Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds
This work reports on the investigation of the sensory properties of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds. Experiments were carried out using the 8-channel sensory system based on the Quartz Crystal Microbalance (QCM) technique. Kinetic responses, concentration depe...
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
2020
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| Cite this: | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds / Z.I. Kazantseva, I.A. Koshets, O.M. Zaharenko, S.G. Kharchenko, V.I. Kalchenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2020. — Т. 23, № 1. — С. 41-45. — Бібліогр.: 17 назв. — англ. |
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| author | Kazantseva, Z.I. Koshets, I.A. Zaharenko, O.M. Kharchenko, S.G. Kalchenko, V.I. |
| author_facet | Kazantseva, Z.I. Koshets, I.A. Zaharenko, O.M. Kharchenko, S.G. Kalchenko, V.I. |
| citation_txt | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds / Z.I. Kazantseva, I.A. Koshets, O.M. Zaharenko, S.G. Kharchenko, V.I. Kalchenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2020. — Т. 23, № 1. — С. 41-45. — Бібліогр.: 17 назв. — англ. |
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| description | This work reports on the investigation of the sensory properties of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds. Experiments were carried out using the 8-channel sensory system based on the Quartz Crystal Microbalance (QCM) technique. Kinetic responses, concentration dependences, and detection limit have been obtained. It has been shown that the interaction of the sensitive layer with the analyte molecules is substantially defined by the chemical structure of thiacalix[4]arene. Thus, thiacalix[4]arene materials considered in this paper are of great interest for application in the sensory systems of “Electronic Nose” type.
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ISSN 1560-8034, 1605-6582 (On-line), SPQEO, 2020. V. 23, N 1. P. 41-45.
© 2020, V. Lashkaryov Institute of Semiconductor Physics, National Academy of Sciences of Ukraine
41
Semiconductor physics
Sensory features of thiacalix[4]arene molecules
towards volatile halogen-aromatic compounds
Z.I. Kazantseva
1
, I.A. Koshets
1*
, O.M. Zaharenko
1
, S.G. Kharchenko
2
, V.I. Kalchenko
2
1
V. Lashkaryov Institute of Semiconductor Physics, NAS of Ukraine,
41, prospect Nauky, 03680 Kyiv, Ukraine
2
Institute of Organic Chemistry, NAS of Ukraine,
5, Murmanska str., 02660 Kyiv, Ukraine
*E-mail: koshets@isp.kiev.ua
Abstract. This work reports on the investigation of sensory properties of thiacalix[4]arene
molecules towards volatile halogen-aromatic compounds. Experiments were carried out
using the 8-channel sensory system based on Quartz Crystal Microbalance (QCM)
technique. Kinetic responses, concentration dependences and detection limit have been
obtained. It has been shown that interaction of the sensitive layer with the analyte
molecules is substantially defined by the chemical structure of thiacalix[4]arene. Thus,
thiacalix[4]arene materials considered in this paper are of great interest for application in
the sensory systems of “Electronic Nose” type.
Keywords: QCM sensor, thiacalix[4]arene, halogen-aromatic compounds.
https://doi.org/10.15407/spqeo23.01.41
PACS 07.07.Df
Manuscript received 30.09.19; revised version received 20.12.19; accepted for publication
18.03.19; published online 23.03.19.
1. Introduction
Similarly to freons, halogen derivatives of carbon
aromatic compounds are actively involved in the
photochemical reactions occurring in atmosphere. As a
result, atmosphere is polluted with both halogen
derivatives and products of their transformation and
interaction with other air pollutants [1, 2]. The analysis
of these compositions of harmful chemicals is quite
complicated. Thus, under sunlight radiation bromo-
benzene, bromide propyl and other bromine and fluorine
compounds (in the presence of pollutants of nitrogen
oxides, sulfur, etc.) are converted to cyclic and other
compounds that are significantly more toxic than the
original ones. For example, chlorobenzene is very toxic
for aquatic flora and fauna with the long-term aftermath.
Not only cyclic but all halogenated carboncarbons are
more toxic to humans and animals than the corres-
ponding hydrocarbons. Halogen derivatives of aromatic
compounds possess light narcotic properties, irritate the
respiratory tract, and harm the liver. The most potentially
dangerous is fluorobenzene, volatility of which is much
higher as compared to other mono-substituted halogen
derivatives. The maximum permissible concentration
(MPC) of fluorobenzene is at the level of several mg/m
3
,
while for chlorobenzene – tens of mg/m
3
[3, 4]. So, the
possibility to create sensors sensitive to these toxic
substances is a very important task.
Calixarenes (СA) are macrocyclic compounds that
due to their bowl-like structure are of great interest in
supramolecular chemistry for the purpose of constructing
new molecules with outstanding complexing properties
based on them [5, 6]. Calixarenes are capable to form
Host-Guest complexes in the gas phase, in solutions, in
the crystalline state and in two-dimensional phases – thin
films [7]. Chemosensors based on calixarene thin films
have been used to create devices capable of recognizing
cations, anions and neutral organic molecules in solutions
(artificial tongue) or in the air (artificial nose) [8-13].
2 Experimental
This paper is devoted to studying the several
thiacalix[4]arene molecules that are potentially capable
to form Host-Guest complexes with halogen-aromatic
volatile compounds. Taking into account the previous
experiments [14], sensitive materials С904, С906, С907,
С908, С912, С913, С917, С920 (nomenclature accepted
at the Institute of Organic Chemistry, NAS of Ukraine,
where these compounds were synthesized) have been
SPQEO, 2020. V. 23, N 1. P. 41-45.
Kazantseva Z.I., Koshets I.A., Zaharenko O.M. et al. Sensory features of thiacalix[4]arene molecules towards …
42
Fig. 1. Chemical formulas of thiacalix[4]arenes.
chosen for our study. Their structural formulas are
presented in Fig. 1. All of them (except C904) are the
thiacalix[4]arenes functionalized with tert-butyl groups
on the upper rim and different (phosphorylated, bromine
and nitrogen containing, etc.) functional groups on the
lower rim. Several halogen-aromatic compounds,
namely: fluorobenzene (C6H5F), chlorobenzene (C6H5Cl)
and bromobenzene (C6H5Br), were used as analytes.
2.1. Experimental set-up
Quartz Crystal Microbalance (QCM) sensors are widely
used in many practical applications in gaseous and liquid
media as mass-sensitive sensors, for material
characterization, etc. The QCM measurement technique
uses the sensitivity of quartz crystal resonator with
respect to any mass change at its surface in according to
Sauerbrey relation [15]. Sensitivity of QCM technique is
quite high – mass change of nanogram (and less) scale
can be easily observed. When being used as a chemical
sensor, the quartz surface covered with special coating is
called the sensitive layer.
QCM-based chemosensory device designed and
fabricated at the V. Lashkaryov Institute of Semi-
conductor Physics, NAS of Ukraine, was used [16]. The
device consists of 8-channel QCM-based sensor array,
operation cell, gas-supplying pathways, vapour injection
system, air filter-drier providing fresh dry air for
purification sensors between sampling, valve for
switching ”sampling” – “purification” and electronics
(quartz oscillators, frequency counters, and interfacing
with PC). Experiment controlling and data acquisition
were carried out by means of original software. Standard
radio-technical quartz elements (10 MHz, AT-cut,
∅ 8 mm) covered with appropriable thiacalix[4]arene
sensitive layers were used as the sensor elements.
O
S 4
N
O
O
1,3-alt
C912
O
S S
PO
OH
2
Br
С904
O
S 4
SN
C917
O
S S
OH
2
С906
S
O
4
P O
C907
S
O
4
P O
C908
Br
O
S 4
P
Ph
(Oct)2
+
1,3-alt
C913
O
OO
S
O
OO
C920
Table. Detection limits (in ppm) of the sensor array with respect to analytes under study.
Sensitive
layer
analyte
C912 C904 C917 C906 C907 C908 C913 C920
fluorobenzene 15 25 20 20 <10 <10 25 500
chlorobenzene 20 25 20 20 <10 10 15 250
bromobenzene 25 100 50 50 10 15 15 700
SPQEO, 2020. V. 23, N 1. P. 41-45.
Kazantseva Z.I., Koshets I.A., Zaharenko O.M. et al. Sensory features of thiacalix[4]arene molecules towards …
43
0 250 500 750 1000 1250 1500 1750 2000
-60
-50
-40
-30
-20
-10
0
10
20
C912
C904
C917
C906
C907
C908
C913
C920
20001000500
∆
f,
H
z
time, s
a)
0 300 600 900 1200 1500 1800 2100
-90
-75
-60
-45
-30
-15
0
15
1000500250
∆
f,
H
z
time, s
b)
0 250 500 750 1000 1250 1500 1750
-100
-80
-60
-40
-20
0
20
500250100
∆
f,
H
z
time, s
c)
Fig. 2. Kinetic responses of sensor arrays on consequent
injection of fluorobenzene (a), chlorobenzene (b) and
bromobenzene (c) into operation cell. The numerical values in
the plots correspond to the analyte concentration in ppm.
0 500 1000 1500 2000
10
20
30
40
50
60
-∆
f,
H
z
concentration, ppm
a)
0 200 400 600 800 1000
10
20
30
40
50
60
70
80
-∆
f,
H
z
concentration, ppm
b)
0 200 400 600 800 1000
0
20
40
60
80
100
120
140
160
-∆
f,
H
z
concentration, ppm
c)
Fig. 3. Concentration dependences of sensor arrays to
fluorobenzene (a), chlorobenzene (b) and bromobenzene (c).
SPQEO, 2020. V. 23, N 1. P. 41-45.
Kazantseva Z.I., Koshets I.A., Zaharenko O.M. et al. Sensory features of thiacalix[4]arene molecules towards …
44
Fluorobenzene Chlorobenzene Bromobenzene
0
20
40
60
80
100
120
140
-∆
f,
H
z
analyte
C912
C904
C917
C906
C907
C908
C913
C920
Fig. 4. Histogram of sensor array responses on 1000 ppm of
each analytes under study.
2.2. Sensitive layers and the deposition method
For immobilization of the thiacalix[4]arene sensing
layers well-proven, the centrifugation (spin-coating) and
the spreading drop methods have been used. For sensory
applications, it is necessary to choose sensitive materials
that are able both to efficiently bind guest-molecules and
quickly release them during the purification stage of
experiment. Therefore preliminary testing of the
thiacix[4]arene sensitive layers was carried out using a
simplified (single-channel) QCM sensor system. Quality
and uniformity of the films obtained were observed with
AFM and ellipsometry. The QCM baseline frequency
shift due to layer loading on the quartz surface
(“effective” film thickness) was within the range
5000…6000 Hz.
3. Results and discussions
Typical kinetic dependences of sensor array responses to
the sequential injection of fluorobenzene (a),
chlorobenzene (b) and bromobenzene (c) into operation
cell are shown in Fig. 2. The numerical values above the
curves correspond to the analyte concentration in ppm.
The legend is given only in the first plot.
As seen from the kinetic responses of the sensory
system, interaction of the sensitive layer with the analyte
molecules is substantially defined by the chemical
structure of CA. Kinetic responses for different analytes
are significantly altered.
The concentration dependences of the sensor array
towards corresponding analytes are presented in Fig. 3.
They are quite linear. Calixarenes C907 and C908
show rather high sensitivity towards analytes under
study. C913 is turned out to be the most sensitive
towards halogen-aromatic compounds, while its
sensitivity to benzene is negligible [17]. C920 is linear
oligomer, not a cyclic one, possesses good sensitivity to
benzene but poorly sensitive to halogen-aromatic
compounds. There are phosphoryl functional groups in
the lower rim of all these three materials.
The structures of these materials contain phosphoryl
functional groups in the lower rim, which distinguishes
them from all other studied CAs, except for C904, which
differs from the others in the structure of the upper rim.
This difference in the adsorption features of C904 and
C907 indicates the important role both of functional
groups and vase-like structure in the specific adsorption
processes.
Measurements of detection limits of the sensor
arrays were carried out as well. The respective results are
summarized in Table.
For better visual perception of the overall picture
regarding to the selectivity, the responses of the sensor
arrays on 1000 ppm of each analyte are represented by
the histogram in Fig. 4. The responses to 1000-ppm
concentration clearly represent rather good selectivity of
thiacalix[4]arenes involved in our experiments. It should
be noted that C913 showed very high sensitivity to
halogen-aromatic compounds, especially to bromo-
benzene even higher than just due to molecular weight
increasing.
4. Conclusion
As stated above, the kinetic response under adsorption
and desorption processes is a significantly informative
parameter, account of which highly increases
discriminative ability of sensor array under analyte
identification. Since the magnitude of signal for the same
analyte concentrations is different, the kinetics of
responses are altered for different gases. Due to this fact,
thiacalix[4]arene materials considered above are of great
interest for application in the sensory systems of
“Electronic Nose” type.
It has been shown that the sensory elements with
thiacalix[4]arene С907, С908, С913 films are sensitive
towards halogen-aromatic compounds at the WEEL
(Workplace Environmental Exposure Level) level and
lower.
Rather large difference in adsorption capability of
the studied thiacalix[4]arene molecules towards aromatic
and halogen-aromatic compounds can be explained in
terms of Host-Guest complexation with applying the
methods of molecular modeling based on quantum-
chemical calculations.
References
1. Pradyot Patnaik. A Comprehensive Guide to the
Hazardous Properties of Chemical Substances.
John Wiley & Sons, 2007.
2. Nicholson W.J., and Moore J.A. Health Effects of
Halogenated Aromatic Hydrocarbons. Ann. N. Y.
Acad. Sci. 1979.
3. https://www.cdc.gov/niosh/ershdb/index_un.html
4. https://www.cdc.gov/niosh/npg/npgd0121.html
5. Gutsche C.D. Calixarenes: An Introduction
(Monographs in Supramolecular Chemistry). 2
nd
ed.
Royal Society of Chemistry, Cambridge, 2008.
6. Vicens J., Harrowfield J. (Eds.) Calixarenes in the
Nanoworld. Dodrecht, Springer, 2007.
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7. MacGillivray L.R., Atwood J.L. Unique guest
inclusion within multi-component, extended-cavity
resorcin[4]arenas. Chem. Communs. 1999. No 2. P.
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8. Koshets I.A., Kazantseva Z.I., Shirshov Yu.M.,
Cherenok S.A., Kalchenko V.I. Calixarene films as
sensitive coatings for QCM-based gas sensors.
Sensors and Actuators. B. 2005. 106. P. 177–181.
https://doi.org/10.1016/j.snb.2004.05.054.
9. Koshets I.A., Kazantseva Z.I., Belyaev A.E.,
Kalchenko V.I. Sensitivity of resorcinarene films
towards aliphatic alcohols. Sensors and Actuators.
B. 2009. 140. P. 104–108.
https://doi.org/10.1016/j.snb.2009.04.014
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412. P. 238–251.
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13. Pinalli R., Pedrini A. and Dalcanale E. Biochemical
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https://doi.org/10.1039/C8CS00271A.
14. Kharchenko S.G., Kazantseva Z.I., Koshets I.A.,
Kozlova T.V., Shishkina S.V., Ryabitskii A.B.,
Kalchenko V.I. Phosphorylthiacalixarenes as
sensors for volatile organic molecules. Functional
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15. Sauerbrey G. Verwendung von Schwingquartzen
zur Wagung dunner Schichten und zur
Mikrowagung. Z. Physik. 1959. 155. P. 206–222.
16. Kalchenko V.I., Koshets I.A., Matsas E.P., Kopylov
O.N., Solovyov A., Kazantseva Z.I., Shirshov
Yu.M. Calixarene based QCM sensors array and its
response to volatile organic vapors. Mater. Sci.
2002. 20, No 3. P.73–88.
17. Unpublished results – report on fulfilment of the
scientific Project “Chemosensory system of
“Electronic Nose” type for biomedical and
ecological application” in the frame of Complex
R&D Program “Sensory systems for medical-
ecological and industrial-technological demands”.
Kyiv-2017.
Authors and CV
Z.I. Kazantseva is Ph.D. in Physics
and Mathematics, Senior Researcher
at the V. Lashkaryov Institute of
Semiconductor Physics, NAS of
Ukraine. The area of scientific
interests of Z.I. Kazantseva includes
thin organized films, LB-technology
and sensory materials.
I.A. Koshets is Ph.D. in Physics and
Mathematics, Senior Researcher at the
V. Lashkaryov Institute of Semi-
conductor Physics, NASU. The area
of scientific interests of I.A. Koshets
includes development of bio- and
chemical sensors, software and
electronics for sensory applications.
O.M. Zaharenko is Junior
Researcher at the V. Lashkaryov
Institute of Semiconductor Physics,
NAS of Ukraine. The area of
scientific interests of O.M. Zaharenko
includes preparations of chemical
sensors and carrying out experiments
on QCM-based chemosensory
systems.
V.I. Kalchenko is Academician of
NAS of Ukraine, Professor, Doctor of
Science in Organic Chemistry, Head
of the Institute of Organic Chemistry,
NASU. The area of scientific interests
of Prof. V.I. Kalchenko includes
calixarenes, organophosphorus che-
mistry, supramolecular chemistry,
design and synthesis of novel
materials.
S.G. Kharchenko is Ph.D. in
Chemistry, Researcher at the Institute
of Organic Chemistry, NAS of
Ukraine. His scientific interests are
chemistry of thiacalixarenes,
supramolecular chemistry, organo-
phosphorus chemistry.
|
| id | nasplib_isofts_kiev_ua-123456789-215664 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 1560-8034 |
| language | English |
| last_indexed | 2026-03-26T19:16:40Z |
| publishDate | 2020 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| record_format | dspace |
| spelling | Kazantseva, Z.I. Koshets, I.A. Zaharenko, O.M. Kharchenko, S.G. Kalchenko, V.I. 2026-03-24T12:21:55Z 2020 Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds / Z.I. Kazantseva, I.A. Koshets, O.M. Zaharenko, S.G. Kharchenko, V.I. Kalchenko // Semiconductor Physics Quantum Electronics & Optoelectronics. — 2020. — Т. 23, № 1. — С. 41-45. — Бібліогр.: 17 назв. — англ. 1560-8034 PACS: 07.07.Df https://nasplib.isofts.kiev.ua/handle/123456789/215664 https://doi.org/10.15407/spqeo23.01.041 This work reports on the investigation of the sensory properties of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds. Experiments were carried out using the 8-channel sensory system based on the Quartz Crystal Microbalance (QCM) technique. Kinetic responses, concentration dependences, and detection limit have been obtained. It has been shown that the interaction of the sensitive layer with the analyte molecules is substantially defined by the chemical structure of thiacalix[4]arene. Thus, thiacalix[4]arene materials considered in this paper are of great interest for application in the sensory systems of “Electronic Nose” type. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Semiconductor Physics Quantum Electronics & Optoelectronics Semiconductor Physics Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds Article published earlier |
| spellingShingle | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds Kazantseva, Z.I. Koshets, I.A. Zaharenko, O.M. Kharchenko, S.G. Kalchenko, V.I. Semiconductor Physics |
| title | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| title_full | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| title_fullStr | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| title_full_unstemmed | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| title_short | Sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| title_sort | sensory features of thiacalix[4]arene molecules towards volatile halogen-aromatic compounds |
| topic | Semiconductor Physics |
| topic_facet | Semiconductor Physics |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/215664 |
| work_keys_str_mv | AT kazantsevazi sensoryfeaturesofthiacalix4arenemoleculestowardsvolatilehalogenaromaticcompounds AT koshetsia sensoryfeaturesofthiacalix4arenemoleculestowardsvolatilehalogenaromaticcompounds AT zaharenkoom sensoryfeaturesofthiacalix4arenemoleculestowardsvolatilehalogenaromaticcompounds AT kharchenkosg sensoryfeaturesofthiacalix4arenemoleculestowardsvolatilehalogenaromaticcompounds AT kalchenkovi sensoryfeaturesofthiacalix4arenemoleculestowardsvolatilehalogenaromaticcompounds |