nanomaterials at analytical chem
DESCRIPTION
Nanomaterial, Chemistry, AnalyticalTRANSCRIPT
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