Selective and sensitive colorimetric sensor for CN- in the absence and presence of metal ions (Cu2+/Ni2+): Mimicking logic gate behaviour

Article abstract of DOI:10.1039/c6ra14237k

Enone based anion sensors have significance due to their colorimetric reaction upon deprotonation and variable occurrence in the conjugated moiety. We have designed a novel and easily forming cromene-isonicotinohydrazide based probe, exhibiting selectivity towards CN^- through the naked eye. A Job's plot displays 1:1 stoichiometry along with a 0.76/0.68 μM detection limit. The results accentuate that upon addition of cations (Cu²⁺/Ni²⁺) to the heteroatom of donor moiety, sensitivity improves. The limits of detection were found to be 3.5/6.3 μM in the presence of Cu²⁺/Ni²⁺. The mechanism was proved by FTIR, NMR, DFT and -OH titration.

Full text of DOI:10.1039/c6ra14237k

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-
Selective and Sensitive Colorimetric Sensor for CN in Absence and
2
+
2+
Presence of Metal Ions (Cu /Ni ): Mimicking Logic Gate
Behaviour†
Received 00th January 20xx,
Accepted 00th January 20xx
Nirma Maurya, Shubhrajyotsna Bhardwaj, Ashok Kumar Singh∗
DOI: 10.1039/x0xx00000x
www.rsc.org/
Indian Institute of Technology-Roorkee, Roorkee (247667) India
Enone based anion sensors have significance due to their colorimetric reaction upon deprotonation and variable
occurrence in the conjugated moiety. We have designed a novel and easily forming cromene-isonicotinohydrazide based
-
probe, exhibits selectivity towards CN through nacked eye. Job’s plot displays 1:1 stoichiometry along with 0.76/0.68 μM
2
+
2+
detection limit. The results accentuate that upon addition of cations (Cu /Ni ) to the heteroatom of donor moiety,
2
+
2+
sensitivity improves. The limit of detection were found to 3.5/6.3 μM in presence of Cu /Ni . The mechanism was proved
by FTIR, NMR, DFT and –OH titration
.
5
,6
2+
subsequent hypoxia. CN¯ increases the concentration of Ca
within the cell, consequently increasing the level of ROS
reactive oxygen species), which inhibit antioxidant defence
Introduction
(
Anion recognition has become
a prevalent area of
7
,8
systems. The lethal concentration of CN¯ has been suggested
9
to be between 23-26 mM in blood of fire victims. The WHO
investigation due to its prospective role in the environmental
1
,2
chemistry and in numerous biological processes etc. Among
anions CN¯ is enormously toxic for mammals, even moderately
lesser amounts (0.5-3.5 mg/kg of body weight) are disastrous
has set a determined tolerant level of CN¯ limit (1.9μM) in
1
0
drinking water. Therefore, the development of selective and
effective CN¯ sensors is essential. In past few years, a number
of recognition approaches such as electrochemical method,
chromatography, flow injection analysis and atomic absorption
3
to human biengs. It has widespread industrial applications
including electroplating, gold mining, textile, metallurgy,
4
plastic and paper industries. Extensive use of CN¯ may also
1
1
spectrometry have been established for CN¯ detection.
However, most of these physical methods are costly, time
consuming and require sophisticated equipment’s. However,
colorimetric sensors have become most attractive due to
induced changes in optical properties of the probe with naked
cause a foremost environmental hazard. CN¯ toxicity arises
due to its binding propensity with cytochrome c oxidase,
disturbing ETC (electron transport chain) and causing
1
2-15
eye detection.
Three foremost methodologies have been
used to develop CN¯ sensors, (i) hydrogen bonding interaction
with the donor site, which changes the electronic properties of
1
2,16
the sensors,
(ii) metal displacement assay, which includes
the development of a stable CN¯ complex with the metal ion
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n
and creates alteration in the microenvironment of the sensor, 1/[CN¯] , where n is the stoichiometry. For H NMR titrations,
1
1
7,18
resulting in changes the chemical properties
6
and (iii) probe and CN¯ were prepared in d -DMSO.
generation of new species via nucleophilic addition with
probe, which produces different optical properties
1
9,20
3
. Results and discussion
(
chemodosimeter approach).
Among these hydrogen bond
1
based sensors comprise a variety of molecules viz. thiourea,
5b
3
.1 Synthesis and characterization of L1 / L2
1
6d
16a
21
imidazole, amide, azophenol etc. However, numerous
sensors for CN¯ detection via hydrogen bonding have poor
selectivity and suffer from coexisting interference by anions
The synthetic method of L1/L2 is validated in Scheme 1. An
ethanolic solution of 3-formyl chromone darivatives (1mmol),
2
4
2
1,22
(which was synthesised by previously reported literature )
and acylhydrazone (1mmol) were mixed & refluxed. After
completion of the reaction mixture (thin layer chromatography
monitored), white colored ppts were obtained with 80% yield.
Characterization of L1- ((6-fluoro-4-oxo-4H-cromen-3-yl)
methylene)isonicotinohydrazide.
such as H
2
PO
4
¯, AcO¯ and F¯.
In this work, we have planned
a cromone containing acylhydazone based pobes, having –NH
group as reaction site (accountable for interface with the
analyte) and -C=O group as signalizing unit (delivers optical
signal signifying the analyte interaction). The ionic interaction
of CN¯ with amidic -NH group via hydrogen bonding affects the
ICT efficiency of probe and induces naked-eye color detection.
The -C=N and –C=O chelating groups have high binding affinity
towards transition metal ions, therefore our probe shows
Anal. calc. (C16
3 3
H10FN O ): Theoretical (%) - C-61.74, H-3.24, N-
1
3.5, O-15.42; Experimental (%) C- 61.95, H-3.118, N-13.63.
IR (KBrcm−1): 3415 (-NH), 3018 (H-C=N), 1708 (N-C=O), 1647
2
+
2+
-
(-C=O), 1611 (-C=N) (Fig. S1).
1
H NMR (d DMSO-500MHz) δ/ppm: 12.19 (s 1H), 8.90 (s 1H),
6
selectivity towards Cu and Ni metal ions. Generally CN has
2
+
2+
strong affinity towards Cu /Ni and the photophysical
1
properties of probe change via displacement approach . In
5
8.80 (d 2H) 8.64 (s 1H), 7.92-7.77 (m 5H) (Fig. S2).
1
3
2
+
2+
C NMR (d
41, 142, 148, 151 (2C), 153, 157, 159, 161, 162, 175 (Fig. S3).
Characterization of L2- N-((4-oxo-4H-cromen-3yl)
methylene)isonicotinohydrazide.
Anal. calc. (C16 ): Theoretical (%) - C-65.53, H-3.78, N-
4.33, O-16.37, Experimental (%) C- 65.77, H-3.78, N-14.48.
IR (KBrcm−1); 3250 (-NH), 3040 (H-C=N), 1690 (N-C=O), 1632
C=O), 1530 (C=N) (Fig. S4).
6
DMSO -500MHz) δ/ppm: 110, 118, 122 (2C), 125
this case, the presence of metal ions (Cu /Ni ) doesn’t affect
on sensing mechanism (deprotonation phenomenon), which
enhances the sensitivity of probe towards CN¯.
1
3 3
H10FN O
1
2
. Experimental section
(
1
2.1 Reagent and apparatus
6
H NMR (d DMSO-500MHz) δ/ppm: 12.18 (s 1H), 8.88 (s 1H),
All the reagents and solvents (DMSO spectroscopic grade and 8.8 (d 2H), 8.65 (s 1H), 8.16 (d 1H), 7.9 (t 1H), 7.88 (d 2H) 7.6 (d
analytical grade) for the experimental work were obtained 1H), 7.76 (t 1H), 7.59 (d H) (Fig. S5).
1
3
from Sigma–Aldrich. Millipore water purification system was
6
C NMR (d DMSO -500MHz) δ/ppm: 118, 119, 121(2C), 125,
used for Distilled water. Elemental investigation for hydrogen, 126, 135, 140, 142, 150(2C), 151, 155, 156, 162, 175 (Fig.S6).
carbon and nitrogen was performed by using vario MICRO
V3.1.1 CHNS. For IR spectra Perkin Elmer FT-IR 1000
13
NH2
NH
1
spectrophotometer was used with KBr as a solid film. H,
C
O
O
C
NMR and titration were carried out by using Bruker DRX500
MHz spectrophotometer having TMS as an internal reference.
Absorption spectra were recorded on double beam Specord S
HN
N
O
O
O
O
O
N
X
00
X
CHO
X
C
N
DMF,POCl
3
EtOH,reflux 1h.
600 Thermo-Scientific UV-visible spectrophotometer with 1 cm
OH
L1, X=F
L2, X=H
quartz cuvette path length. Density functional Theory (DFT)
method were implemented in gas phase by Gaussian 09 W
programme, using a B3LYP/6-31G basis set.
Scheme: 1. Synthesis of Probe L1and L2
2.2 General procedure for experiments
3
.2 Anion sensing without metal ions: colorimetry and
The stock solution of probe (1 mmol) was prepared in DMSO
and used as proper dilution for all spectroscopic studies. UV-
vis spectroscopy was carried out by addition of anions (as their
spectrophotometry
The probes were insoluble in water and protic solvents, so the
supramolecular interface with tested anions such as F¯, CI¯,
tetrabutylammonium salts) (0.01 M) in H
HEPES buffer pH 7.4), while keeping the probe concentration
0 μM. The antagonism experiment was carried out with
2
O- DMSO (10% v/v,
2
2
2
Br¯, I¯, CN¯, N ¯, SCN¯, AcO¯, AsO ¯, CO ¯, NO ¯, PO ¯, SO ¯,
3
2
3
3
4
4
2
H PO ¯ and HPO ¯ (as tetrabutylammonium salts) were
2
4
4
2
-
examined in H O-DMSO (10% v/v, HEPES buffer pH 7.4). As
2
various anions with CN in the ratio of 1:2. Benesi-Hilderbrand
3
2
shown in Fig. 1, the absorption band of probes L1 / L2 (λmax
–
Plot was used for calculation of binding constant, involving
plotting the inverse of the changes in its absorbance against
3
16 / 311 nm) shifted towards bathochromic region with
emergence of a new band (λmax – 470 / 464 nm, Δλ = 154 / 153
nm) as one solution changed from colorless to yellow only with
0
the inverse of the anion concentration 1/(A- A ) versus
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CN¯. The high charge separation between donor and acceptor (ACN, DMSO, MeOH). Polar solvents relax the ICT excited state
unit, subsequently causes tremendous electron delocalization by dipole relaxation. This result suggests that free probe is
into the isoniazid unit. The discriminating sensing ability of solvent independents; the excited state and ground state have
-
probes towards CN can be revealed through anions basicity almost identical dipole moment and weak charge transfer,
-
pKa value) and hydrogen bonding ability (hydration energy). while the probe-CN complex displays stronger solvent
(
-
In pure DMSO AcO ,
-
-
F
and
H
2
PO
4
display deleterious dependence. This
emphasizes that the dipole moment
interference, which was removed by using 10% H
2
O-DMSO between ground and excited state is moderately high charge
2a
1
binary solution (Fig. S8a). Upon increasing the water content transfer generated by electronic excitation is shown in Fig. 2
the effect of interfering anions is completely avoided through (Table: S1). For Interference study, L1 was tested with 10 eq.
-
hydrogen-bonding. CN has less hydration energy (ΔHhyd = -67 of other competing anions in presence of 5 equiv. of CN¯. The
-1
-
kJ mol ) as paralleled to other competing anions like F (ΔHhyd result shows that these anions don’t affect the absorption
-
1
-
-1
-
=
-505 kJ mol ), AcO (ΔHhyd = -375 kJmol ) and H
2
PO
260 kJmol ), which block its interaction with probe in
aqueous medium. Further, the p values for HF, CH COOH,
4
(ΔHhyd
=
spectra of the probe-CN¯ system (Fig. 3).
-1
-
K
a
3
H3PO4 and HCN in water are 3.17, 4.76, 2.12 and 9.21
¯
respectively, which indicates that CN is a stronger base than
2
5
other competing anions in aqueous medium.
Fig. 2
Solvatochromic studies of L1 with CN- in different polar solvent.
Fig. 3
Competition studies of L1 by absorption spectra of CN- with 10eq. of
different anions.
Fig. 1
Interaction of L1/L2 upon 5 eq. of anions in 10% aq.-DMSO solution (HEPES
buffer 7.4).
Furthermore, the red shift in the absorption band of
the probe suggests intramolecular charge transfer (ICT)
-
transition upon CN addition by deprotonation phenomenon,
2
6
based on Bhattacharya’s suggestion. To determine the ICT
property of L1 and L1-CN¯, illustrate the change in absorption
spectra in both non-polar solvent (DCM) and polar solvents
Fig.4
Absorption titration spectra of L1 upon addition 0–3 eq. of CN- , Inset: Jobs
plot shows 1:1, in 10% aq.-DMSO solution (HEPES buffer 7.4).
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The binding affinities of probes were determined by The pH dependency of L1 and CN¯ complex was examined at
titration experiment with sequential addition of CN¯ (Fig. 4; different pH values (4-8.3) at 470 nm. As shown in (Fig. 6b), the
Fig. S7a). Absorption titrations of L1 / L2 shows the peak at 316 L1 and L1-CN¯ complex is almost stable between 4.0-6.5 pH
/
311 nm steadily decreases and temporarily a new peak values, but above 6.5 pH values, the absorbance increases
concentrated at 470 / 464 nm increasingly with a clear dynamically. The selectivity of CN¯ decreased pointedly under
isosbestic point at 353 349 nm, designated an acidic conditions and gave increased absorbance under basic
/
interconversion into single distinct chemical species conditions due to protonation-deprotonation of the –NH
throughout the titration progression upon addition of CN¯. The group. This signifies that L1 and CN¯ detection was stable at
binding approach between CN¯ and L1 / L2 was resolute over neutral pH (Fig. 6b). The appreciation of quick reaction with
and done with Job’s plot, which displays a 1:1 binding CN¯ is noteworthy for the probe in its hands-on application.
interaction. The values of association constants were The kinetic result showed that the reaction is accomplished
calculated by using nonlinear fitting curve analysis (Benesi– within 2 min (Fig. 6c).
2
3
4
4
Hildebrand equation) and found to be 3.83 × 10 / 2.56 × 10
5
which are within the range of (1.0 – 1.0 × 10 ) as 3.3 Anion sensing in presence of metal ions: colorimetry and
-1
M
previously reported CN¯ sensor. The detection limits was spectrophotometry
calculated by (3σ/slope) and found to be 0.76 / 0.68 μM (Fig.
Since L1 / L2 have a hetero-atom binding position, so its
5, Fig. S7b).
2+
selectivity towards different cations (Ba , Sn , Pb , Mn ,
2+
2+
2+
2
+
2+
2+
2+
+
2+
2+
+
2+
Ni , Fe , Cu , Co , Ag , Zn , Cd , Hg , Hg ) has been
examined through absorption spectra. L1 shows a charge
2
transfer band at 355 nm with Ni and 440 nm with Cu metal
+
2+
2
+
2+
ions (Fig. S8b). Upon gradual addition of Cu / Ni into the
probe L1, a clear isosbestic point appeared at 347 / 333 nm
with 2:1 / 1:1 binding stoichiometry respectively (Fig. S9).
Fig. 5
(a) Benesi Hilderbrand Plot (b) Limit of detection for the binding of CN¯
with L1.
−
Fig. 6
(a) Reversibility of L1 upon sequential addition of CN and HCl, (b) pH
2+
2+
Fig. 7
Interaction of L1+Cu complex and L1+Ni complex with 5 equiv. of
−
dependent, (c) Time-dependent absorption intensity of Probe with 5 eq. CN in 10%
different anions in 10% aq.-DMSO solution (HEPES buffer 7.4).
aq.-DMSO solution (HEPES buffer 7.4).
2
+
2+
The selectivity of CN¯ in presence of Cu / Ni was
analysed by absorption spectra. Results showed that only CN¯
was selective in presence of both metal ions (Fig. 7). Upon
To observe the recyclability of probe toward CN¯ in a
mixture of H
2
O-DMSO (10% v/v, HEPES buffer pH 7.4) solution,
2
eq. HCl was added, color changed from yellow to colorless
2
+
sequential addition of CN¯ to L1-Cu complex (0.5 eq.),
shifting occurs in peak from 440 nm to 464 nm with a clear
and 470 nm peak entirely disappeared with redevelopment of
free probe (Fig. 6a). The color variation was almost changeable
with alternative addition of HCl and CN¯. This result further
promotes that detection of CN¯ by deprotonation mechanism.
2
+
isosbestic point at 360 nm. Similarly in presence of Ni (1eq.)
the absorption band at 355 nm decreases with a concomitant
increase of 464 nm band with a clear coexistent point at 385
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-1
-1
-1
nm (Fig. 8). Both absorption titrations showed analogous cm (-C=O), 1647 cm (N-C=O), 1611 cm (-C=N). Upon
pattern as in absence of metal ions, only difference in interaction with CN¯ the –NH peak disappeared with slight
saturation point. The saturation limits were attained with 2 eq. shifting of other peaks. It validates that CN¯ binds with –NH
2
+
2+
of CN¯ in presence of Cu and 1.5 eq. with Ni . The binding protons (Fig. 9b).
2
+
2+
constant of L1 for CN¯ in presence of Cu / Ni was found to
5
−1
5
−1
be 1.72 × 10 M / 2.8 × 10 M with 3.5 / 6.3 μM detection
limit (Fig. S10). The higher binding constant than that in free
4
−1
ligand (3.83 × 10 M ) proved that -NH proton of metal
complexes is somewhat more acidic than free probe due to
electron withdrawing character of metal ions, thus metal
complexes can turn as a superior H-bonded donor moiety for
¯
CN .
1
Fig. 9 (a) Stacked H NMR titration in d
6
-DMSO, (b) IR spectra of L1 without and with
TBACN.
2
+
2+
Fig. 8
Absorption titration spectra of L1+Cu and L1+Ni complex upon addition
-
of CN in 10% aq.-DMSO solution (HEPES buffer 7.4).
3
.4 Nature of interaction of L with CN¯
1
To analyse host–guest interaction between CN¯ and probe, H
NMR titrations were executed in the absence and presence of
CN¯. L1 has singlets at 10.19 and 8.90 ppm corresponding to -
NH and HC=N proton whereas the aromatic protons appeared
in the region of 8.80–7.77 ppm. Similarly L2 has singlets at
1
2.18, 8.88 ppm equivalent to the –NH, HC=N proton and
.65–7.59 ppm to the aromatic protons. Upon slow addition of
8
CN¯, the NH proton disappears in L1 / L2 (Fig. 9a; Fig.S11). In Fig. 10
addition, no extra peak was generated within the range of 4-5
ppm, which designates prohibiting of the nucleophilic attack
DFT Optimized structure and HOMO/LUMO energy band gap.
The binding procedures of CN¯ with probes were also
supported by advanced computational DFT calculation in gas
phase by Gaussian 09 W programme, using a B3LYP/6-311+G
via CN¯. The interaction between CN¯ and L1 was also
confirmed by infrared spectra which shows the stretching
-1
-1
vibration peaks at 3415 cm (–NH), 3018 cm (H-C=N), 1708
1
6b-d,27
(d, p) basis set.
There are hydrogen bonding exchanges
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between isoniazid -CO and -NH group (2.356 / 2.359 Å- L1 / L2 The probe has widespread applications for CN¯ determination
1
2,21
respectively) in the gas phase. The optimized structures of in different waste water testers.
which was composed
probe-CN¯ openly designated that CN¯ reduces the exchange from River Ganga of Haridwar, Roorkee and tap water of
of hydrogen bonding, which can be proved that CN¯ interact Roorkee. The insoluble materials were removed by 0.22 mm
with the acidic hydrogen. Furthermore, the HOMO / LUMO membrane filter paper. A known amount of CN¯ (20 μM) was
energy gap between L1 / L2 and CN¯ are smaller (ΔE = 3.015 eV spiked in water sample. These water analytes were used as a
/
3.047 eV) in comparison to L1 / L2 (ΔE = 4.025 eV / 4.197 eV), solvent constituent with DMSO (10%). Table S3 shows the
which are also suggested by the bathochromic shift due to ICT results were investigated by direct absorption study and were
transition upon deprotonation of -NH by CN¯ (Fig. 10, Fig. S12). found to be in agreement with AAS (atomic absorption
To further prove deprotonation is the possible sensing spectroscopy) method.
2
+
2+
mechanism (even in the presence of Cu / Ni ), interaction 4.2 Application as logic gate
2
+
2+
between L1, L1-Cu complex and L1-Ni complex was titrated
with TBAOH instead of CN¯. An analogous UV-vis spectral
change was observed as addition of CN¯, which proved
deprotonation phenomenon (Fig. S13).
+
Based on the reversibility of L1-CN¯ and
H
ions with
consequent changes in its absorption intensity at 470 nm, we
have applied our system as a molecular switch, which perform
on Boolean logic operations. In order to explain the design of
the logic gate, we assign logic 0 and 1 to the inputs and
outputs. The four probable (0, 0), (1, 0), (0, 1) and (1, 1) input
combinations are shown in Fig. 11. It has been detected that
It comes out to be clear that hydrogen-bonding
exchange is essential for anion binding sites. Shape, charge
and mixed solvent system are also exceptionally significant
between the guests-host interactions. Consistently, both the
probes have ability of sensing for CN¯ possibly binding through
+
both the input signals: in absence or presence of CN¯ & H
+
CN¯, H = 1 or CN¯, H = 0) no output signals were achieved,
+
(
1
deprotonation of the -NH groups. H NMR titration, IR
+
while in the presence of CN¯ only input signal (CN¯ = 1, H = 0),
absorption maxima at 470 nm was observed as the output
+
signal but inverse of that (CN¯ = 0, H = 1) bring about no
spectroscopy, OH titration and DFT calculations are provided
enlightening picture of the real host
–
guest interaction. All
results showed that the mechanism proceeds via
deprotonation which affects intramolecular charge transfer
output signal (Fig. 11). Thus, the logic circuit integrating the
+
truth table with two inputs as CN¯ (In ) and H (In ), L1 has the
1
2
(
ICT) transition. Thus based on all the spectroscopic
ability to reveal INHIBIT job via absorption output. In fact it
12a,16b
experiments, the suggested binding mode of probe with CN¯
are shown in scheme 2.
exemplifies an AND logic gate with an inverter
input
in its
O
O
CN-
H
NC
O
H
N
N
N
N
O
O
N
N
O
F
F
O
N
O
H
H
O
N
N
N
N
N
N
HN
N
O
N
O
N
Cu
O
F
TBACN
Cu
O
F
Cu2+
O
O
O
O
N
N
O
O
F
H
F
H
N
N
CN-
O
O
Ni2+
N
N
F
O
O
O
O
O
O
H
3
C
Ni
NH
H
3
C
Ni
NH
N
CN-
O
N
TBACN
F
O
F
Fig. 11 Changes in the absorption intensity at 470nm (L1) under four different input
conditions; Inset: implication logic diagram.
O
O
-
.
Scheme: 2. Suggested sensing mechanism of L1 with CN .
The sensing property of probe was related with some
easily synthesized reported probes (containing –NH moiety)
for anions by colorimetric method (Table S2). The data shows
that the probe is highly selective for CN¯ with high binding
Conclusions
In summary, we have developed a simple –NH containing
Schiff base, which accentuates the detection of CN¯ via
deprotonation of the –NH group in presence of anions and
renders the appreciation due to the shift of the charge transfer
band. The binding constant and 1:1 stoichiometry of the probe
2
8
constant.
-
4
. Application
with CN was calculated from BH and Job’s plot. However,
-
selectivity and sensitivity for CN¯ increased in the presence of
4
.1 Analysis of CN in water samples
2
Cu and Ni due to its coordinating aptitude with probe and
+
2+
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PleaseRd So Cn oA t da vd aj un s ct ems argins
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DOI: 10.1039/C6RA14237K
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increased the acidity, which stimulates the deprotonation of 16 (a) J. H. Hu, J. B. Li, J. Qi and Y. Sun, New J. Chem., 2015, 39,
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041-4046; (b) M. K. Chahal and M. Sankar, Anal. Methods,
015, 7, 4552–4559; (c) Ashwani Kumar and Hong-Seok Kim,
the –NH. In disparity, selectivity for CN¯ over other anions was
described by anion basicity in aq. medium. There are some
advantages associated to probe such as (i) inexpensive and
simple synthesis (ii) displaying high sensitivity for CN¯ over
other coexistent anions, instead in presence of metal ions.
New J. Chem., 2015, 39, 2935—2942: (d) A. Sarkar, S.
Bhattacharyya and A. Mukherjee, Dalton Trans., 2016, 45,
1166-1175.
17 X. Lou, D. Ou, Q. Li and Z. Li, Chem. Commun., Rev. 2012, 48,
8
462–8477; (b) I. Takashima, A. Kanegae, M. Sugimoto, and
A. Ojida, Inorg. Chem. 2014, 53, 7080 7082; (c) Z. Xu, J. Pan,
D. R. Spring, J. Cui and J. Yoon, Tetrahedron, 2010, 66, 1678–
683.
8 (a) K. H. Jung and K. H. Lee, Anal. Chem. 2015, 87, 9308
314; (b) M. Shahid, S. S. Razi, P. Srivastava, R. Ali, B. Maiti
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Acknowledgement
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Ms. Nirma Maurya is thankfully acknowledges to UGC New
Delhi, India for given that financial funding.
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and Arvind Misra, Tetrahedron, 2012, 68, 9076-9084; (c) L.
Tang and M. Cai, Sens. Actuators B, 2013, 173, 862– 867.
9 (a) P. B. Pati, Sens Actuators B. 2016, 222, 374–390; (b) M.
Shahid and A. Misra, Anal. Methods, 2013, 5, 434–437.
0 (a) M. K. Chahal and M. Sankar, RSC Adv., 2015, 5, 99028-
99036; (b) S. S. Razi, R. Ali, P. Srivastava, M. Shahid and
Arvind Misra, RSC Adv., 2014, 4, 22308-22317.
(a) N. Maurya, S. Bhardwaj and A. Kumar Singh, Sens
Actuators B, 2016, 229, 483-491; (b) D. Udhayakumari, S.
Velmathi, and M. S. B., J. Fluorine Chem., 2015, 175, 180-
1
2
1
2
Reference
1
(a) A. P. de Silva, D. B. Fox, A. J. M. Huxley and T. S. Moody,
Coord. Chem. Rev., 2000, 205, 41–57; (b) M. Dutta and D.
Das, Trends Anal. Chem., 2012, 32, 113–132.
2
2
1
2
(a) R. Martinez, A. Espinosa, A. Tarraga and P. Molina,
Tetrahedron, 2008, 64, 2184–2191; (b) H. Han, M. Wang and
H. Wang, New J. Chem., 2014, 38, 914–917.
84; (c) V. Reena, S. Suganya, S. Velmathi, J. Fluorine Chem.,
013, 153, 89–95.
3
4
5
X. Huang, X. Gu, G. Zhang and D. Zhang, Chem. Commun.,
012, 48, 12195–12197.
(a) F.J. Baud, Toxicol. 2007, 26, 191–201. (b) R. Koenig,
Science 2000, 287, 1737–1738.
B. Vennesland, E.E. Comm, C.J. Knownles, J. Westly and F.
Wissing, Academic Press, London, 1981; (b) J.Y. Noh, I.H.
Hwang, H. Kim, E.J. Song, K.B. Kim and C. Kim, Bull. Kor.
Chem. Soc., 2013, 34, 1985–1989.
2
2 (a) V. K. Gupta, A. K. Singh and N. Gupta, Sens. Actuators B.,
014, 204, 125-135; (b) V. Kumar, M.P. Kaushik, A.K.
2
Srivastava, A. Pratap, V. Thiruvenkatam and T.N. G. Row,
Anal. Chim. Acta, 2010, 663, 77-84; (c) M. V. Sigalov, B. A.
Shainyan, N. N. Chipanina, and L. P. Oznobikhina, J. Phys.
Chem., 2013, 117, 11346
3 H.A. Benesi, J.H. Hildebrand, J. Am. Chem. Soc., 1947, 71,
703-2707.
−11356.
2
2
6
(a) G.J. Park, I.H. Hwang, E.J. Song, H. Kim and C. Kim,
Tetrahedron, 2014, 70, 2822–2828; (b) L. Tang, P. Zhou, K.
Zhong and S. Hou, Sens. Actuators B, 2013, 182, 439–445; (c)
X. Chen, S. Nam, G. Kim, N. Song, Y. Jeong, I. Shin, S. Park, K.J.
Kim, S. Park and J. Yoon, Chem. Commun. 2010, 46, 8953–
2
4
P. A. Nikitina, L. G. Kuz’mina , V. P. Perevalov and I. I. Tkach,
Tetrahedron, 2013 69, 3249-3256; (b) K. M. Khan, N.
Ambreen, U. R. Mughal, S. Jalil, S. Perveen and M. I.
Choudhary, Eur. J. Med. Chem., 2010, 45, 4058-4064.
5 (a) S. Mardanya, S. Karmakar, D. Mondal and Sujoy Baitalik,
Dalton Trans., 2015, 44, 15994-16012; (b) Y. Jeong Na, G. J.
Park, H. Y. Jo, S. A. Lee and C. Kim, New J. Chem., 2014, 38,
8
955.
2
7
8
9
J. D Johnson, T. L Meisenheimer and G. E. Isom, Toxicol Appl.
Pharmacol., 1986, 84, 464-469.
B. K Ardelt, J. L Borowitz and G. E. Isom, Toxicol., 1989, 56,
5
2
769-5776; (c) H. J. Mo, Y. Shen and B. H. Ye, Inorg. Chem.
012, 51, 7174 7184; (d) S. Saha, A. Ghosh, P. Mahato, S.
1
47-154.
S. I. Baskin and T. G. Brewer, Washington, DC, 1997, 271–
86; (b) R. A. Greenfield, B. R. Brown, J. B. Hutchins, J. J.
−
Mishra, S. K. Mishra, E. Suresh, S. Das and Amitava Das, Org.
Lett., 2010, 12, 3406-3409.
6 (a) N. Kumari, S. Jha and S. Bhattacharya, J. Org. Chem.,
2
Iandolo, R. Jackson, L. N. Slater and M. S. Bronze, Am. J. Med.
Sci., 2002, 323, 326-340.
2
2
2
2
011, 76, 8215–8222; (b) L. Li, F. Liu and H. Li, Spectrochim.
1
1
1
0 Guidelines for Drinking-Water Quality, World Health
Organization, Geneva, 1996.
1 H.M. Nie, C.B. Gon, Q. Tang, X.B. Ma and C.f. Chow, Dyes
Pigm., 2014, 106, 74-80.
2 (a) S. Bhardwaj and A. K. Singh, J. Hazard. Mater., 2015, 296,
Acta, Part A, 2011, 79, 1688–1692; (c) P. Xie, F. Guo, S. Yang,
D. Yao, G. Yang and L. Xie, J. Fluoresc., 2013, 1316-5.
7 (a) R. Ali, S. S. Razi, R. C. Gupta, S. K. Dwivedi and Arvind
Misra, New J. Chem., 2016, 40, 162-170; (b) A. Misra, M.
Shahid and P. Srivastava, Sens Actuators B, 2012, 169, 327–
54-60; (b) V. K. Gupta, A. K. Singh; S. Bhardwaj and K. R.
Bandi, Sens. Actuators B, 2014, 197, 264-273.
3 (a) A. Mouradzadegun and F. Abadast, Chem. Commun.,
2014, 50, 15983-15986; (b) Y. Ding, T. Li, W. Zhu and Y. Xie,
Biomol. Chem., 2012, 10, 4201-4207.
3
40.
8
(a) G. Vinithra, S. Suganya and S. Velmathi, Tetrahedron
Lett., 2013, 54, 5612–5615.; (b) M. S. Kumar, S. Loganathan,
A. Kumar and A. Sreekanth, Anal. Methods, 2013, 5, 6401–
1
1
6
410.; (c) K. Y. Ryu, J. J. Lee, J. A. Kim, D. Y. Park and C. Kim,
4 C. Zhang, K. Ji, X. Wang, H. Wu and C. Liu, Chem. Commun.,
2
RSC Adv., 2016, 6, 16586-16597.; (d) V. Kumara, M. P.
Kaushika, A. K. Srivastavaa, A. Pratapa, V. Thiruvenkatamb
and T. N. Guru Row, Anal. Chim. Acta, 2010, 663,77–84.; (e)
C. Parthibana, S. Ciattinib, L. Chelazzib, K. P. Elangoa, Sens.
015, 51, 8173—8176; (b) J. Jo and D. Lee, J. AM. CHEM.
SOC., 2009, 131, 16283–16291; (c) D. Singhal, N. Gupta, A. K.
Singh Mater. Sci. Eng., C, 2016, 58, 548–557.
D. Aldakov and P. Anzenbacher Jr., J. Am. Chem. Soc., 2004,
1
5
Actuators
B.,
2016,
231,
768–778
126, 4752–4753; (b) R. K. Konidena and K. R. J. Thomas, RSC
Adv., 2014, 4, 22902–22910.
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