Highly selective flurogenic chemosensor for cyanide ion in aqueous medium and its applications of logic gate and Hela cells

Article abstract of DOI:10.1016/j.molliq.2021.116076

We have successfully synthesized triphenylamine-based fluorophores (MK and HK) with cyanoacrylic acid as a receptor for CN^– ion sensing in a 99% aqueous medium. From the emission titration spectra, the detection limit of cyanide ion calculated towards MK and HK, respectively, are 234 nM and 11 nM. The observed binding constants for MK and HK, respectively, are 27 × 10^-3 M and 10 X 10^-2 M. The plausible sensing mechanism is confirmed by various methods such as Job's plot experiment, proton NMR titration, and density functional theory. Furthermore, the prominent application is the naked-eye detection of cyanide from non-fluorescent to greenish-yellow fluorescent under 365 nm UV light. Based on the observed data from fluorescence spectroscopic studies, a new logic circuit is designed. Moreover, the potential application of HK and MK in the Hela cell line exhibited turn on fluorescence image for cyanide ion through the inhibition of the ICT process. In addition to that, the probe MK and HK is successfully applied in the analysis of the real sample for the rapid detection of cyanide ions.

Full text of DOI:10.1016/j.molliq.2021.116076

Journal of Molecular Liquids 334 (2021) 116076
Contents lists available at ScienceDirect
Journal of Molecular Liquids
journal homepage: www.elsevier.com/locate/molliq
Highly selective flurogenic chemosensor for cyanide ion in aqueous
medium and its applications of logic gate and Hela cells
a
a
a
b
Harikrishnan Muniyasamy , Chithiraikumar Chinnadurai , Malini Nelson , Aravind Manikka Kubendran ,
b
b
a
a,
⇑
Karthika Sukumaran , Ashokkumar Balasubramaniem , Murugesan Sepperumal , Siva Ayyanar ,
Mani Govindasamy , Ayman Ghfar , Fehaid Mohammed Alsubaie
Supramolecular and Organometallic Chemistry Lab, Department of Inorganic Chemistry, School of Chemistry, Madurai Kamaraj University, Madurai 625021, Tamil Nadu, India
School of Biotechnology, Madurai Kamaraj University, Madurai 625021, Tamil Nadu, India
Advanced Materials Research Chair, Chemistry Department, College of Science, King Saud University, Riyadh 11451, Saudi Arabia
NationalCenter for Chemical Catalysis, King Abdulaziz City for Science and Technology, P.O. Box 6086, Riyadh 11442, Saudi Arabia
c
c
d
a
b
c
d
a r t i c l e i n f o
a b s t r a c t
Article history:
We have successfully synthesized triphenylamine-based fluorophores (MK and HK) with cyanoacrylic
acid as a receptor for CN ion sensing in a 99% aqueous medium. From the emission titration spectra,
Received 29 November 2020
Revised 29 March 2021
Accepted 3 April 2021
Available online 09 April 2021
–
the detection limit of cyanide ion calculated towards MK and HK, respectively, are 234 nM and
-3
-2
1
1 nM. The observed binding constants for MK and HK, respectively, are 27 Â 10 M and 10 X 10 M.
The plausible sensing mechanism is confirmed by various methods such as Job’s plot experiment, proton
NMR titration, and density functional theory. Furthermore, the prominent application is the naked-eye
detection of cyanide from non-fluorescent to greenish-yellow fluorescent under 365 nm UV light.
Based on the observed data from fluorescence spectroscopic studies, a new logic circuit is designed.
Moreover, the potential application of HK and MK in the Hela cell line exhibited turn on fluorescence
image for cyanide ion through the inhibition of the ICT process. In addition to that, the probe MK and
HK is successfully applied in the analysis of the real sample for the rapid detection of cyanide ions.
Ó 2021 Elsevier B.V. All rights reserved.
Keywords:
Triphenylamine dyes
Cyanide sensor
Theoretical studies
Logic circuit
Hela cells
1
. Introduction
Triphenylamine based organic dye molecules have been broadly
[12]. Moreover, the revelation of cyanide in the least quantity
causes queasiness, convulsion, loss of cognizance, and ensuing
death [13,14]. Interestingly, fluorescent chemosensors could detect
–
betrothed for optoelectronics, hole transporting materials, sensors,
and dye sensitized solar cells due to their good electron donating
and transporting capability [1–3]. Based on these striking features,
CN ions either by fluorescence enhancement or by fluorescence
quenching in consequence of hydrogen bonding, displacement
approach, nucleophilic addition, intra/intermolecular charge trans-
fer, fluorescence resonance energy transfer and photoinduced elec-
tron transfer mechanism [15–16]. To date, numerous literature
were reported for cyanide detection by various methods. Amidst
those, recently, Lin et al. [17] established an efficient probe of
cyclometallated phosphorescent iridium complex for selective cya-
nide detection in 95% of acetonitrile solvent. Kim et al. [18]
described potential dependent electrochemiluminescence for
selective molecular sensing of cyanide but the sensing medium is
acetonitrile and water in equal ratio. Sarkar et al. [19] employed
pyridine appended poly alkyl ether based ionogels to detect cya-
nide ion by colorimetric method and in the absence of fluorescence
methods. Mondal et al. [20] described a tandem detection of sub-
molecules with D À
p
À D and D À A type architecture with triph-
enylamine core were effectively used for energy and environmen-
tal applications [4,5]. Instantaneously, the booming of fluorescent
chemosensors for anion recognition fascinated a prodigious com-
pact of consideration over the past two eras on account of the sig-
nificance of various anions in an extensive range of ecological and
–
biological advancements [6]. Of these anions, cyanide (CN ) plays a
protruding role in all aspects because of its toxic and lethal nature.
Despite its disastrous nature, CN ions involved in unprecedented
application in gold mining, chemical warfare agent, electroplating,
medicine and plastic manufacturing etc. [7–11]. The indorsed level
–
of cyanide in drinking water was ascertained by WHO as 1.9
lM
À
2+
nanomolar level CN and Hg by a suitable molecular sensor. Li
et al. [21] reported that the detection of cyanide ion in THF solvent.
Dalkilic et al. [22] reported the triphenylamine based probe for the
⇑
Corresponding author.
E-mail address: siva.chem@mkuniversity.org (S. Ayyanar).
https://doi.org/10.1016/j.molliq.2021.116076
167-7322/Ó 2021 Elsevier B.V. All rights reserved.
0

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
selective detection of cyanide ions in DMSO/water (90:10) ratio.
Lin et al. [23] reported the detection of cyanide ion in THF: water
rate, cells were treated with different concentrations of the probe
and analyte ranging from 0.1 mM to 1.0 mM for 24 h in triplicates.
Later, cells were gently washed twice with phosphate buffer and
100 mL of MTT (5 mg/ml) were treated for 4 h. Finally, DMSO was
mixed followed by removal of MTT, and measurement was taken
at 570 nm in a microplate reader. The untreated cell lines treated
as control were expressed as 100% viability to delineate the cyto-
toxic effects of the probes and analyte.
(
70:30) medium. All the above-mentioned reports are not applied
for real sample analysis, and the sensing medium is a partially
aqueous medium. A. Ozdemir et al. [24] discussed the tripheny-
lamine based receptor for cyanide ion detection in acetonitrile sol-
vent and performed the application in real sample analysis. Qi et al.
[
25] reported cyanide detection by using a green fluorescent emis-
sive probe in an aqueous medium applied for biological cell imag-
ing studies with cytotoxicity of 0.1 mM. They have not done real
sample analysis. Among these reported results, the reported opti-
mum medium for the detection of cyanide ion is a partial aqueous
or non-aqueous medium, which is quite difficult for the real sam-
ple analysis. In this view, we planned to design and developed the
chemosensors for the selective detection of cyanide ions in the
environmental system and biological fields under an aqueous med-
2
.5. Visualization of fluorochrome spectrum of probe & probe-cyanide
complex in Hela cell-lines
Hela cells were treated with probe and probe-cyanide with the
assigned IC50 concentration in order to visualize the emission and
excitation spectrum under the fluorescent microscope. For that,
cells were seeded in 12 well plates and incubated up-to 80% con-
fluency. Subsequently, the probes HK, MK and their corresponding
cyanide complex were treated for an hour. Later, cells were washed
thrice and suspended with phosphate buffer saline for the fluo-
rochrome observation under the fluorescent microscope.
ium. To the best of our knowledge, this is the first D À
p
À D À A
type triphenylamine based molecular structural design employed
for the worthwhile detection of cyanide ion in 99% aqueous med-
ium and applied in live cell imaging at a higher wavelength with
low cytotoxicity.
3
. Results and discussion
2
. Experimental methods
3
.1. UV–vis and emission spectral responses of MK and HK towards
2.1. 1. Materials and methods
–
CN ion
All reagents and materials were bought from Sigma Aldrich and
The photophysical properties of synthesized probes were deter-
Alfa Aesar without further purification. Further, the analytes used
were purchased from Sigma-Aldrich. The Mizoroki-Heck cross cou-
pling reaction was carried out under nitrogen atmospheric condi-
tions. Silica gel-G plates (Merck) were used for thin-layer
chromatography (TLC) analysis with a mixture of petroleum ether
and ethyl acetate as an eluent.
mined by both absorbance and emission spectroscope in an aque-
ous medium (Fig. 1). In the absorbance spectrum, MK exhibited
three absorbance bands at 300, 380 and 440 nm. The bands at
3
00 and 380 nm were attributed due to p-p* and n-p* transition
respectively. Another lower energy 440 nm band is observed by
the intramolecular charge transfer from methoxy substituted phe-
nyl to cyano acrylic acid through the triphenylamine moiety. The
HK absorbance spectrum shows that one broadband from 313 to
2
.2. Instrumental method
3
79 nm, this band may be due to the p-p* and n-p* transition
The H and 13C NMR spectra were recorded on Bruker (Avance)
1
and the 445 nm band of HK can be attributed to the intramolecular
charge transfer from hexyloxy substituted phenyl to cyano acrylic
acid through the triphenylamine moiety. Hereafter, emission spec-
tra were recorded using the maximum absorbance band of absor-
bance spectra. The emission spectra of MK and HK show a
maximum intensity at 614 nm and 604 nm, respectively, this emis-
sion band may be due to the intramolecular charge transfer from
donor to acceptor of the cyanoacrylic acid.
4
00 NMR instrument, and the chemical shifts were recorded as d
values in parts per million (ppm) relative to tetramethylsilane with
coupling constant (J) values in hertz (Hz). We carry out absorption
spectra using JASCO V-630 UV À vis spectrophotometer and fluo-
rescence spectra were carried out using JASCO F-8500 fluorescence
spectrophotometer. The slit width was 5 nm for the use of each
absorption and fluorescence spectra. Both spectra analysed by
using the quartz cuvette with 1 cm path length.
2.3. Preparation of stock solution
The stock solution of the probe (1 mM) was dissolved in DMSO
solvent. The stock solution of the analyte was dissolved in double
-4
distilled water. The stock solution (1 Â 10 M) of the synthesized
probes were prepared in 3 ml of DMSO solvent after that 2 L of
l
the stock solution was taken into 2 ml of double distilled water sol-
vent placed in a 3 ml cuvette, and the total concentration of sam-
ples was 100 nM for the selectivity and competitive experiments in
both absorbance and emission spectroscopy. The emission spectra
of probe and probe with analyte were measured by using the max-
imum absorbance wavelength of the probe as an excitation point.
2.4. Biological experiments
The cytotoxicity effects of the probes (HK & MK) and analyte
–
(
CN ) were scrutinized by MTT assay prior to bio-imaging. Initially,
Hela cell lines were counted in haemocytometer and seeded
0,000 cells in each well on a 96-well plate. At the 80% confluency
1
Fig. 1. Normalized absorbance and emission spectra of receptors.
2

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
As seen in Fig. 2, receptor MK alone displayed a single weak
emission band at 614 nm, hereafter enhancement of emission
intensity was witnessed in the existence of CN– ion on the other
hand no spectral discrepancies were perceived for other interrupt-
ing anions, MK produced a strong intense sharp emission band at
–
5
74 nm with the hypsochromic shift in the presence of CN ions.
The competitive experiment results show that the probe alone
and probe with the analyte (except cyanide ion) shown only weak
emission, but in the presence of cyanide ion strong emission band
at 574 nm has appeared, this clearly shows that MK selectively
senses cyanide ion over other analytes (Fig. 3). The emission titra-
tion of the receptor MK with different concentration of cyanide ion
is shown in Fig. 4 the titration spectra shows the gradual addition
–
of CN into probe MK, the probe MK shows a hypsochromic shift
from 614 nm to 574 nm.
The probe HK alone exhibits a weak emission, but, over the
selected anions, the addition of cyanide ion attributes to the
increased emission intensity with the hypsochromic shift from
6
04 to 564 nm (Fig. 5a). Then the interference experiment shows
–
–
-
–
3
Fig. 3. Interference study of 1. MK alone 2. MK + CH COO +CN , 3. MK + Br +CN , 4.
that the probe alone, the probe with other analytes (except cyanide
ion) has weak emission at 604 nm, furthermore, probe with cya-
nide ion only and probe with cyanide in presence of other interfer-
ing anions shows strong intense emission at 564 nm. This clearly
shows that our HK receptor selectively senses cyanide ion even
in the presence of some other interfering anions (Fig. S3). As it
can be seen with the gradual addition of cyanide anion into the
probe HK, fluorescence emission intensity was gradually increased
with a hypsochromic shift from 604 nm to 564 nm (Fig. 5b). The
limit of detection (LOD) for receptor was calculated based on the
-
–
-
–
-
–
–
–
–
2-
–
2–
-
2-
–
3 4
CN , 9. MK + S +CN , 10. MK + CO +I , 11. MK + SO +CN .
emission titration spectra by using the equation 3r/K, where r
is the standard deviation of the probe, K is the slope which was
derived from a titration curve, and LOD of MK and HK are
2
34 nM and 11 nM respectively. The binding constant value for
MK and HK were determined by using modified Benesi - Hilde-
brand equation, 1/I-Imin = 1/ Imax-Imin + (1/K[C]) (1/ Imax-Imin) here,
Imin is the emission intensity of probe alone, I is the emission inten-
sity of receptor with any given concentration of cyanide ion, Imax is
the emission intensity of receptor at a concentration of complete
saturation, K is the binding constant, [C] is the concentration of
the receptor. The binding constant value has been determined from
the slope of the plot (Imax-Imin) / (I-Imin) vs 1/[C] for probe-analyte.
2
À1
2
The binding constant of MK and HK are 2.7 X 10 M and 10 X 10
À1
M
respectively. (See Scheme 1)
-7
Fig. 4. Sensitivity of MK (1X10 M)with different concentration of cyanide ion
from 1X10-7 M to 40 X10 M.
-7
3.2. Sensing mechanism of the probe with the analyte
The stoichiometric ratio of the probe and analyte plays a major
role to predict the sensing mechanism so that we find out the bind-
ing stoichiometries of our receptors MK and HK with cyanide ion
with the help of Job’s plot. The Job’s plot experiment shows that
the binding stoichiometry of MK with cyanide ion is 1:1 stoichio-
metric ratio (Fig. 6a), and HK probe binds with cyanide ion via
1
:1 binding mode which is represented in Fig. 6b. This binding sto-
ichiometry shows that one molecule of the probe reacts with one
molecule of the analyte.
Furthermore, the sensing mechanism of the probe with the ana-
lyte was investigated by the proton NMR titration method. NMR
spectra of MK shows (Fig. 7), the peak at 3.80 ppm corresponds
to the methoxy proton. Singlets observed at 6.78 and 6.42 are
attributed to methoxyl substituted phenyl proton, and the signal
at 8.08 ppm is equivalent to the vinyl proton of the acceptor and
the remaining peaks are aromatic proton of triphenylamine amine
moiety, after the addition of one equiv. of cyanide ion to the MK
Fig. 2. Selectivity spectra of MK(1X10-7 M) with various anions (1X10-6 M).
3

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
Fig. 5. (a) Selectivity spectra of HK (1X10-7 M) (b) Sensitivity spectra of HK with various concentrations of cyanide ion from 0.5 X10-7 M to 10X10-7 M.
Scheme 1. Schematic representation of the target probe MK and HK. Reagents and Conditions: (a) KIO
3 3
/KI, CH COOH, 80 °C; (b) sodium hydride, DMF, 0 °C (c)
Methyltriphenylphosphonium iodide, DCM, KOtBu, rt; (d) Pd(OAc)
acetonitrile, rt. [26–28]
2
, tetra butylammoniumbromide, triethylamine, DMF/toluene (1:1), 95 °C; (e) cyanoacetic acid, piperidine,
probe, the vinyl proton at 8.08 ppm was disappeared and at the
same time, the new peak appeared at 5.46 ppm which is represen-
tative of the vinyl ethyl proton and the remaining triphenylamine
proton is slightly upfield. The next probe HK displayed four singlets
at 8.43, 8.10, 6.74 and 6. 38 ppm represents the carboxylic acid
proton, vinyl proton, and hexyloxy substituted aromatic proton
respectively. The remaining aromatic region is from the tripheny-
lamine moiety proton. After the addition of one equiv. of cyanide
ion to the receptor of HK, the vinyl proton vanished and the new
peak appeared at 5.54 ppm, which may be due to the vinyl ethyl
proton and the triphenylamine proton gets slightly upfield. The
NMR results clearly show that our receptor and analyte have 1:1
binding mode and the nucleophilic substitution was carried out
by cyanide ion. (See Figs. 8-10)
4

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
Fig. 6. Jobs plot analysis of (a) MK and (b) HK, 1X10-7 M concentration of probe and analyte solutions were used.
Fig. 7. 1HNMR titration of MK alone and MK with one equiv. of cyanide ion.
In addition to that, our sensing mechanism was investigated by
density function theory through Gaussian 09 software. The theo-
retical calculation was optimized by using restricted B3LYP/6-
changes the conjugation system, which restricts the intramolecular
charge transfer process. This study also further supports our plau-
sible sensing mechanism (Scheme 2).
3
1G (d, p) functions as a basis set for both probe and analyte.
The electron density of both MK and HK has donor and center core
of the triphenylamine in the ground state energy level, but in the
excited state energy level electrons are transferred from tripheny-
lamine to the cyanoacrylic acid this transition clearly shows that
our receptors have an intramolecular charge transfer. After that,
a receptor with analyte ground state energy level electron density
present in the donor group and triphenylamine moiety but in the
excited state electrons are does not delocalized into the acceptor
part of cyanoacrylic acid, this phenomenon is due to the nucle-
ophilic addition of cyanide to the b-carbon of the vinyl group
3.3. Naked eye detection
From the naked eye system (under UV light), among the various
–
2–
–
-
-
-
-
-
–
2-
anions analyzed CH
3
COO , CO
3 2 4 2
, CN , Br , Cl , F , H PO , I , NO , S
2
-
and SO
4
, the probes MK and HK effectively interact with cyanide
anion. We observed weak fluorescence of MK and HK in an aque-
ous medium which changed into strong yellow fluorescence,
respectively, when the cyanide anion was added to MK and HK
(Fig. 11 and Fig. 12 respectively).
5

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
Fig. 8. 1H NMR titration of MK alone and MK with one equiv. of cyanide ion.
Fig. 9. (a) Optimized structure of MK, molecular orbitals of (b) MK alone (c) MK with cyanide ion.
–
3
.4. Real sample analysis
of CN at concentration levels of 50–80 and 20–50
lM for MK and
–
HK respectively. These concentrations of CN solution were spiked
in all real samples. All the characteristics data were tabulated in
Table S1 and S2. The detection of CN ion concentration was very
close to the concentration of added CN ions. The recovery of MK
and HK in the range of 97–108% and 96 to 115% respectively, indi-
More importantly, the probe MK and HK was successfully used
to further detection of CN– in the real water samples containing
reverse osmosis water and tap water, samples were collected from
Madurai district, Tamilnadu, India. We prepared the stock solution
–
–
6

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
Fig. 10. (a) Optimized structure of HK (b) Molecular orbitals of HK alone and (c) HK with cyanide ion.
Scheme 2. Plausible sensing mechanism of receptors with CN– ion.
cates the excellent selectivity and high sensitivity of MK and HK for
detection of CN ion in commercial water samples with high
accuracy.
Primarily the cytotoxicity of the receptor was inspected by MTT
assay. Hela cells were treated with receptors and cyanide ions sep-
arately with the assigned IC50 concentration in order to visualize
the emission and excitation spectrum under a fluorescent micro-
scope. This study exposes the less toxicity of probe MK and HK
À
3.5. Live cell imaging studies of Hela cells
against Hela cell line, respectively, is 7.1 X 10- M and 4.0 X 10
4
-4
After that, our optical study proves that our probe selectively
M which is compared to other literature reports [21,25]. Among
these two probes, the HK has high toxicity compared to MK, the
reason is the long alkyl chain presence in the HK receptor. The
senses cyanide ion over other analytes, so that we move on to
the biological applications and the detection efficiency of our
receptors towards cyanide ion was examined with Hela cells.
receptors MK (7.1 X 10- M) and HK (4.0 X 10 M) pre-treated Hela
4
-4
7

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
3 3 2 4 2 4
Fig. 11. Photograph of fluorometric response of MK with various anions. MK, CH COO , CO , CN , Br , Cl , F , H . (From left to right).
PO- , I , NO–, S2- and SO
–
2–
–
-
-
-
-
2-
3 3 2 4 2 4
Fig. 12. Photograph of fluorometric response of HK with various anions. HK, CH COO , I , CO , Br , CN , Cl , F , H . (From left to right).
PO- , NO–, S2-, and SO
–
-
2
-
–
-
-
2-
Fig. 13. Fluorescence microscopic imaging of Hela cells, A- Bright field image; B- Florescent image of probe; C- bright field image; D - Florescent image of probe-cyanide
complex.
cells showed weak yellow fluorescence, while those are turned to
greenish yellow color in the presence of cyanide ions (1.2 X 10-4
Table 1
M) (Fig. 13). These studies prove that our receptor has a high
potential for in-vitro applications.
Truth table for molecular logic circuit.
Input (HK alone)
Input (HK-CN-)
Output (kemi = 564 nm)
0
0
1
1
0
1
0
1
0
1
0
1
3.6. Logic gate
The laws of Boolean algebra, the tailor-made chemosensors
can be viewed as computational devices that are used in
8

H. Muniyasamy, C. Chinnadurai, M. Nelson et al.
Journal of Molecular Liquids 334 (2021) 116076
Fig. 14. Molecular logic circuit.
physical or chemical inputs to generate outputs based on a set
of logical operators [29]. The chemosensor HK was examined to
design the two input logic systems, probe alone and probe with
cyanide ion and the output of the logic system is 564 nm emis-
sion band. We construct the truth table based on the emission
data in probe alone and probe with cyanide, based on the truth
table, we mimic the logic gate with the help of various gates
such as NOT, OR, AND, XOR (Table 1). The role of the logic
circuit of HK for the detection of cyanide ions will be of great
importance in the field of molecular electronics and
nanodevices (Fig. 14).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.molliq.2021.116076.
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Declaration of Competing Interest
The authors declared that there is no conflict of interest.
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We acknowledge the financial support from the Council of Sci-
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EMR-II, New Delhi and the Department of Science and Technology,
SERB, Extramural Major Research Project (Grant No.
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