Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films
This work is devoted to development of a multi-element gas sensor based on surface plasmon resonance (SPR) to recognize some alcohols. As sensitive layers capable to change their optical properties when interacting with volatile alcohol molecules, we investigated bulk-porous sorbents – calixarene...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2011
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Kostyukevych, K.V. Khristosenko, R.V. Shirshov, Yu.M. Kostyukevych, S.A. Samoylov, A.V. Kalchenko, V.I. 2017-05-26T16:31:18Z 2017-05-26T16:31:18Z 2011 Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films / K.V. Kostyukevych, R.V. Khristosenko, Yu.M. Shirshov, S.A. Kostyukevych, A.V. Samoylov, V.I. Kalchenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 3. — С. 313-320. — Бібліогр.: 28 назв. — англ. 1560-8034 PACS 73.20. Mf, 07.07.Df https://nasplib.isofts.kiev.ua/handle/123456789/117767 This work is devoted to development of a multi-element gas sensor based on surface plasmon resonance (SPR) to recognize some alcohols. As sensitive layers capable to change their optical properties when interacting with volatile alcohol molecules, we investigated bulk-porous sorbents – calixarenes (tret-butyl-calix[4,6,8]arenes (С[4]А, С[6]А, С[8]А), tetra-amyl-calix[4] resorchinolaren (C[4]Re). Each calixarene was studied to obtain its kinetic concentration SPR characteristics for interaction with ethanol, isopropanol and penthanol vapors. To realize SPR measurements, the sensitive calixarene films (d ∼ 100 nm) were deposited on a gold film (d ∼ 45 nm) by using the method of thermal evaporation in vacuum. Experimental multi-element SPR device was designed as based on the analysis of TV image obtained for the studied array of calixarene films and tested using saturated ethanol vapors. The authors are grateful to S.A. Zynio for the preparation of thin films and A.S. Pavluchenko for his interest to the work and the fruitful discussions. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films Article published earlier |
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Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
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Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films Kostyukevych, K.V. Khristosenko, R.V. Shirshov, Yu.M. Kostyukevych, S.A. Samoylov, A.V. Kalchenko, V.I. |
| title_short |
Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
| title_full |
Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
| title_fullStr |
Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
| title_full_unstemmed |
Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
| title_sort |
multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films |
| author |
Kostyukevych, K.V. Khristosenko, R.V. Shirshov, Yu.M. Kostyukevych, S.A. Samoylov, A.V. Kalchenko, V.I. |
| author_facet |
Kostyukevych, K.V. Khristosenko, R.V. Shirshov, Yu.M. Kostyukevych, S.A. Samoylov, A.V. Kalchenko, V.I. |
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2011 |
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English |
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Semiconductor Physics Quantum Electronics & Optoelectronics |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| format |
Article |
| description |
This work is devoted to development of a multi-element gas sensor based on
surface plasmon resonance (SPR) to recognize some alcohols. As sensitive layers capable
to change their optical properties when interacting with volatile alcohol molecules, we
investigated bulk-porous sorbents – calixarenes (tret-butyl-calix[4,6,8]arenes (С[4]А,
С[6]А, С[8]А), tetra-amyl-calix[4] resorchinolaren (C[4]Re). Each calixarene was
studied to obtain its kinetic concentration SPR characteristics for interaction with
ethanol, isopropanol and penthanol vapors. To realize SPR measurements, the sensitive
calixarene films (d ∼ 100 nm) were deposited on a gold film (d ∼ 45 nm) by using the
method of thermal evaporation in vacuum. Experimental multi-element SPR device was
designed as based on the analysis of TV image obtained for the studied array of
calixarene films and tested using saturated ethanol vapors.
|
| issn |
1560-8034 |
| url |
https://nasplib.isofts.kiev.ua/handle/123456789/117767 |
| citation_txt |
Multi-element gas sensor based on surface plasmon resonance: recognition of alcohols by using calixarene films / K.V. Kostyukevych, R.V. Khristosenko, Yu.M. Shirshov, S.A. Kostyukevych, A.V. Samoylov, V.I. Kalchenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2011. — Т. 14, № 3. — С. 313-320. — Бібліогр.: 28 назв. — англ. |
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2025-11-25T21:07:27Z |
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| fulltext |
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
PACS 73.20. Mf, 07.07.Df
Multi-element gas sensor based on surface plasmon resonance:
recognition of alcohols by using calixarene films
K.V. Kostyukevych1, R.V. Khristosenko1, Yu.M. Shirshov1, S.A. Kostyukevych1,
A.V. Samoylov1, V.I. Kalchenko2
1 V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine,
41, prospect Nauki, 03028 Kiev, Ukraine, khristosenko@ukr.net
2 Institute of Organic Chemistry, National Academy of Sciences of Ukraine,
5, Murmanskaya St., 02094 Kiev, Ukraine
Abstract. This work is devoted to development of a multi-element gas sensor based on
surface plasmon resonance (SPR) to recognize some alcohols. As sensitive layers capable
to change their optical properties when interacting with volatile alcohol molecules, we
investigated bulk-porous sorbents – calixarenes (tret-butyl-calix[4,6,8]arenes (С[4]А,
С[6]А, С[8]А), tetra-amyl-calix[4] resorchinolaren (C[4]Re). Each calixarene was
studied to obtain its kinetic concentration SPR characteristics for interaction with
ethanol, isopropanol and penthanol vapors. To realize SPR measurements, the sensitive
calixarene films (d ∼ 100 nm) were deposited on a gold film (d ∼ 45 nm) by using the
method of thermal evaporation in vacuum. Experimental multi-element SPR device was
designed as based on the analysis of TV image obtained for the studied array of
calixarene films and tested using saturated ethanol vapors.
.
Keywords: Surface plasmon resonance, imaging gas sensor, sensor array, calixarene
films, alcohols.
Manuscript received 31.01.11; accepted for publication 14.09.11; published online 21.09.11.
1. Introduction
In the recent decade, the problem of recognizing odors
transform into real challenge to physicist, chemists and
engineers [1]. While camcorders and microphones
became excellent artificial organs for sighting and
hearing, olfaction remains unattainable for changing it
with artificial sensors. Up-to-date gas-analytic systems
“electronic nose” consist of an array of sensors that
being in contact with a complex mixture of volatile
molecules generates a set of electric signals suitable for
further input to computer and logical processing [2]. But
sensitive materials in these devices do not reveal specific
high-selective interaction traditioinally inherent to
biochemical sensor systems. These materials are
characterized by low-selective cross-reactivity. It means
that each element of this array responds to various
studied chemical reagents to some extent [3].
When analyzing complex molecular interactions in
gas medium, the most popular sensor arrays are based on
optical principles of transduction. There arise new
reports of designing such devices for food and fragrance
industries, for solving ecological tasks, development of
new drugs, and even for space investigations [4 – 8].
Optical transducers use light absorption effects [9],
reflection [10], diffraction [11], interference [12], optical
fibers [13], as well as SPR [14]. To design a sensor
array, one can use, for example, the spectrum of optical
absorption for a thin organic film, which can change
when being in contact with studied gas mixture and
defines its color. It is visual estimation of this effect that
was used in creation of the miniature “artificial nose” for
one-shot application [15]. However, a noticeable change
in the absorption spectrum of this organic film sorbing
gas molecules is usually related with strong chemical
transformations and, as a rule, is non-reversible.
Thereof, this method did not get any further
development.
Recently in our work [16], successfully realized
was the method for digital registration of changes in
color components (RGB) inherent to interferentially
colored calixarene thin films. The essence of this method
consists in changing the thickness and refraction index
of organic films when binding the studied volatile
molecules, which causes color changes. Measuring the
refraction coefficient and thickness of the molecular
layer, one can draw a conclusion of the type of
molecules in ambient atmosphere. This method showed
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
313
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
rather high sensitivity and specificity in the course of
detecting volatile molecules of some alcohols.
However, measuring the reflection amplitude for
three wavelengths is not the most sensitive method to
determine the thickness and refraction index for organic
films. Sensitivity of the SPR effect to changes in the
refraction index is at least one order higher. For instance
in [17], the authors demonstrate the possibility to measure
a difference in refraction indexes for dried air and helium
by using the SPR method. This method is based on the
energy transfer from an optical beam to a surface
evanescent wave propagating parallel to a metal/dielectric
interface, and this coupling is very sensitive to a local
change of the refractive index of the dielectric medium,
induced for example by the surface hybridization of bio-
molecules. One of the ways to realize the SPR sensor
array is to measure variations of the reflection coefficient
at some fixed wavelength and angle of incidence on 2D
surface by using CCD camera [18].
However, application of SPR to register the
refraction coefficient and thickness of the organic film
array is not a trivial task. The matter is that, when
depositing the organic film on a plasmon-supporting
gold layer, the SPR angle is shifted by tens degrees,
which causes the necessity to specially choose the prism
design. Some additional difficulties arise when trying to
create an SPR array, since in this case one should choose
the thickness and refraction index of this organic film in
such a manner that the SPR angle would be
approximately the same for all the samples. Only in this
case registration of SPR signal changes becomes
possible in the mode of fixed angle. In creation of multi-
element sensor arrays based on the SPR effect, one
problem more is to choose material of a sensitive
organic film. This sensitive material should be porous to
increase the adsorption volume, noticeably expand when
adsorbing molecules-analytes and have different
selectivity with regard to various classes of volatile
molecules.
Solution of the above problems is the aim of this
work.
2. Experimental setups and materials
2.1. SPR sensor instrumentation
To study adsorption properties of sensitive organic films
for sensor arrays, we used the single-channel device
BIOSUPLAR-201, developed in V. Lashkaryov Institute
of Semiconductor Physics (NAS of Ukraine) in
cooperation with Mivitec GmbH-Analytical μ-Systems
(www.micro-systems.de). This device provides
measurements of the total SPR curve in the angle
configuration that corresponds to the Kretchmann
scheme [19] with mechanical scanning the angle of
incidence within the range 18 degrees in air (12 degrees
in glass) and accuracy 5 arc seconds as well as the
possibility to make absolute calibration by the angle.
Excitation of surface plasmons (SP) in thin gold film is
realized using the p-polarized laser beam (λ = 670 nm)
and a glass prism (refraction index n = 1.61, base angle
65°, base face 20×20 mm2). It allows to register SPR
curves within the range of incidence angles 56 to 68
degrees (in glass). It is this range where the SPR
minimum is located, if depositing a sensitive organic
film with the thickness 50 – 200 nm on gold. Measured
in these experiments as a device output signal was the
angle position of the SPR minimum during adsorption
and desorption of molecules-analytes.
The multi-channel SPR sensor is developed and
constructed using the same principle, but without
automated scanning by the angle. The idea of this multi-
channel SPR analyzer is to realize visualization of the
SPR response for each sensing element by using TV
camera. The optical scheme of this device is shown in
Fig. 1. The central unit of the experimental facility is the
glass prism (n = 1.51) with the base angle 70° and base
face 60×120 mm. The base face of the prism is equipped
through immerse liquid with the SPR chip containing
several sensors and flow-through cuvette to input-output
a studied sample. The prism is located on a rotating
goniometric table with a special pantograph providing
equality of angles of incidence and reflection within the
range 55 - 75°. All the system of sensors is illuminated
with a broad uniform beam of p-polarized light
(λ = 0.65 μm) and a fixed angle of incidence. A
stationary image of the sensor surface is captured by a
black-and-white CCD camera.
The developed facility allows to use recent
achievements in the field of TV technologies, computer
input and analysis of images. The essential advantage of
this method is the possibility to simultaneously test all
the cells of the multi-element sensor. Besides, there
arises the opportunity to study dynamics of the process
with further analysis of every its stage and the static
image recorded in the corresponding time moment. The
system for processing the image consists of three main
components, namely: electronic TV camera, device for
input and registration of video frames as well as
computer soft to process the image. Used in this facility
is the CCD camera Spacecam 300 operating in the mode
of receiving white-and-black images with the resolution
corresponding to 250,000 pixels. The system of
automatic gain control (AGC) in this camera was
switched off, which gave the possibility to calibrate the
facility. To input and register the video frames, we used
a specialized universal serial bus (USB). The white-and-
black image captured with the camera one could observe
at the computer display and register it in a definite
moment. For high-speed processing and storage of
images, we used a specific soft.
2.2. SPR detector element
As a sensitive element of the SPR sensor, we used gold
films with the thickness (45±5) nm on the glass substrate
of the size 20×20×1 mm and refractive index n = 1.515.
Glass substrates were mechanically cleaned and
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
314
http://www.micro-systems.de/
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
chemically processed with further washing in distilled
water by using an ultrasonic bath. Then these were
finished using glow discharge directly before deposition.
Metal layer was deposited by thermal evaporation in
vacuum (ВУП-4 facility, residual vapor pressure 4⋅10-4
Pa, speed of sputtering 40 to 50 Å/s). To improve
adhesion, we used a thin chromium layer (∼ 1 nm). To
increase stability, the chips were annealed at Т ∼ 120°С
[20]. The gold layer was covered with thin organic films
consisting of calixarenes sensitive to studied analytes.
Optical contact of these SPR chips with the glass prism
was achieved using immerse liquid with the same
refraction index.
2.3. Sensitive materials
To construct gas sensors, commonly used are such
materials as: phtalocyanines [21], macro-cyclic
compounds [22, 23], metal-proteins [24], calixarenes
[25]. The latter possess apparent advantages, as
compared to metal-proteins and phtalocyanines, due to
their porous structure and high value of expansion
coefficient in the course of adsorption [26, 27].
In [28], the authors studied four ways to deposit
calixarene layers onto substrates of gas sensors, namely:
“thin and thick drop”, Langmuir-Blodgett (LB)
technique, “air-brush”, thermal evaporation in vacuum.
Their investigations showed that, regardless of the
method of deposition, adsorption capability of calixarene
films to alcohol molecules within the thickness range 50
to 1,000 nm remains practically the same and is in
proportion to the film volume. To prepare sensor arrays,
they usually used the method of thermal evaporation in
vacuum, as it provides the highest uniformity of the film
in thickness under the condition of thermal stability for
this material.
In this work, as sensitive materials of a multi-
sensor array we investigated thin calixarene films: tret-
butyl-calix[4,6,8]arenes (C[4]A, C[6]A, C[8]A) and
tetra-amyl-calix[4]resorchinolaren (C[4]Re) synthesized
in the Institute for Organic Chemistry, NAS of Ukraine
(Kyiv). Molecules of these materials are closed
compositions of several phenol rings with the cage
dimensions 0.63 (1.36) nm for С[4]А up to 0.79
(1.8) nm for С[8]А. The thickness of the order of
100 nm was chosen as optimal, because this calixarene
film thickness provides the shift of the SPR angle to the
range 55 – 60°, which is suitable to the chosen prism
dimensions. Since this class of calixarene films is
thermally stable, the films were deposited using thermal
evaporation in vacuum without heating the substrate
(ВУП-4 facility, residual vapor pressure 4⋅10-4 Pa, speed
of sputtering 1 nm/s). Thickness calibration of films was
carried out using atomic force microscopy.
2.4. Analytes
Used in this work as analytes were the following
alcohols: ethanol, penthanol and isopropanol of super-
high purity. To study concentration dependences, we
used saturated alcohol vapors dilute with dry cleaned air.
Dilution was realized using a special syringe of 20 ml
capacity made of material inert to the studied substances.
3. Results and discussion
3.1. SPR investigations of calixarene films
Development of this multi-element SPR sensor for
recognition of alcohols was begun from studying the
sensitivity and specificity of calixarene films towards
studied analytes. With this aim, the samples with
Fig. 1. Scheme of the experimental SPR setup.
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
315
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
calixarene (С[4]А, С[6]А, С[8]А, C[4]Re) films were
one-by-one placed to the cell of the single-channel
device BIOSUPLAR-201, and the kinetics of changes in
the angular position of SPR minima with time were
recorded when injecting ethanol, penthanol and
isopropanol vapors in various concentrations as well as
after pumping with pure air. The obtained kinetic curves
are shown in Fig. 2.
0 500 1000 1500 2000 2500 3000 3500
46,8
46,9
47,0
47,1
47,2
47,3
47,4
47,5
47,6
6
5
4
3
2
1
SP
R
an
gu
la
r p
os
iti
on
, d
eg
.
time, s
C[4]Re
isopropanol
pentanol
etanol
0 500 1000 1500 2000 2500 3000 3500
53,95
54,00
54,05
54,10
54,15
54,20
54,25
54,30
54,35 6
5
4
3
2
1
SP
R
an
gu
la
r p
os
iti
on
, d
eg
.
time, s
C[8]A
pentanol
isopropanol
ethanol
0 500 1000 1500 2000 2500 3000 3500
55,75
55,80
55,85
55,90
55,95
56,00
56,05
56,10
56,15
6
5
4
3
2
1
SP
R
an
gu
la
r p
os
iti
on
, d
eg
.
time, s
C[6]A
isopropanol
pentanol
ethanol
Fig. 2. Relative change of the SPR angle versus time in the
cases of letting-to and pumping-out the ethanol, penthanol and
isopropanol vapors in various concentrations for the following
calixarene films: C[4]A, C[6]A and C[8]A. Changes in the
analyte concentration was reached by dilution of alcohol
saturated vapors with pure air: 1 – calixarene film under air
action; 2 – dilution 1/10; 3 – dilution 2/10; 4 – dilution 3/10; 5
– dilution 4/10; 6 – dilution 6/10.
It can be seen that the SPR response, when alcohols
are absorbed by calixarene (C[4]Re and С[8]А) films,
has the shape close to the rectangular one: the signal
grows to some value and then comes back to its initial
value after pumping with pure air. At low vapor
pressures (considerable letting down), the top of the
signal is rather flat. However, when the concentration
grows, the shape of response complicates and
demonstrates a pronounced peak. As it was shown
earlier in [16], this peak can be related with changes in
film elastic constants in the course of adsorption.
Contrary to C[4]Re and С[8]А, the С[6]А films
demonstrate practically no peak during vapor action.
Their response grows slowly in time up to the moment
of pumping with pure air. This behavior is related with
diffusion of vapors inside the film with time. The
maximal amplitudes of SPR minimum shift as a result of
alcohol vapor action were obtained with the calixarene
C[4]Re.
Displayed in Fig. 3 are the concentration
dependences for the SPR response amplitude in the case
of calixarene C[4]Re film adsorbing volatile molecules
of ethanol, penthanol and isopropanol. In practice, the
amplitude of SPR responses grows linearly with the
concentration of these alcohols. It is noteworthy that the
weaker SPR response to penthanol molecules is related
with the low pressure of saturated vapors (5 mm Hg) for
this heavy alcohol, as compared to isopropanol
(40 mm Hg) and ethanol (44 mm Hg). Similar
dependences were obtained for calixarene С[6]А and
С[8]А films. The results of respective measurements are
summarized in Table 1.
Being based on the experimental results of serial
measurements of the SPR response corresponding to
C[4]Re, С[8]А and С[6]А films adsorbing isopropanol,
ethanol and penthanol molecules, one can perform a
recognition procedure by application of any
mathematical classification method, for example, use
statistic methods or neuron networks. To estimate the
capability of the chosen array in recognition of the
studied alcohols, it is necessary to represent amplitude
values of the obtained SPR responses in n-dimensional
space of sensors and consider distances between them.
To make a preliminary estimation, one can use
geometric formalism, i.e., calculate distances between
these vectors in some metrics (find the distance
function), for instance, in the Euclidean one. Fig. 4
shows geometric constructions for the SPR response
amplitudes in Cartesian coordinates for the studied
sensor pairs.
Fig. 4 shows a comprision of responses for
different sensor pairs to various concentrations of
ethanol, isopropanol and penthanol. It can be easily seen
that the pairs containing C[4]Re allow to reliably
distinguish ethanol and isopropanol regardless of the
concentration within the letting down range 1/10...6/10.
At the same time, penthanol cannot be practically
recognized.
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
316
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
0 10000 20000 30000
46,8
46,9
47,0
47,1
47,2
47,3
47,4
47,5
SP
R
a
ng
ul
ar
p
os
iti
on
, d
eg
.
gas concentration, ppm
C[4]Re
ethanol
pentanol
isopropanol
Fig. 3. Amplitude values of the SPR angle shift versus the
concentration of the studied alcohols when the latter act on the
calixarene C[4]Re films.
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
20 40 60 80 100 120
0
20
40
60
80
100
120
C
[6
]A
C[8]A
- ethanol
- pentanol
- isopropanol
50 100 150 200
0
20
40
60
80
100
120
C[
6]
A
C[4]Re
- ethanol
- pentanol
- isopropanol
0 50 100 150 200
0
20
40
60
80
100
120
C[
8]
A
C[4]Re
- ethanol
- pentanol
- isopropanol
Fig. 4. Comprision of SPR response amplitudes for various
alcohols in Cartesian coordinates when using sensor pairs.
Table 1. SPR response of C[4]Re, С[8]А,С[6]А films
adsorbing the studied molecules
Pressure of molecular vapors, p/ps
0.1 0.2 0.3 0.4 0.6
Isopropanol
C[4]Re 35 55 80 90 170
С[8]А 25 40 50 70 110
С[6]А 38 55 70 85 120
Ethanol
C[4]Re 38 75 98 140 200
С[8]А 20 30 38 50 70
С[6]А 30 45 60 70 90
Pentanol
C[4]Re 15 18 23 27 39
С[8]А 8 11 15 18 23
С[6]А 6 20 24 28 40
Thus, after the performed experiments one can
draw the following conclusions: i) thermally deposited
calixarene C[4]Re, С[8]А and С[6]А films demonstrate
different sensitivity when adsorbing ethanol, isopropanol
and penthanol molecules; ii) С[4]А films do not
pronounce any noticeable sensitivity to the studied
analytes, therefore the respective curves were not
presented in this paper; iii) even using two films -
C[4]Re and С[8]А – one can distinguish ethanol and
isopropanol as well as determine their concentration.
3.2. Operational demonstration of multi-element SPR
gas sensor
To demonstrate operation of the multi-element
sensor based on SPR phenomenon, we used a chip
containing four calixarene films: tret-butyl-
calix[4,6,8]arenes (С[4]А, С[6]А, С[8]А), tetra-
penthylyl-calix[4] resorchinolaren (C[4]Re). The sensor
chip was fixed on the prism base face via immerse liquid
by using a special flow-through cuvette to input-output
the studied assay and illuminated with a wide laser beam
of p-polarized light (λ = 0.65 μm) with a fixed angle of
incidence (51° in glass). Light reflected from the sensor
surface entered to the objective of CCD camera and
brought information about the SPR response. Thus, the
SPR image could be observed in display and recorded in
definite time moments. Processing the held image
provided a possibility to determine the value of changes
in the intensity of reflected light and, consequently, to
obtain quantitative data upon interaction of sensitive
films with the studied analytes.
An analyzed gas mixture was supplied to the
studied samples via the flow-through cuvette.
Monitoring the changes in light reflection from surfaces
of all four sensors being under action of ethanol vapors
was performed simultaneously. The respective image
was recorded at the initial stage with pure air (Fig. 5a),
directly after introduction of the studied assay (Fig. 5b),
317
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Fig. 5. Time dependence of the ethanol vapor influence on the sensor chip containing four calixarene films: tret-butyl-
calix[4,6,8]arenes – C[4]A – 1, C[6]A – 2, C[8]A – 3, and tetra-pentyl-calix[4]resorchinolarene. a – pure air, b – directly after
introduction of the studied assay (saturated ethanol vapors), c – in 5 min later, d – after pumping-through with pure air.
in five minutes after this introduction (Fig. 5c), and after
pumping with pure air (Fig. 5d). It is seen that the image
brightness of the sensors 2, 3 and 4 (С[6]A, C[8]A and
С[4]Re, respectively) is changed under action of ethanol
vapors, while that of the sensor 1 (С[4]А) remains
unchanged. After pumping-through with pure air, the
image brightness of all the sensors was recovered. It
means that the interaction between calixarene film
material and ethanol molecules is reversible, and the
studied sensor chip can be used repeatedly.
After transformation of the image into digital form
and processing the data, one can obtain not only
qualitative but quantitative information about interaction
of the studied assay with different calixarene films. The
program developed by the authors for these analysis
allows to find data about reflected light intensities in any
image point. With this aim, it is necessary to put the
cursor to the point of interest and set a respective
command. Besides, it is possible to build a map for the
sample with lines of identical reflection intensity.
0 23
64
b
a
re
fle
ct
ed
li
gh
t i
nt
en
si
ty
, R
U
image coordinate, pixel
Fig. 6. Distribution of the reflected light intensity along the
chosen cross-section of the samples (C[8]A on the left and
C[4]Re on the right) in Figs 5a and 5b. The curves: a – sensors
under action of pure air, b – sensors under action of saturated
ethanol vapors.
Fig. 6 demonstrates the intensity of reflected light
in relative units for the sensors 3 and 4 (C[8]A on the
left and С[4]Re on the right) versus the image
coordinate. The curve a corresponds to the initial state of
the samples (pure air in cuvette), curve b characterizes
changes in the light reflection intensity directly after
introduction of the ethanol assay with the concentration
close to that of its saturated vapors. In Figs 5a and 5b,
horizontal lines show the coordinate position of the
analyzed profile. It is seen that the signal is increased in
both cases. The coordinate of vector that corresponds to
augmentation of the signals from the sensors 3 and 4 is
shown in Fig. 4b with asterisk. Despite the absence of
binding between the measured signals in concentration,
the asterisk position is close to the points corresponding
to ethanol. In our opinion, this fact proves a technical
foundation for the efficiency of creation of multi-
channel, high-speed and efficient gas sensor based on
the SPR principle.
4. Conclusion
Shown in this work is the possibility to construct the
multi-element gas sensor for alcohols, which consists of
a surface plasmon resonance transducer and sensor array
with cross-reactivity. As sensitive materials for this
multi-sensor array, we used thin calixarene films: tret-
butyl-calix[4,6,8]arenas (C[4]A, C[6]A, C[8]A) as well
as tetra-amyl-calix[4]resorchinolarene (C[4]Re) prepared
by thermal evaporation in vacuum. Using the automated
single-channel device BIOSUPLAR-201, for each
calixarene we studied kinetic concentration
characteristics describing interaction with ethanol,
penthanol and isopropanol vapors. The calixarene films
C[4]A, C[6]A and C[8]A demonstrated different
sensitivity and specificity to adsorption of molecules of
the studied alcohols. C[4]A films did not pronounce any
noticeable sensitivity to chosen analytes. To estimate
capability of the investigated sensor array in recognition
of analytes, we performed geometrical constructions for
© 2011, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
318
Semiconductor Physics, Quantum Electronics & Optoelectronics, 2011. V. 14, N 3. P. 313-320.
amplitudes of SPR responses to ethanol, penthanol and
isopropanol vapors in Cartesian coordinates for pairs of
sensors. It has been shown that even using two films -
C[4]A and C[8]A – one can recognize ethanol and
isopropanol in any concentration as well as to determine
the analyte concentration. The obtained results coincide
with analogous data of interferential colorimetry for tret-
butyl-calixarene films. It is indicative of reliability of
results following from the above experiments and
confirm the opportunity to design multi-element SPR
gas sensor. Experimental multi-element SPR device has
been designed as based on the analysis of TV image
obtained for the studied array of calixarene films and
tested using saturated ethanol vapors.
Acknowledgements
The authors are grateful to S.A. Zynio for the
preparation of thin films and A.S. Pavluchenko for his
interest to the work and the fruitful discussions.
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2.3. Sensitive materials
2.4. Analytes
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