Nanomaterials at Analytical Chem

Nanomaterials in analytical chemistry

• Nanofibers and nanowires and their applications

• Nanoparticles and bio imaging applications

• Nanoparticles detection at the environment

• Nanoparticles in the water remediation

Electrospinning

• Polymer solution loaded into a

syringe

• + electrode was connected to

the needle of syringe

• - electrode connected to the Al

foil covered collector

• High voltage applied, ~10-30kV

• Jet stream ejected and forms interconnected web of nanofibers on collector forming a membrane

Nanofibrous Membrane

High Voltage

Power Supply

Syringe

Polymer solution

Jet stream

Taylor cone

Collector

Fig. 2: Schematic diagram for electrospinning experimental set-up

OH

C12H25O

n

Functionalised poly(p-phenylene)

Polymeric nano network structures

(a−d) SEM micrographs of CN-TFMBE, THIO-G, THIO-Y, and DM-R NWs generated by solution drop casting (0.5 wt % in 1,2-

dichloroethane/methanol (9:1 v/v)), respectively. (e−h) Fluorescence microscopy images of CN-TFMBE, THIO-G, THIO-Y, and

DM-R NW structures generated by the method described for (a−d), respectively. Inset photos show the fluorescence colors of

the isolated molecular state in THF solution (I) and the aggregated nanoparticle state in THF/water (1:4 v/v) (A), respectively.

The concentration of all solutions is 2 × 10−5 mol/L.

Published in: Byeong-Kwan An; Se Hoon Gihm; Jong Won Chung; Chong Rae Park; Soon-Ki Kwon; Soo Young Park; J. Am. Chem. Soc. Article

ASAP

DOI: 10.1021/ja806162h

Copyright © 2009 American Chemical Society

(a) Photo and fluorescence images of CN-TFMBE (blue), THIO-G (green), THIO-Y (yellow), and DM-R (red) 2D-NFs with

various shapes. The black-and-white photo shows the contact angle of a water drop on each 2D-NF. (b) Fluorescence

microscopy and SEM images of multilayer structures of CN-TFMBE, THIO-G, and DM-R 2D-NFs deposited on glass substrates

without wrinkling. The vertical fluorescence microscopy image shows the cross section of the multilayers of the 2D-NFs. (c) Flat

(upper inset) and curved form of the THIO-G 2D-NFs (∼100 μm) and fluorescence image of the curved form (lower inset). (d)

Photo and SEM images of the CN-TFMBE 2D-NFs deposited on a plastic ball substrate (a volume of 36π mm3).

Published in: Byeong-Kwan An; Se Hoon Gihm; Jong Won Chung; Chong Rae Park; Soon-Ki Kwon; Soo Young Park; J. Am. Chem. Soc. Article

ASAP

DOI: 10.1021/ja806162h

Copyright © 2009 American Chemical Society

a, Optical image of the cryptomelane membrane. b, SEM image of cross-sectional area of the

membrane, showing a layered structure. c, Low-magnification SEM image showing surface

morphology of the membrane. d, SEM image of the interpenetrating nanwire networks. e, High-

magnification SEM image of a nanwire bundle. f, TEM image of a single cryptomelane nanowire. g,

High-magnification TEM image of the nanowire shown in f. Inset: the corresponding selected-area

electron pattern. h, Wetting time values as a function of the number of water droplets sequentially

deposited at time intervals of 60 s and 120 s, respectively. Inset: video snapshots of the wetting of a

water droplet on the membrane.

Nature Nanotechnology 3, 332 - 336 (2008)

Super hydrophobic Nanowire Membrane

a, Absorption capacities of the

membrane for a selection of organic

solvents and oils in terms of its

weight gain.

b,c, A layer of gasoline can be

removed by addition of the self-

supporting membrane to the

gasoline followed by the removal of

the paper. The gasoline was

labelled with Oil Blue 35 dye for

clear presentation.

Super hydrophobic Nanowire Membrane

Nature Nanotechnology 3, 332 - 336 (2008)

Potential applications of Polymeric nanofibers

2-amino-9H-dipyrido[2,3-b]indole

(AαC)

1-methyl-9H-pyrido[4,3-b]indole

(Harman)

9H-pyrido[4,3-b]indole

(Norharman)

2-amino-methyl-6-phenyllimidazo[4,5-b]pyridine

(PhIP)

3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole

(Trp-p-2)3-amino-1,4-dimethyl-5H-pyrido[4,3-b]indole

(Trp-p-1)

Target Analyte:

Heterocyclic Aromatic Amines

Optimized Extraction Conditions

PhIP

0.0 10.0 20.00

250

500

mV

min

Sample extract

Standard mixture

NH

H

Trp-p-2

Trp-p-1

AαC

Optimized Conditions:

20 min extraction in sample solution with neutral pH & no salt content, 10

minute desorption in MeOH

Real Sample Analysis - Beer

Beer Brand

Concentration / ng mL-1

NH H Trp-p-2 PhIP Trp-p-1 AαC

Tiger Beer 0.3708 0.5653 - - - 1.069

Victoria

Bitter 1.4688 - 0.1179 - - -

Oranjeboom 1.3460 0.4153 - - - 0.1222

Carlsberg - - - - -

Stella Artois - + - - - +

+: Detected but not quantifiable

-: Not detected

0

5

10

15

20

25

L3 L2-PT L1-PT

Up

take (

ng

)Network fibre

30 um PDMS

100 um PDMS

PDMS/DVB

CAR/PDMS

PA

CW/DVB

Lewisite 1 (L-1) or 2-chlorovinyldichloroarsine, Lewisite 2 (L-2) or bis(2-

chlorovinyl)chloroarsine and Lewisite 3 (L-3) or tris(2-chlorovinyl)arsine.

Lewisite was considered as the best arsenical war gas

AsCl

Cl

ClAs

Cl

Cl ClAs

Cl Cl

Cl

L-1 L-2 L-3

Chemical warfare agents detection

propanedithiol was used as derivatization agent

SPME of Polymeric

nano network

structures

Fig. 1 Profiles of the nanofibre membranes. (a)

Conventional technique by sol–gel coating; and (b)

schematic process of in situ formation of the

nanofibres in the pores of the support

Fig. 2 Permeation selectivity and surface charge of

BSA and BHb as a function of pH. The ratio of BSA to

BHb in the initial solution was adjusted to 1.

Chem. Commun., 2009, 1264-1266

Ceramic membranes for separation of proteins and DNA through in situ growth

of alumina nanofibres inside porous substrates

Quantum Dots

Inorganic semi conductor nanocrystals (~102-103 atoms)

• Size determines exact wavelength

3 nm CdSe -> 520 nm emission

5.5 nm CdSe -> 630 nm emission

Size increasesFluorescence arises due to the

radiative recombination of an

excited electron –hole pair in

between the conductance band

and the valence band.

http://www.answers.com/topic/fluorescence-in-various-sized-cdse-quantum-dots-png

Optical properties of QD

Advantages:─ Highly luminescent (high absorptivity and quantum

yields)

─ High extinction coefficient

─ High photostablity

─ Broad excitation and narrow emission spectra

─ ~ 20 times brighter than the typical organic fluorescent dye molecules

─ ~ 100 times more stable than fluorescent dye molecules

─ Size-tunable emission

─ Single wavelength excitation of multiple color quantum dots

Disadvantage: Toxicity

16

CdSe/ ZnS

CdSe: Luminescent core

ZnS: Passivating agent + protects from

Cd leaking

MAA: Solubilizer + Protein attachment

site

Luminiscence image of cultured HeLa cells incubated with (A) Marcapto QDs (B)

QD- Transferrin conjugates using fluorescence microscope

Warren, C. W.C.; Shuming, N. Science, 1998, 281, 2016-2018

CdSe-ZnS quantum dots labeled with transferrin undergo receptor mediated endocytosis in cultured HeLa cells

No QDs inside the cells, image is due to cellular auto fluorescence

Application of Quantum Dots

1) CdSe/ZnS core-shell

17

Near IR imagingSilica – Au nanoshells

Au nanorods

Au nanocages

Au nanoparticle assemblies

SPR wave length comes in Biological NIR window

( 650-900 nm)

a) Silica Au nanoshells:

SPR extinction of nanoshells. Red shift of SPR

wave length with increasing core/ shell ratio

Human breast carcinoma cell

incubated with nanoshells ( Si = 55nm,

Au = 10 nm) has SPR extinction at

around 800 nm.

Additional advantage:

Irreversible tissue damage

due to localized high

temperature.

Jain, P.K.; El-Syed, I.H.; El-Syed, M.A. Nanotoday, 2007, 18

Solid tumor

Apply magnetic

field to

concentrate

particles

Imaging

Inject MPs by

IV

MP will circulate

through the blood

stream

Site specific Magnetic targeting

Published in: Vadym N. Mochalin; Yury Gogotsi; J. Am. Chem. Soc. Article ASAP

Copyright © 2009 American Chemical Society

Excitation monitored at 450 nm emission (1) and emission at 410 nm excitation (2) spectra of ND-ODA dispersion in

dichloromethane; photographs of ND and ND-ODA (0.004% wt) dispersions in dichloromethane with visible (upper row) and UV

(365 nm, lower row) illumination.

Chemical structures of the amphiphilic polymers

a) A photograph of single-walled CNTs

dispersed in water by each of two polymers.

(b) Transmission electron microscopy image of

poly-1 coated CNTs where the scale bar is 100

nm. (c) A photograph of Tween-20 and poly-1

coated CNTs after incubation in 10% serum-

containing medium for 7 days.

Rational design of amphiphilic polymers to make carbon nanotubes water-

dispersible, anti-biofouling, and functionalizable

Chem. Commun., 2008, 2876-2878

Optical images of the representative developmental stages of a normally developing zebrafish in egg water (in the absence of

nanoparticles): (A) 1.25–1.50 hpf (8-cell-stage embryo); (B) 2–2.25 hpf (64-cell-stage embryo); (C) 24 hpf (segmentation-stage

embryo); (D) 48 hpf (hatching-stage embryo); (E) 72 hpf (pharyngula-stage embryo); and (F) a completely developed zebrafish

at 120 hpf. Scale bar = 500 µm. hpf = hours post-fertilization.

Published in: Kerry J. Lee; Prakash D. Nallathamby; Lauren M. Browning; Christopher J. Osgood; Xiao-Hong Nancy Xu; ACS Nano 2007, 1, 133-

143.

Nanoparticles in Early Development of Zebrafish

Embryos

Representative optical images of (A) normally developed and (B–G) deformed zebrafish. (A) Normal development of (i) finfold,

(ii) tail/spinal cord, (iii) cardiac, (iii,iv) yolk sac, cardiac, head, and eye. (B–G) Deformed zebrafish: (B) finfold abnormality; (C)

tail and spinal cord flexure and truncation; (D) cardiac malformation; (E) yolk sac edema; (F) head edema, showing both (i)

head edema and (ii) head edema and eye abnormality; (G) eye abnormality, showing both (i) eye abnormality and (ii) eyeless.

Scale bar = 500 µm. More zebrafish deformations observed in these experiments are summarized in Table I of the Supporting

Information.

Published in: Kerry J. Lee; Prakash D. Nallathamby; Lauren M. Browning; Christopher J. Osgood; Xiao-Hong Nancy Xu; ACS Nano 2007, 1, 133-

143.

Published in: Amrita Chatterjee; Mithun Santra; Nayoun Won; Sungjee Kim; Jae Kyung Kim; Seung Bin Kim; Kyo Han Ahn; J. Am. Chem. Soc.

2009, 131, 2040-2041.

Rhodamine derivative 1, prepared from Rhodamine B

Detection of nanoparticles in the environmental water

samples?

(a) Fluorescence response of 1 (10 μ M) after 10 min upon addition of 0−2 equiv of Ag+ in 20% ethanolic water at 25 °C

(excitation at 530 nm). Inset: a fluorescence intensity plot depending on the equiv of Ag+. (b) Color change and (c) fluorescence

change of 1 (50 μM) upon addition of 1.0 equiv of Ag+ in 20% ethanolic water, after 10 min.

Published in: Amrita Chatterjee; Mithun Santra; Nayoun Won; Sungjee Kim; Jae Kyung Kim; Seung Bin Kim; Kyo Han Ahn; J. Am. Chem. Soc.

2009, 131, 2040-2041.

(a) Fluorescence spectral change of 1 (10 μM) when treated with 1.0 equiv of each metal ion, taken after 1 h of each addition.

(b) A fluorescence intensity profile of 1 upon addition of Ag+ (0.050−0.54 ppm) (the intensity was taken at the peak height at

584 nm). Both data were obtained in 20% ethanolic water at room temperature.

Published in: Amrita Chatterjee; Mithun Santra; Nayoun Won; Sungjee Kim; Jae Kyung Kim; Seung Bin Kim; Kyo Han Ahn; J. Am. Chem. Soc.

2009, 131, 2040-2041.

(a) Changes in fluorescence spectra of 1 (20 μM) upon addition of AgNPs (10 μM) in the presence of 1.0 mM H2O2 and 1.0 μM

H3PO4. (b) Fluorescence intensity changes of 1 after 1 h upon addition of AgNPs (1.0, 2.0, 4.0, 6.0, 8.0, and 10 μM each) in the

presence of the acidic H2O2 solution. Inset: changes in the fluorescence intensity profile of 1 at 584 nm.

Fig. (A) Separated (top) and dispersed (bottom) solutions of typical

NMs with sizes ranging from about 5 to over 100 nm by using TX-

114, (a) CdSe/ZnS, (b) Fe3O4, (c) TiO2, (d) Ag, (e) Au, (f) C60, (g)

SWCNT; (B) UV-vis spectra of Au NPs in the surfactant-rich phase;

(C) UV-vis spectra of Au NPs in the aqueous phase before and after

extraction.

Triton X-114 based cloud point extraction: a thermoreversible approach for

separation/concentration and dispersion of nanomaterials in the aqueous

phase

Chem. Commun., 2009, 1514-1516

Fig. Effects of TX-114, temperature and NaCl on the

particle hydrodiameter in aqueous dispersions of Au NPs

Fig. TEM images of Au NPs in the aqueous phase

at 20 °C without (A) and with TX-114 (B), and in

aqueous solutions of TX-114 before centrifugation

at 35 °C without (C) and with (D) the presence of

NaCl.

Wastewater Remediation

Ideal Technique

Economically-viable Environmentally-friendly Efficient

• UV photodegradation:– Renewable solar energy

– Natural elimination

• Titanium dioxide catalyst:– Accelerates oxidation process

– Affordable

– Chemically stable over wide pH range

Degradation Profiles – β-blockers

Norephedrine

0

20

40

60

80

100

0 50 100 150 200

Time (min)

% o

f o

rig

inal

am

t

Without UV No catalyst 0.2 0.4

Alprenolol

0

20

40

60

80

100

0 50 100 150 200

Time (min)

% o

f o

rig

inal

am

t

Without UV No catalyst 0.2 0.4

Propanolol

0

20

40

60

80

100

0 50 100 150 200

Time (min)

% o

f o

rig

inal

am

t

Without UV No catalyst 0.2 0.4