have just placed paper titleThe group did a good job in having graphics on each of the slides –

however, one or two slides did not have any graphicsAll of the graphics were referenced – good job

We did not like the way the slides end – maybe need an overall conclusion slide to tie things together

The group presented well – the other two members presented for this presentation

Both presenters kept good eye contact with the audience and good posture (Both were also dressed in business clothes)

The first speaker spoke too fast – more practice could have helped him pace his talk better instead of making the presentation look rushed

The second speaker was very thorough in his analysis of the two papers and did a good job in explaining the researchhttp://www.beatsworking.tv/greatrex/eyecontact.jpg

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Critique – Technical Content Introduction was a bit rushed because of pace of speaker

It was, however, concise and gave a good overview of metal organic frameworks

Choice of research papers seemed relevant to topic discussedThree papers discussed which gave a good range of information on current

researchThe second and third papers were more in-depth with the analysisThe paper on drug carriers was the most interesting since to us – the

research could assist advanced in the medical fieldEach of the papers covered recent research in the field

The motivation for each paper given at the beginning - something we really liked

Further research was incorporated at the end of the slides for each paper – would have liked to see the impact of this research in the future

Like we said before, the presentation ended abruptly – would have liked to see a conclusions/summary slide or an overall further research slide

We feel that there should have been a “Works Cited” slide to let the audience know which references were used – they were not all cited well in the presentation

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Review for U4

Jung Hwan Woo

• Overall, the presentation and the slides were great.

• The presentation contained several different applications. It was a good approach as it could introduce more applications of MOF’s to the audience. However, this approach resulted in the lack of depth in some of the research topics introduced.

• Some of the slides were a bit crowded with text but it was ok.

• I liked the “option 1, option 2, etc.” approach.

MoF

Documents

joseph della

unique electrical

replace liquid

potential

good job

drug carriers

metalorganic

htmamp