A phenyl glycinol appended calix[4]arene film for chiral detection of ascorbic acid on gold surface

Article abstract of DOI:10.1016/j.ab.2019.113373

This paper describes the synthesis of new chiral calix [4]arene derivative having (R)-2-phenylglycinol moiety (compound 6), and its chiral recognition studies for ascorbic acid (AA) enantiomers by using Quartz Crystal Microbalance (QCM). Initial experiments indicated that the outstanding selective chiral recognition (α) was observed as 2.61 for l-enantiomer of AA. The sensitivity (S) and the limit of detection (LOD) values for L-AA were calculated as 0.0226 Hz/μM and 0.63 μM, respectively. Furthermore, the sorption behavior and mechanism of AA onto compound 6 film were evaluated and the sorption data exhibited a good correlation with the Freundlich isotherm models. The maximum uptake of L-AA by the sensor was found as 5895.76 mg/g. In conclusion, chiral recognition of AA enantiomers as real-time, sensitive, selective and effective was performed by a calixarene derivative coated QCM sensor.

Full text of DOI:10.1016/j.ab.2019.113373

Analytical Biochemistry 583 (2019) 113373
Contents lists available at ScienceDirect
Analytical Biochemistry
journal homepage: www.elsevier.com/locate/yabio
A phenyl glycinol appended calix[4]arene film for chiral detection of
ascorbic acid on gold surface
Merve Akpinara,b, Farabi Temela,b, Begum Tabakci , Egemen Ozcelika,b, Mustafa Tabakcia,b,*
c
a
Konya Technical University, Department of Chemical Engineering, 42130, Konya, Turkey
Selçuk University, Department of Chemical Engineering, 42130, Konya, Turkey
Selçuk University, Department of Chemistry, 42130, Konya, Turkey
b
c
A R T I C L E I N F O
A B S T R A C T
Keywords:
Ascorbic acid
Calixarene
Chiral detection
Quartz crystal microbalance sensor
Sensing
This paper describes the synthesis of new chiral calix [4]arene derivative having (R)-2-phenylglycinol moiety
(compound 6), and its chiral recognition studies for ascorbic acid (AA) enantiomers by using Quartz Crystal
Microbalance (QCM). Initial experiments indicated that the outstanding selective chiral recognition (α) was
observed as 2.61 for L-enantiomer of AA. The sensitivity (S) and the limit of detection (LOD) values for L-AA were
calculated as 0.0226 Hz/μM and 0.63 μM, respectively. Furthermore, the sorption behavior and mechanism of
AA onto compound 6 film were evaluated and the sorption data exhibited a good correlation with the Freundlich
isotherm models. The maximum uptake of L-AA by the sensor was found as 5895.76 mg/g. In conclusion, chiral
recognition of AA enantiomers as real-time, sensitive, selective and effective was performed by a calixarene
derivative coated QCM sensor.
1. Introduction
Additionally, it allows detecting a mass change even at a nanogram
level by interactions between analyte and sensing material in both dry
Ascorbic acid (AA) is an indispensable component in terms of teeth,
and aqueous conditions. Advantages of the QCM technique are high
sensitivity and selectivity for the sensing of biologic analytes such as
carbohydrates, antibiotics, bacteria, and DNA [5–8].
bone and skin health. Also, it is a carbohydrate-like chemical substance
that participates in metabolic functions such as absorption of iron,
collagen synthesis, and maintenance of the structure of blood vessels,
the formation of some amino acids, hormone synthesis and secretion of
the adrenal glands. Ascorbic acid has two isomers which are called L-
ascorbic acid and D-ascorbic acid. Although D-isomer is in an inactive
form, the L-isomer is in a biologically active form and it also is known as
vitamin C. Chiral recognition of biomolecules and drugs such as AA is
an essential phenomenon for various areas of chemistry and life sci-
ences. Therefore, designing efficient analytical methods is an essential
task for sufficient sensitive and selective recognition of AA enantiomers.
For the determination of AA, several methods like chromatographic [1],
spectroscopic [2], electrochemical [3] have been developed and used.
However, this kind of methods may have some disadvantages such as
over time-consuming, expensive investment cost and analysis, and
qualified staff requirement. In recent years, the sensor devices and
methods which are acoustic systems have been widely used for in-
vestigation of sensor-analyte interaction in sensor applications [4].
Quartz Crystal Microbalance (QCM) system, which is one of the
acoustic sensor systems, is based on piezoelectric and its usage is gra-
dually increasing due to easy, rapid and cheap detection of the analyte.
In the literature, some macromolecules, polymers, and nano-
particles have been widely used for the determination of biological
molecules [9–11]. Among macromolecules, calixarenes, which are or-
ganic macromolecule having a cyclic structure by phenolic units are
interconnected each other and can be designed with various functional
groups easily and have excellent interaction ability [12]. These mac-
romolecules which are conical shaped consist of upper and lower rims
and, an annulus. Calixarenes as the promising materials have received
great attention for the sensor applications due to their outstanding
sensing properties [13–15]. In past recent years, many chiral calixar-
enes which were functionalized with chiral residues at either the lower
or upper rim have been used in past recent years as chiral receptors or
catalysts [16–23].
To best of our knowledge, using the calixarenes as sensor materials
for the chiral recognition of AA enantiomers by QCM system has never
been encountered in current literature. Therefore, in this study, we
reported a simple and quick chiral discrimination strategy for AA en-
antiomers (Fig. 1) using QCM sensor which is modified the new chiral
calix [4]arene building block bearing chiral phenyl glycinol moiety on
*
Corresponding author. Konya Technical University, Department of Chemical Engineering, 42130, Konya, Turkey
E-mail addresses: mtabakci@selcuk.edu.tr, mtabakci@ktun.edu.tr (M. Tabakci).
https://doi.org/10.1016/j.ab.2019.113373
Received 19 January 2019; Received in revised form 17 July 2019; Accepted 21 July 2019
Available online 22 July 2019
0003-2697/ © 2019 Elsevier Inc. All rights reserved.

M. Akpinar, et al.
Analytical Biochemistry 583 (2019) 113373
2
. Materials and methods
.1. Reagents and instrumentations
Melting points were measured on a Stuart-SMP3 melting point ap-
2
paratus. NMR spectra were taken on a Varian 400 MHz NMR spectro-
meter. FTIR spectra were recorded on a PerkinElmer 100 FTIR spec-
trometer. Elemental analyses were performed on a Leco CHNS-932
analyzer. Analytical TLC was carried out using precoated silica gel
plates (SiO Merck F254). All reagents used in the experiments were of
2
standard analytical grade from Merck, Sigma-Aldrich, Fluka and used
without further purification.
A time-resolved QCM 200 system which is 5-MHz AT-Cut quartz
crystals (1 inch) with gold electrodes on both sides were commercially
available and purchased from SRS (California, USA) to measure the
frequency change of quartz crystals between gold electrodes. The QCM
crystals were ultrasonically cleaned using an Isolab ultrasonic bath. The
QCM sensor surface which was modified with chiral calix [4]arene was
characterized by an NT-MDT atomic force microscope (AFM, NTEGRA
Spectra, Russia) and contact angle instrument (DSA 25, Krüss, Ger-
many). We constructed the flow system with a peristaltic pump (An
ISM940E from Ismatech, Wertheim, Germany) to transfer the solutions
of AA on the sensor surface. The sensing experiments were performed in
a glove box unit (Labconco-5220120, Kansas City, USA).
Fig. 1. Used chiral ascorbic acid (AA) derivatives in the current study.
its lower rim and also thiol moiety on its upper rim (compound 6)
Scheme 1). The chiral calix [4]arene film on QCM gold surface ex-
(
hibited good and more than doubled selectivity towards L-AA. Sig-
nificantly, the chiral discrimination factor (α) [24] of the sensor was
specified by the evaluation of sensor response [25]. Accordingly, the
limit of detection (LOD) [26] and sensitivity (S) [27] of the sensor were
calculated from the analyte concentration studies to elucidate the
sensing property of the sensor. Langmuir and Freundlich isotherm
models that were also evaluated to fit the experimental data indicated
the sorption phenomena of AA enantiomers by the sensor. Furthermore,
the reproducibility of chiral calix [4]arene film on QCM gold surface
was also studied.
2.2. Synthesis
Compounds 1–4 were prepared according to literature methods
[
28–31]. Other calix [4]arene compounds 5 and 6 were synthesized for
the first time using the known procedures (please see supplementary
data for synthesis procedures).
2.3. Fabrication of sensor and sensing studies
According to Sauerbrey equation (Eqn. (1)) [32], the working
principle of QCM sensor system is based on the response (ΔF) that took
Scheme 1. Synthetic route for compound 6 (i) Dry
toluene, phenol, AlCl
Acetone, K CO , methyl bromoacetate, reflux, 24 h,
5% (iii) Toluene-methanol (1:2), (R)-(−)-2-phe-
nylglycinol, 120 h, reflux, 82% (iv) CHCl SnCl
chloromethyl methyl ether, 1 h, −10 °C, 65% (v)
MeCN, thiourea, KOH/H O, reflux, 24 h, 55%.
3
, room temperature, 4 h, 78% (ii)
2
3
7
3
,
4
,
2
2

M. Akpinar, et al.
Analytical Biochemistry 583 (2019) 113373
place according to mass change on quartz crystal (Δm).
logqe = logKf + (1/n)logCe
(4)
2
Δf (Hz) = −(56.6 Hz cm /μg) × Δm(μg)
(1)
f
where K and n are Freundlich sorption isotherm constants related to
adsorption capacity and adsorption intensity, respectively.
Initially, QCM crystal surface was properly cleaned in the ultrasonic
bath by chloroform before use to eliminate all impurities on gold sur-
face and then taken out and coated with compound 6. For deposition of
compound 6, the QCM crystal was immersed into baker containing
compound 6 solution in chloroform (3 μL, 1.0 mM) and chloroform
3. Results and discussion
3.1. Synthesis and characterization
(
[
3 mL) at room temperature and the solvents evaporated overnight
33]. AFM analysis was performed to evaluate the morphology and
In this work, a chiral phenyl glycinol-based thiol calix [4]arene
(
compound 6) was synthesized in order to investigate its chiral re-
surface roughness of compound 6 film on QCM gold surface. Further-
more, the existence of compound 6 film on QCM gold was characterized
by contact angle measurement. The coating frequency of the film was
estimated by measuring the frequency shift before and shortly after
deposition of the sensing layer [34]. Besides, the mass change on the
QCM sensor was calculated by Eqn. (1).
The chiral discrimination ability of compound 6 film on QCM gold
surface was performed according to the following procedure respec-
tively. The QCM sensor was placed in a QCM flow cell. After the fre-
quency reached the steady state during circulation of deionized water
cognition abilities towards AA enantiomers through the QCM method.
The synthesis of compound 1–4 was carried out according to previous
literature methods [28–31]. The newly synthesized compound 5 and 6
were characterized by a variety of spectroscopic techniques such as FT-
IR, 1H and 13C NMR. Their spectroscopic information was given in
supplementary data in detailed.
3.2. Analysis of the sensor film
Thiol moieties of the sensing materials can be strongly adsorbed on
(
DW) into the QCM flow cell, the frequency shifts corresponding to the
the gold surface to afford stable and ordered layers due to the high
affinity of thiol groups to a metal surface such as gold [39]. For this
reason, newly synthesized thiol functionalized compound 6 was coated
on the QCM gold surface by the soaking method. For the character-
ization of compound 6 film, topographies of QCM sensors were taken
using AFM to evaluate the changes on their surface morphologies after
deposition of compound 6 on a bare gold surface. Topographies of bare
gold surface and compound 6 coated QCM sensor were given in Fig. S7
analyte-sensor interaction by injecting 1000 μM of AA enantiomers
solutions in DW were measured for determination chiral discrimination
ability of the QCM sensor. Frequency changes of the QCM sensor were
recorded by the frequency counter and then the shifting on a frequency
was monitored from the frequency-time curve during the circulation of
AA enantiomer solutions in sensing system [35]. A home-made liquid
phase sensing system (please see supplementary data, Fig. S1) consisted
of a compound 6 film on QCM gold surface, a flow cell, an oscillator and
a QCM controller connected to a personal computer. It was observed
that the interaction between AA enantiomers and as-prepared QCM
sensor at first led to frequency shifts. After the frequency shift reached
the steady state, DW was circulated into the QCM cell to break down
the interaction between analyte and sensor. The completing of the
desorption process has been understood by reaching of frequency re-
sponse to its initial level.
(
please see supplementary data), respectively. The bare gold surface
seems to be almost smooth and homogenous (Fig. S7a) whereas it was
monitored that there are different surface morphologies occurred on the
sensor surfaces due to forming disulfide bonds between compound 6
molecules and gold surface after the coating [40]. So, the coated sensor
surface (Fig. S6b) has a number of large peaks which are the same
height and wideness. This means that compound 6 molecules may have
been irregularly coated on the sensor surface or may have overlapped
each other. The average roughness (S
bare crystal surface) to 3.62 nm after deposition of compound 6 mole-
cules. Furthermore, the increase of peak-to-peak height (S ) from
7.91 nm to 73.08 nm indicated the formation of compound 6 film on
QCM gold surface.
a
) increased from 1.66 nm (for
2
.4. Modeling of adsorption phenomena
y
The sensing process of compound 6 film towards AA enantiomers
2
was evaluated in terms of adsorption phenomena. As known, adsorp-
tion isotherms are generally used to describe the adsorption me-
chanism. For this reason, there are various adsorption models which are
reported to describe the adsorption phenomena in the literature.
Among them, Langmuir and Freundlich isotherm models are frequently
used in adsorption studies. Langmuir isotherm is represented by the
following equation [36]:
Contact angles (CA) measurements were performed for determina-
tion of wettability properties or the evidence to deposition of compound
6
molecules on the bare gold surface. Wettability properties of sensor
surface can be classified as high wettability (θ«90°) or low wettability
θ»90°) [41]. The CA of the bare gold surface was 68° (Fig. S6a, please
(
see supplementary data). After deposition of compound 6 molecules,
the surfaces of gold became hydrophobic. So, CA of the coated sensor
surface has been determined as 84.9° (Fig. S6a, please see supplemen-
tary data). Hence, the increases at CA values due to the hydrophobic
moieties of calix [4]arene molecules confirmed that the deposition of
compound 6 molecules was performed on a bare gold surface.
Ce/q = (1/q b) + (Ce/q )
(2)
e
0
0
where C
e
is the equilibrium concentration (mg L−1) in solution, q
e
is the
−1
0
adsorption capacity (mg g ) at equilibrium, q indicates the adsorp-
−1
tion capacity (mg g ) and b is a constant related to the adsorption
energy (L mmol ).
−1
To determine whether the adsorption processes of AA enantiomers
by the current QCM sensor are favorable or not to the Langmuir type
adsorption process, the favorable nature of adsorption can be expressed
in terms of dimensionless equilibrium parameter [37]:
3
.3. Real-time chiral discrimination and quantification of AA enantiomers
The compound 6 film on QCM gold surface was employed for re-
cognition assays of AA enantiomers as demonstrated in methods. Fig. 2
illustrated the frequency-response curves of the sensor towards the AA
enantiomers. As is seen in Fig. 2, the frequency responses of the QCM
were decreased quickly and reached equilibrium within 5 min after AA
enantiomers were injected into the QCM flow cell. The decreasing of
frequency responses indicated that interactions between AA en-
antiomers and compound 6 molecules. The affinity of compound 6 to L-
AA enantiomer was approximately more than doubled when it was
compared with D-AA enantiomer which depends on their
R
L
= 1/(1 + bC
0
)
(3)
where b is Langmuir constant (L mmol−1). The values of R
the type of the isotherm:
0
indicates
R = 1, linear;
L
L
R
L
> 1, unfavorable;
= 0, irreversible.
The Freundlich isotherm was also applied for the adsorption of AA
L L
< R < 1, favorable; R
enantiomers by the current QCM sensor. Freundlich isotherm model is
given by the following equation [38]:
3

M. Akpinar, et al.
Analytical Biochemistry 583 (2019) 113373
stereochemistry [24]. According to the “Lock-and-Key Principle”, the
difference in recognition ability of the QCM sensor for AA enantiomers
may be explained with the size-fit concept, three-dimensional structures
of molecules, steric effects and interaction between moieties of the
sensible film layer and analyte molecules such as hydrogen bonding
interactions [42–44]. Therefore, it is believed that the hydrophobic
cavity of compound 6 and stereochemically position of phenyl glycinol
moieties on compound 6 preferred L-enantiomer to D-enantiomer of AA.
The effectiveness of the QCM sensor can be well specified by the
chiral discrimination factor αsens, which is defined as [45];
ΔfL
ΔfD
αsens =
(5)
Here, Δf
L
and Δf
D
denote frequency changes of the QCM sensor towards
the same concentration of respective enantiomers of AA, respectively.
The αsens for compound 6 film towards AA enantiomers was calculated
by Eqn. (5) as 2.61 which indicated that AA enantiomers were easily
discriminated by the sensor [24].
In further experiments, sensing performance of the QCM sensor was
tested towards AA solutions having different concentrations (100, 250,
Fig. 2. Individual sensing curves of AA enantiomers (1000 μM) by the QCM
sensor.
500 and 1000 μM). The frequency responses increased proportionally to
the increase of AA concentrations. These changes on frequency re-
sponses of the QCM sensors towards AA enantiomers were given in Fig.
S8 and Fig. S9 (please see supplementary data), respectively. Ad-
ditionally, the calibration curves for frequency responses of the QCM
sensor towards AA enantiomers are plotted in Fig. 3. Both the QCM
sensor responses and the chiral discrimination factor (inset of Fig. 3)
increased by the increasing of AA concentrations.
Sensor sensitivity (S) was determined as 0.0226 (for L-AA) and
0.0083 (for D-AA) Hz/μM by the ratio of frequency changes (Hz) versus
AA solutions in different concentrations (μM) which is the slope of
calibration curves (Fig. 3) [46]. Limit of detection (LOD) of the QCM
sensor was determined as 0.63 μM and 0.27 μM towards L-AA and D-AA
enantiomers, respectively [47]. The limit of detections of the QCM
sensor towards AA enantiomers was compared with their linear range
in the literature (Table 1).
3.4. Adsorption evaluation for AA sensing
Fig. 3. Calibration curves of the QCM sensor towards AA enantiomers in dif-
ferent concentrations. The inset figure depicts the changing of the chiral dis-
crimination factors corresponding concentrations of AA enantiomers.
The Langmuir and Freundlich isotherm models were used to specify
the adsorption mechanism. For this reason, the C /q versus C was
e e e
plotted for Langmuir isotherms using the sensing results of AA en-
antiomers (please see supplementary data, Fig. S10). The constants of
0
Langmuir isotherm model, q and b, were calculated as 5895.76 mg/g
and 0.0284 (for L-AA) L/mmol from the slope and intercept of the
linear plots, respectively and were given in Table 2. These results
suggested that the adsorption of L-AA onto compound 6 film occurred
with the formation of a monolayer and that the weak force (small value
for the parameter b) between the adsorbent and the adsorbate is the
result of physical interaction [54]. Furthermore, dimensionless equili-
brium parameters were calculated and given in Table 2. These values
were between zero and one at the range of 100 and 1000 μM initial AA
concentrations indicating favorable adsorption.
Table 1
Comparison of the recently reported methods for AA detection.
Methods
Analyte
Linear range
LOD
Ref.
Electrochemical
Electrochemical
UV–Vis
Fluorescent
Colorimetric
AgNPs-HPLC
QCM
AA
AA
AA
AA
AA
AA
D/L-AA
10–800 μM
9.6 μM
[48]
[49]
[50]
[51]
[52]
[53]
This work
50 μM - 7.4 mM
12.5–100 μM
1–100 μM
20.0 μM
1 μM
0.59 μM
2 nM
14.63 μM
0.27/0.63 μM
0.01–100 μM
25–150 μM
100–1000 μM
The values of K
of the plots of log q
S11). Freundlich isotherm data were also given in Table 2. On the
f
and n were calculated from the intercept and slope
e
versus log C (please see supplementary data, Fig.
e
Table 2
Equilibrium adsorption parameters of AA enantiomers according to Langmuir and Freundlich models.
Enantiomers
Langmuir
(mg/g)
Freundlich
q
0
b (L/mmol)
R2
R
L
K
f
n
R2
D-AA
L-AA
223.08
5895.76
0.3917
0.0284
0.8393
0.8332
0 < R
0 < R
L
< 1
< 1
0.776
0.982
1.175
1.011
0.9993
0.9999
L
4

M. Akpinar, et al.
Analytical Biochemistry 583 (2019) 113373
Fig. 4. The repeatability test of compound 6 film towards L-AA enantiomer ([L-AA]: 1000 μM).
comparison of the R2 values, it can be concluded that Freundlich
equations represent the better fit to the experimental data in adsorption
of AA enantiomers onto the surface of compound 6 film. The maximum
adsorption capacity of compound 6 is higher than other adsorbents for
L-AA in the literature [55–58]. As known, the polymeric materials were
widely used in adsorption applications. For this reason, a polymeric
derivative of compound 6 may be useful adsorbent for AA adsorption
applications in aqueous media.
film was produced on the QCM sensor surface of compound 6 which has
outstanding properties such as real-time, sensitive, effective and selec-
tive chiral detection for AA enantiomers, durable and easily recoverable
with distilled water.
Acknowledgments
We thank the Scientific and Technological Research Council of
Turkey (TUBITAK-Grant Number 115Z249) and the Research
Foundation of the Selçuk University (SUBAP-Grant Number 17201035)
and for financial support of this work produced from Merve Akpinar's
M.Sc. Thesis.
3.5. Repeatability of the sensor
One of the most important parameters of sensors is well known as
repeatability. In order to examine the repeatability of compound 6 film
on the gold surface (it was prepared again which has 110 Hz mass
loading) towards L-AA, it was exposed to a solution of L-AA (1000 μM)
at least five times and the changes on frequency responses of the sensor
was recorded and given in Fig. 4. After every adsorption progress,
desorption processes were performed via DW injection into the QCM
system. The results showed that the differences in the responses of the
QCM sensor remained almost constant after each process. This de-
monstrated that the compound 6 film on gold sensor showed a superior
reproducibility in sensing of L-AA.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://
doi.org/10.1016/j.ab.2019.113373.
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