Poster

Surface developed molecularly imprinted polymer
for isomer sensing
Piyush Sindhu Sharma,1 Marcin Dabrowski,1 Krzysztof Noworyta,1 Alexander Kuhn,2
3
1,4
Francis D’Souza, and Wlodzimierz Kutner,
1. Institute of Physical Chemistry, Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland
2. University of Bordeaux 1, Bordeaux, France
3. Department of Chemistry, University of North Texas, Denton, TX 76203-5017, USA
4. Faculty of Mathematics and Natural Sciences, School of Science, Cardinal Stefan Wyszynski University in Warsaw,
Wóycickiego 1/3, 01-815 Warsaw, Poland
E-mail: [email protected]
Research goals: (1) To design a selective recognition unit of chemosensor for sensing of chiral compounds. (2) Development of surface are of
recognition unit of chemosensor for enhancement of transduction signal.
Toward that, for designing of selective recognition unit, a well known molecularly imprinting procedure is used. We present here results obtained from both thin
and surface developed molecularly imprinted polymer (MIP) films as recognition unit of piezoelectric microgravimetry chemosensor under flow injection analysis
conditions.
Research background
Preparation of selective recognition unit of
chemosensor
Designing of selective molecular cavity
Sensitivity of thin film based sensor is limited because of slow
diffusion of analyte through the film. Macroporosity can help to
enhance the diffusion of analyte through film.
2,2'-Bithiophene-5-boronic acid
S
(Functional monomer)
S
S
S
O
HO
OH
B
B
O
HO
Deposition of
silica beads
HO
OH
Complex formation
HO
O
OH
B
O
OH
OH
L-Arabitol
S
B
S
HO
(Template)
S
S
S
Electropolymerization
of complex
S
Cross-linker
Electropolymerization
S
S
S
S
O
HO
B
0.1 M HCl
HO
B
O
HO
Template removal
OH
HO
O
B
B
O
S
Dissolution of
nanobeads
Scheme 2. Steps of preparation of macroporous MIP film
Acetonitrile
-199,2
-159,2
-153,3
-10
-20
-30
-40
Water
-154,6
0
5
10
15
20
25
30
0.15
0.075
0.62
1.25 mM
0
-10
-20
OH
-30
OH
HO
Rybitol
OH
-40
OH
0
d
10
20
30
-30
-40
b
0
5
10
15
20
25
30
35
10 0.009
0.31 0.625
1.25 mM
0
-10
-20
-30
-40
-50
40
0.037 0.15
c
0
10
20
30
Time, min
40
50
60
70
80
Time, min
20
10
0.15
0.075
0.31
1.25 mM
0.62
0
-10
-20
OH
-30
OH
HO
D-arabitol
OH
-40
e
OH
-50
40
1.25 mM
-20
20
0.31
0.62
0.31
-10
35
Time, min
0.15
0.075
0
-50
10
-152,5
0
5
10
15
20
25
30
10 0.075
0.15
0.31
0.62
1.25 mM
0
-10
-20
OH
OH
-30
HO
Xylitol
OH
-40
f
OH
-50
0
10
20
Time, min
Time, min
30
40
Time, min
Figure 3. The time dependence resonant frequency change due to consecutive FIA injections of L-arabitol
solutions of concentration indicated at peaks recorded at 10-MHz quartz crystal resonator coated with (a)
L-arabitol extracted MIP (inset is SEM image of a thin film), (b) NIP, (c) Macroporous MIP film. Frequency
changed recorded at L-arabitol extracted MIP after injection of different interferents (c) rybitol (d) D-arabitol
(e) xylitol.
Table 1: Changes in the enthalpy of formation of non-covalent
complexes between functional monomer (2,2'-bitiofeno-5boronic acid) and template.
Determination of D-arabitol with piezoelectric microgravimetry under flow-injection analysis (FIA) condition
-10
-20
-30
-40
a
10
20
Time, min
30
0.31
0.15
0.62
1.25 mM
0
-10
-20
-30
-40
b
0
5
10
15
20
25
30
10
0.15
0.31
10
0.62
1.25 mM
0
-10
-20
-30
L-arabitol
-40
-50
0
Time, min
10
20
20
Time, min
c
0.075
0.31
0.15
0.62
1.25 mM
0
-10
-20
OH
-30
OH
HO
OH
Xylitol
-40
d
OH
-50
0
10
20
30
10
Resonant frequency change, Hz
0
10
Resonant frequency change, Hz
0.62
Resonant frequency change, Hz
0.31
1.25 mM
20
20
20
20
Resonant frequency change, Hz
B
a
10
Resonant frequency change, Hz
0
-50
20
Resonant frequency change, Hz
-187,7
Resonant frequency change, Hz
Resonant frequency change, Hz
D-Arabitol
1.25 mM
Resonant frequency change, Hz
Vacuum
0.62
20
Resonant frequency change, Hz
L-Arabitol
0.31
0.15
10
-50
Enthalpy change
ΔG / kJ∙mol-1
Solvents
Resonant frequency change, Hz
L-Arabitol templated polymer film
Figure. 1. Scheme of preparation of MIP
20
20
Figure 2: The structure of the complex optimized by means of the
DFT method B3LYP/3-21G * level at T = 298 K in a vacuum (a)
complex formation by non-covalent interactions and (b) complex
formation by covalent interactions.
0
S
Determination of L-arabitol with piezoelectric microgravimetry
under flow-injection analysis (FIA) condition
A
0.15
S
Imprinted polymer film
Scheme 1. Steps of preparation of the molecularly imprinted
polymer (MIP) [1].
10
S
0.15
0.075
0.31
0.62
1.25 mM
0
-10
-20
OH
-30
OH
HO
OH
Rybitol
-40
e
OH
-50
0
10
Time, min
20
30
Time, min
Figure 4. The time dependence resonant frequency change due to consecutive FIA injections of D-arabitol solutions of concentration indicated at peaks recorded at 10-MHz quartz
crystal resonator coated with (a) D-arabitol extracted MIP, (b) NIP. Frequency changed recorded at D-arabitol extracted MIP after injection of different interferents (c) L-arabitol (d)
xylitol (e) rybitol.
Conclusions: (1) The developed chemosensors are highly selective with respect to its template isomers, for instance MIP prepared with L-isomer does not recognize
D-isomer, and vice versa. Additionally developed chemosensors show appreciable selectivity for other structural analogue, such as rybitol and xylitol. (2) Compared to thin
film, macroporous MIP film shows two times enhancement of the signal. (3) Detectability of devised chemosensor (9 µM L-arabitol) is quite efficient to measure chiral
sugar in biological samples.
Acknowledgements: The National Science Centre, 2011/01/N/ST4/03491, and
the European union 7th Framework Program, FP7-REGPOT-CT-2011-NOBLESSE, are
acknowledged for financial support.
Reference:
1. C. Alexander et al. J Mol. Recog. 19 (2006) 106-180.