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M.A. Proskurnin and D.S. Volkov
D.A. Nedosekin and V.P. Zharov
M. Proskurnin
• Improving detection methodology
Advancing techniques • Microspectroscopy and microdetection
• Previously unused or unknown reactions
Unraveled chemistry • Nanoanalytics and suprachemsitry
• Polymeric substances
Organized media • Green solvents (ionic liquids)
• Broad-action sensing materials
Sensors • Flow sensors
• Spectroscopy and electrochemistry
Combining the uncombined • Atomic and molecular techniques
• In situ analysis
Biomedical analysis • Complex factors
High-sensitivity
chemical analysis
Determination of
Determination of
Photothermal characteristic constants
light-absorption
spectroscopy of physical and chemical
parameters
processes
Determination
of thermophysical
parameters of substances
Reagentless
Coupling
Selective
(destructive)
M. Proskurnin
10
LODexper/LODtheor
8
6
4
2
0
Lowly absobing Non-contrast Lowly absobing Reactions with Kinetic systems
substances reactions kinetic systems disperse with disperse
products products
mirror
Diode laser
lens, 185 mm cw probe beam,
flow system 808.0 nm, 1 mW
adjustment chopper, cw excitation beam,
Primary
dichroic plate 0.5–30 Hz (532), 615, 635,
(photometric) cell
mirror plate plate 660 and 690 nm, 20 mW
photodetector
Diode lasers
dichroic
mirror lens, wavelength-selecting
Stained-glass 330 mm chopper,
bandpass filter 0.5–30 Hz
Synchronising Power meter
Secondary
Pinhole, photodiode (ground signal)
(scattering)
2 mm photodetector
Recording system
Primary (photothermal)
photodetector
M.A. Proskurnin, T.V. Zhidkova, D.S. Volkov, M. Sarimollaoglu, E.I. Galanzha, D. Mock, D.A. Nedosekin, V.P.
Zharov In vivo multispectral photoacoustic and photothermal flow cytometry with multicolor dyes: A
potential for real-time assessment of circulation, dye-cell interaction, and blood volume // Cytometry A.
2011, V. 79A, N. 10, P. 834–847. DOI: 10.1002/cyto.a.21127 PMID: 21905207
A
Concentrations: MB, 1, 1.3 × 10–4 М; 2, 6 × 10–5 М; 3, 2.2 × 10–
5 М; 4, 1.3 × 10–5 М; CV: 1, 1.2 × 10–4 М; 2, 6.5 × 10–5 М; 3,
3.3 × 10–5 М; 4, 1.6 × 10–5 М; 5, 1.1 × 10–5 М.
Signal averaging N = 30 (A) and N = 1000 (B).
Laser parameters: pulse rate, 10 kHz; energy
fluence, 50 mJ/cm2.
Ломоносов-2012. М.А. Проскурнин, кафедра
23.02.2013 13
аналитической химии
I
1 I = f(k, c, Cp, ρ)
0.8
0.6
0.4 I I0
0.2 I
0
0 1000 2000 3000 4000 5000
t, c
I = f(Сp, c, k, ρ)
Now 50 nm
Resolutions
Thermal Optical over
signal signal diffraction
limit
10 0.000
10 0.000
0.3000
0.3000
0.4000
0.4000
8 0.7000 8 0.7000
A 1.000 1.000
1.200 1.200
distance, m
distance, m
6 1.400 6 1.400
1.800 1.800
2.100
2.100
4
4
2
2
2 4 6 8 10
B
2 4 6 8 10 distance, m
distance, m 0.000 0.000
dem o dem o dem o dem o dem o
0.3000 0.3000
dem o dem o dem o dem o dem o
0.4000 0.4000
8 dem o dem o dem o dem o dem o
0.7000 8 0.7000
dem o dem o dem o dem o dem o
1.000 1.000
1.200 1.200
dem o dem o dem o dem o dem o dem o dem o dem o dem o dem o
1.400 1.400
6 1.800
6 1.800
distance, m
distance, m
dem o dem o dem o dem o dem o dem o dem o dem o dem o dem o
2.100 2.100
4 dem o dem o dem o dem o dem o
4 dem o dem o dem o dem o dem o
dem o dem o dem o dem o dem o
C dem o dem o dem o dem o dem o
2 2
dem o dem o dem o dem o dem o
dem o dem o dem o dem o dem o
0 0
0 2 4 6 8 0 2 4 6 8
distance, m distance, m
Unique properties compared to
metal nanoparticles carbon materials
New applications biomedical
various
materials
technological applications.
biomedical
contrast
composites agents
catalysts antibiotics
biolabels
0.000
0.002069 0.000
0.016 0.004138 2.850E-04
0.006206 5.700E-04
0.014 0.0020
0.008275 8.550E-04
sig na l
0.012 0.01034 0.001140
sig na l
0.01241 0.001425
0.010 0.0015
Th erma l len s
0.001710
0.01448
Th erma l len s
0.008 0.01655
0.001995
0
0.006 0.001 0.002280
4
0.00
05
2 0.00
0.00
0
0.00
0 40
00
000 80
0.00
00
nm
Xd 0 ce, 60
m
ista 2 0 0 tan
00
e, n
20
00
Xd
nce dis ista 40
anc
dist
, nm Y nce 50
00 00
00 , nm 20 Y
40 0
00
0
Poster presentation: Application of Photothermal and Photoacoustic Spectroscopy
for the Monitoring of Aqueous Dispersions of Carbon Nanomaterials
Poster presentation: Application of Photothermal and Photoacoustic Spectroscopy
for the Monitoring of Aqueous Dispersions of Carbon Nanomaterials
Data
treatment
Methodology
Reaction Process
(Chemistry) (Physics)
Методологические подходы традиционных методов
нуждаются в переосмыслении и доработке
Отсутствуют стандартные образцы сравнения,
сертифицированные материалы и т.п.
Существуют несколько пересекающихся или даже
противоположных по смыслу аналитических задач
Высокая концентрация
определяемого
компонента
Проблематика высоких
Определение веществ в
Высокая концентрация
концентрированных
концентраций
матрицы
растворах
Малые количества в
сверхтонких слоях или Малое время жизни
микрообъемах
Анализ в потоке
Solid Photothermal
samples instruments
Organized
media
Chemistry
• Solid/surface
Go photometry
• Advanced solvents
• PT/PA combos
Steady • Heterogeneous
solutions
Ready • In situ bioanalysis
• Flow sensors
The heat-transfer equation for a single generic source for the
heat generation in the sample and the heat transfer to the
surrounding medium:
Q(r , z , t )
Tsamp (r , z , t ) Dsamp Tsamp (r , z , t )
2
t СP ρ
Tmedium (r , z, t ) Dmedium 2 Tmedium (r , z, t ) 0
t
Temperature distribution is related with the total temperature
response Ttotal of a sample with the equation
4 Dt0
I 4 Dt Tlong Trad
3/2
Ttotal (r , z , t )
πωe k π
2
Tlong and radial Trad are longitudinal and radial components
of the temperature profile
• Dr. I.A. Veselova (MSU)
• Dr. S.V. Muginova (MSU)
• Prof. S.A. Eremin (MSU)
• Prof. Yu.M. Dedkov (MOPI)
• Dr. V.M. Shkinev (GeoKhi)
Photometric Photothermal Photonic
Linear kinetic Solvent
Convection Photoinduced
curve properties
Colloidal Autoacceler
Luminescence
products ation
slope Thermooptical signals Lum.
Convection signals
intensity
Advantages of kinetic methods
High sensitivity Large number of reactions
Advantages of photothermal lensing
High sensitivity Solvent properties
Laser as a monitoring tool
Elucidation of mechanisms
New rate/photothermal based effects
A solid quartz support with a
chitosan or cellulose layer
An enzyme is immobilized in this layer
The layer is “flavoured” with PEG or
an ionic liquid to mildly change the
chemical properties of enzyme
A color reaction developed in time is
sensitively probed with photothermal
lensing
LOD for phenolic compounds is
100 nmol/L
Analytical forms (not numerical models)
of equations for signal vs. concentration
Long linear calibration ranges
High sensitivity
• Broad-action sensing materials
Solid Samples/Sensors • Flow sensors
Specially prepared polymers with active groups
glass/quartz samples with thin layers of natural polymers
(chitosans) grafted reagents
the analytical reaction occurs in a polymer chip
or in a thin layer on a substrate
same laws and instruments as photometry
Various samples, from transparent solids to films or resins
Significant selectivity
Chemical
Photothermics analysis
Considerable preconcentration of test substances
Batch/flow analysis conditions are the same
More stable than solutions, usable for unstable samples
Signal enhancement by nanomaterials
• Previously unused/ unknown reactions
Unraveled chemistry • Nanoanalytics/suprachemsitry
Reactions with low sensitivity for routine methods
Noncontrast reactions
Kinetic indicator systems
Reactions producing disperse solutions
1.40
1.20
2.50
y = 6.9340x + 0.3396
1.00 R2 = 0.9944
2.00 2
R = 0.9765
0.80
1.50
0.60
1.00
0.40
0.50
0.20
c Hg, ppm A
0.00
0.00 0.080 0.130 0.180 0.230 0.280
0 0.05 0.1 0.15
Determination of Hg(II) in water samples
LOD 9 ppb Hg(II) With concentration into the polymethylmethacrylate
matrix pre-treated with copper(II) dithizonate
