Chromogenic hydrazide Schiff base reagent: Spectrophotometric determination of CN? ion

Article abstract of DOI:10.1016/j.saa.2019.117471

A Schiff base reagent, Picolinohydrazide-naphthol (HL), is used for trace level detection of toxic CN^? selectively in presence of eighteen other anions (SCN^?, OCN^?, S₂O₃ ^2?, HPO₄ ^2?, H₂PO₄ ^?, I^?, ClO₄ ^?, HSO₄ ^?, SO₄ ^2?, AsO₄ ^3?, NO₂ ^?, AsO₂ ^?, Cl^?, F^?, HF₂ ^?, NO₃ ^?, Br^?, N₃ ^?) by visual color change, colorless to yellow, in DMSO/H₂O (9:1, v/v) at pH, 7.2 (HEPES buffer) medium. The sensitivity of the probe shows that the limit of detection (LOD) is 7.08 μM. The probable mechanism for the sensing behavior involves the deprotonation of naphthol-OH by CN^? that has been authenticated by ¹H NMR titration and Mass spectra. The composition (1:1 mol ratio) is supported by Job's plot and binding constant (K_a, 1.5 × 10⁴ M^?1) is reported by Benesi-Hildebrand plot. Furthermore, a simple paper strip device is fabricated for the determination of CN^? ion in water. DFT computation is carried out to explain the electronic spectral feature of the sensor.

Full text of DOI:10.1016/j.saa.2019.117471

Journal Pre-proof
Chromogenic hydrazide Schiff base reagent: Spectrophotometric
determination of CN− ion
Sunanda Dey, Chandana Sen, Chittaranjan Sinha
PII:
S1386-1425(19)30861-3
https://doi.org/10.1016/j.saa.2019.117471
SAA 117471
DOI:
Reference:
Spectrochimica Acta Part A: Molecular and Biomolecular
Spectroscopy
To appear in:
Received date: 14 June 2019
Revised date:
8 August 2019
14 August 2019
Accepted
date:
Please cite this article as: S. Dey, C. Sen and C. Sinha, Chromogenic hydrazide Schiff
base reagent: Spectrophotometric determination of CN− ion, Spectrochimica Acta Part
A: Molecular and Biomolecular Spectroscopy(2018), https://doi.org/10.1016/
j.saa.2019.117471
This is a PDF file of an article that has undergone enhancements after acceptance, such
as the addition of a cover page and metadata, and formatting for readability, but it is
not yet the definitive version of record. This version will undergo additional copyediting,
typesetting and review before it is published in its final form, but we are providing this
version to give early visibility of the article. Please note that, during the production
process, errors may be discovered which could affect the content, and all legal disclaimers
that apply to the journal pertain.
© 2018 Published by Elsevier.

Journal Pre-proof
1
Chromogenichydrazide Schiffbasereagent:spectrophotometricdetermination
ofCN- ion
a,
Sunanda Deya, Chandana Sena,b, Chittaranjan Sinha *
aDepartment of Chemistry, Jadavpur University, Kolkata 700 032, India, crsjuchem@gmail.com
bDepartment of Chemistry, Sripat Singh College, Jiaganj , Murshidabad , Pin –742123, West
Bengal , India
Abstract: A Schiff base reagent, Picolinohydrazide-naphthol (HL), is used for trace level
2-
detection of toxic CN- selectively in presence of eighteen other anions (SCN−, OCN-, S2O3 ,
2-
-
−
−
2-
3-
−
-
-
−
−
HPO4 , H2PO4 , I-, ClO4 , HSO4 , SO4 , AsO4 , NO2 , AsO2 , Cl−, F-, HF2 , NO3 , Br−, N3 ) by
visual colour change, colorless to yellow, in DMSO/H2O (9:1, v/v) at pH, 7.2 (HEPES buffer)
medium. The sensitivity of the probe shows that the limit of detection (LOD) is 7.08 M. The
probable mechanism for the sensing behavior involves the deprotonation of naphthol-OH by CN-
1
that has been authenticated by H NMR titration and Mass spectra. The composition (1:1 mole
ratio) is supported by Job’s plot and binding constant (Ka, 1.5 × 104 M-1) is reported by Benesi-
Hildebrand plot. Furthermore, a simple paper strip device is fabricated for the determination of
CN- ion in water. DFT computation is carried out to explain the electronic spectral feature of the
sensor.
Keywords: Hydrazide based fluorescent probe, naphthyl, cyanide, colorimetric ion sensor.

Journal Pre-proof
2
1. Introduction
Cyanide (CN-) is well known toxic anion and has been released from manufacturing gas plants as
by-product; extremely used in crimes; extensively included in the production of plastics, dyes,
pigments, nylon, pharmaceuticals, insecticides, road salts, extraction of gold and silver ore and
metal degreasing. Besides, tobacco smokers generate CN-/HCN in their blood. Thus there is
enough scope of entry of CN- in food chain and environment. Selective sensing of anions has
incessantly received significant attention due to their wide variety of roles in environmental,
chemical, clinical and biological applications [1-3]. Because of severe toxicity of cyanide (CN-)
to living organisms and easy binding with heme-proteins, the blockage of cytochrome C oxidase
functions hampers the mitochondrial electron transfer chain process [4]. Toxic cyanide (HCN)
can be inhaled or absorbed via skin; entered through unclean food and contaminated drinking
water into human body [5]. In the last few years, a number of experimental methods for detection
of cyanide ion have been adopted, for example, electrochemical, chromatographic technique and
also flow injection analysis [6-8]. However, spectrophotometric methods have advantageous
over the others because of easy to operation, time-saving and low cost technique [9-12].
Therefore, it is important to develop a colorimetric probe with simple structure and high
selectivity towards specific anion. A colorimetric sensor generally possess two main parts, one is
signaling unit and the other one is binding site; the color change occurs when the binding site
interacts with the corresponding ions in the recognition route [13]. There is upsurge in the design
of sensors for CN- detection [14-16]. The chemosensors like carbazole-based molecules [17],
imidazolyl-naphthoquinone [18], anthraquinone derivatives [19], pyromellitic diimides [20],
Rhodamine-B derivatives [21] etc. have been used for trace level determination of Cyanide ion.
Most interesting, certainly in public domain, is the use of visual detection of the anion. Azo-

Journal Pre-proof
3
azomethine (-N=N----C=N-) chemosensor has been used as chromogenic reagent for naked-eye
determination of CN- [13]. Sensitivity to CN- is largely dependent on the nature of binding site
with various functional groups like fluoroactophenone [22], benzyl [23], hydrazone [24],
indolium [25-29], boronic acid [4, 30-33], dicyanovinyl [34-40], aldehyde [41-43], amide,
pyrrole, indole, phenols, hydrazine based salicyladehyde derivatives [44-50]. In this work, we
have
designed
a
very
simple
probe,
(E)-N'-((2-hydroxynaphthalen-1-
yl)methylene)picolinohydrazide (HL), obtained from picolinohydrazide and 2-hydroxy-1-
naphthaldehyde which is selective colorimetric sensor for CN- in semi-aqueous solution. Detail
of probe characterization, sensing of CN- in presence of large number of anions is reported in
this work along with theoretical computation.
2. Experimental Section
2.1. Materials and methods
2-Picolinic acid bought from High-Media and used without further purification. All other
chemicals were purchased from Merck. The aqueous solutions were prepared by using Milli-Q
(Millipore) water. Elemental analyses (C, H, and N) were done by Perkin-Elmer CHN analyzer
(2400 Series-II), USA elemental analyzer. Perkin Elmer Lambda 25 spectrophotometer was used
to get UV-Vis spectra. FT-IR spectra obtained from a Perkin Elmer LX-1 FTIR
-1
1
spectrophotometer with KBr disk (4000–400 cm ). The H and 13C NMR spectra were acquired
from Bruker (AC) 500 MHz FT-NMR spectrometer with TMS as an internal standard. ESI mass
spectra were obtained from a Water HRMS model of XEVO-G2QTOF#YCA351 spectrometer.

Journal Pre-proof
4
2.2. Synthesis of HL
Picolinohydrazide was prepared starting from 2-Picolinic acid [51]. Dry MeOH (10 ml)
solution of Picolinohydrazide (137 mg, 1.0 mmol) was added to methanol solution (10 ml) of 2-
hydroxy-1-naphthaldehyde (172 mg, 1.0 mmol) and was stirred for 6 h and a greenish-yellow
solution was obtained. Then this solution was allowed to evaporate slowly keeping in air. After
few days solid yellow mass of (E)-N'-((2-hydroxynaphthalen-1-yl)methylene)picolinohydrazide
(HL) were obtained (Yield, 87%), M.P., 186°C (Scheme 1). Microanalytical data: C17H13N3O2
1
calcd (found): C, 70.09 (69.55); H, 4.50 (4.54); N, 14.42 (13.85) %. H NMR (500 MHz,
DMSO-d6) (δ, ppm): 12.73 (s, 1H, -OH), 12.387 (s, 1H, -NH), 9.628 (s, 1H, imine-H), 8.573-
8.582 (d, 1H), 7.976-8.010 (t, 2H), 7.899-7.917 (dd, 1H), 7.740-7.758 (d, 1H,), 7.699-7.715 (d,
1H), 7.507-7.531 (dd, 1H), 7.404-7.434 (t, 1H), 7.205-7.234 (t, 1H), 7.034-7.052 (d, 1H) (Fig.
S1); 13C NMR (in DMSO-d6) (δ, ppm): 160.49, 158.63, 149.41, 149.15, 149.04, 138.65, 133.34,
132.33, 129.45, 128.27, 128.24, 127,49, 124.06, 123.30, 120.99, 119.43, 108.99 (Fig. S2); ESI-
MS peak for HL at 292.1084 (calculated mass, 291.1086) corresponds to [M+H+] and base peak
-1
-1
at 314.0985 for [M+Na+], (Fig. S3); FTIR for HL: ν 3482 cm (OH), ν 3191 cm (NH), ν 1661
-1
-1
cm (C=O), ν 1620 cm (C=N) (Fig. S4).

Journal Pre-proof
5
Scheme 1. Synthetic scheme of the probe, HL.
2.3. Analytical Experiments
For UV−Vis measurements stock solution of HL was prepared by dissolving the probe
which required producing 1.0 × 10−3 M solution. All the required anion of 1.0 × 10−3 M solution
was prepared in deionized water. In this case sodium, potassium, ammonium or tetra ethyl
ammonium salts of different anions (NH4SCN, NaOCN, Na2S2O3.5H2O, K2HPO4, KH2PO4, KI,
NaClO4, NaHSO4, Na2SO4, (C2H5)4N(CN), Na2HAsO4.7H2O, NaNO2, NaAsO2, NaCl, NH4F,
NH4HF2, NaNO3, KBr, NaN3) are used. For checking sensitivity, selectivity and all the UV−Vis
spectral measurements towards anions, 50 M main solution in 9:1 DMSO/water (v/v) (HEPES
buffer, pH 7.2) were prepared and to this solution 1.00 equivalent anion salts were added.
The limit of detection (LOD) was calculated from the UV-Vis titration measurements.
For the determination of standard deviation the absorbance of HL without any analyte was
measured. The limit of detection of HL for CN- ion sensing were determined by following
equation: LOD = 3  and  = (Sb1)/(S); Sb1 = standard deviation of the blank solution; S = slope
of the calibration curve.
The binding constant value of cyanide with HL was determined from the absorbance data
and using Benesi–Hildebrand equation, 1/ΔA = 1/ΔAmax +(1/K[C])(1/ΔAmax). Here ΔA = A-Amin
and ΔAmax = Amax-Amin, where Amin, A, and Amax are the absorbance values of HL measured in
the absence of anion, at an intermediate anion concentration, and at a concentration of complete
saturation where K is the binding constant and [C] is the anion concentration respectively. In this
report of work we represent Amin as A0. From the plot of (Amax-A0)/(A-A0) against [C]-1 for
anions, the value of K has been determined from the slope.

Journal Pre-proof
6
2.4. Theoretical Computation
For the optimisation of ligand and ligand with CN-, DFT/B3LYP method by Gaussian 09
software was used with basis set 6-311G [52]. For approval the optimized geometries,
Vibrational frequency calculations were performed which represents the local minima and
positive eigenvalues. The absorption energies are theoretically examined by time-dependent DFT
(TDDFT) by considering DMSO as a solvent through the conductor-like polarizable continuum
model (CPCM) approach [53-55], The fraction of influences of various groups in each of the
molecular orbitals were calculated by using GAUSSSUM [56].
3. Result and Discussion
3.1. Synthesis and Formulation of Probe
The structure of (E)-N'-((2-hydroxynaphthalen-1-yl)methylene)picolinohydrazide (HL) is
1
supported by H NMR spectrum in DMSO-d6 which shows prominent peaks at 12.73 (s, 1H) for
NH, 12.38 (s, 1H) for OH, 9.62 (s, 1H) for imine-H (Fig. S1). ESI-MS spectrum also shows ion
peak at 292.1084 which is characteristic formation of [HL+H]+ and base peak at 314.0985 for
[HL+Na+] (Fig. S3). The IR spectrum confirms the presence of functional groups like C=N
-1
-1
-1
(1620 cm−1), C=O (1661 cm ), N-H (3191 cm ) and phenolic-OH (3482 cm ) (Fig. S4) and
supports the structure of the probe.
3.2. Colorimetric Detection of CN-
Use of spectrophotometric method for the detection of CN-/HCN is well known in
literature [57]. Herein experiment is performed on adding equimolar concentration of anions viz.
2-
2-
-
−
−
2-
3-
−
-
SCN−, OCN-, S2O3 , HPO4 , H2PO4 , I-, ClO4 , HSO4 , SO4 , CN-, AsO4 , NO2 , AsO2 , Cl−,
-
−
−
F-, HF2 , NO3 , Br−, N3 to the 50 M ligand solution in 9:1 DMSO-H2O (v/v) (HEPES buffer,

Journal Pre-proof
7
pH 7.2). Out of this large number of anions, a rapid color change has been observed from
colorless to yellow for CN- only (Fig. 1). Furthermore, the selectivity and sensitivity of CN- is
3-
-
also confirmed by UV-Vis spectroscopic measurements (Fig. 2). AsO4 and AsO2 are
responding weakly in the absorption spectra and do not affect the CN- determination.
Fig. 1. Visualization test of the probe, HL (A) with the anions (left to right) SCN− (B), OCN- (C),
-
−
−
S2O32- (D), HPO42- (E), H2PO4 (F), I- (G), ClO4 (H), HSO4 (I), SO42- (J), CN- (K), AsO43- (L),
−
-
-
−
−
NO2 (M), AsO2 (N), Cl− (O), F- (P), HF2 (Q), NO3 (R), Br− (S), N3 (T) under normal light.
Fig. 2. Change in absorption spectrum of HL (50 µM) upon addition of different anions (50 µM
each) in 9:1 DMSO/H2O (v/v) (HEPES buffer, pH 7.2), inset: vial image of HL and HL+CN-.

Journal Pre-proof
8
The sensitivity of the probe, with CN- ion has been examined with gradual addition of
CN- ion followed by recording of UV-Vis spectral changes. The probe shows four absorption
maxima at 314, 328, 365 and 380 nm, on adding CN-, the absorption maxima are decreased with
generation of a new characteristic band at 460 nm forming an isobestic point at 400 nm (Fig. 3).
The absorption spectral intensity has changed linearly at 460 nm on adding CN- (0-50 µM) to HL
in DMSO-H2O medium (Fig. 3 inset). The limit of detection (LOD) determined from UV–Vis
titration is 7.08 M (3/m method, Fig. S5) and is comparable with some published data (Table
S1) [46, 58-61]. The binding constant of the probe, HL with CN- ion is 1.5 × 104 M-1 (Fig. S6).
From Job’s plot, 1:1 stoichiometry between the probe, HL and CN- ion has further been validated
a 1:1 complex formation (Fig. S7).
Fig. 3. Change in absorption spectrum of HL (50 µM) upon incremental addition of CN- (0-50
µM) in 9:1 DMSO/H2O (v/v) (HEPES buffer, pH 7.2).

Journal Pre-proof
9
1
The mechanism of binding of HL with CN- has been established by the H NMR titration
experiment (Fig. 4). The spectra show the deprotonation of hydroxyl (-OH) group and the peak
(OH) of the probe at 12.73 ppm is vanished while -NH proton peak at 12.38 ppm is retained and
broadened. The widening of –NH proton signal may be due to the formation of –CN---H–N type
hydrogen bonding. Upon addition of excess CN- ion the broad peak of -NH persists which has
proposed that CN- ion cannot deprotonate the -NH proton. Therefore, the sensing of CN- ion
could be recognized by the probe via deprotonation of –OH and hydrogen bonding with –NH
and proposed anion complex may be [HCN---L]- (Scheme 2). The mass spectrum shows a peak
at m/z = 290.1808 (Fig. S8), which has agreed with the expected mass of one -H deprotonated
mass peak of HL (i.e L, m/z 290.2961) and has confirmed the 1:1 complexation.
Fig. 4. 1H NMR spectra of HL on gradual addition of CN- ion in DMSO-d6.
3.3 Theoretical Studies
The interaction of CN- ion with the HL has been verified by theoretical studies using
density functional theory (DFT) calculations. The optimized structure of the probe, HL and
HL+CN- ion was gained in the gas phase by using the Gaussian 09 computational package with

Journal Pre-proof
10
B3LYP functions and 6-311G basis sets (Fig. 5). In HOMO of the probe the electron density is
localized over the naphthalene moiety whereas in the LUMO, the electron density is spreading
over the picolinyl hydrazide unit and the HOMO-LUMO band gap was 3.43 eV. By
deprotonating agent CN-, the electron density in HOMO-LUMO of probe HL was effected and
the band gap decreased to 1.84 eV (Fig. 6). The CN-, a weak base, assists deprotonation of
phenolic-OH and hence effects the electron density of the probe, HL and the energy of MOs
(Table S2-S3, Fig. S9-10).
Scheme 2. Proposed interaction of CN- ion with HL.
HL
Fig. 5. The DFT optimized structure of the probe HL and probe HL with CN- ion.
HL+CN-=L-

Journal Pre-proof
11
Fig. 6. The energy band gap between probe HL and probe HL with CN- ion.
3.4. Paper Strip Detection Kit
The probe shows no impressive color in DMSO but the addition of CN- changes to high
intense yellow color. For public use, a low cost paper strip transportable detection kit for sensing
CN- is fabricated. A filter paper (Whatman 41) paper strip is coated with HL by dipping into the
solution of probe (10 μM) in DMSO and is dried in air. Later, the HL impregnated paper strip is
soaked in 20 μM solution of CN-, immediately white paper strip turns to yellow. It is dried in air,
and then images are taken under normal light (Fig. 7). This technique could be conveniently used

Journal Pre-proof
12
to detect CN- ion without instrumental analysis, which is valuable practical application of
cyanide sensor.
Fig. 7. Normal light image of test strips of probe HL and HL with CN-.
4. Conclusion
The probe HL is characterized by different spectroscopic techniques and shows high selectivity
and sensitivity to the toxic CN- in presence of other biologically permissible anions. It acts as a
naked eye detection of CN- ion with detection limit 7.08 M. The probable binding mode of the
probe, HL with cyanide was established by ESI-MS and NMR titration. This probe is also useful
in handy detection of CN- ion by using simple test paper strips.
Acknowledgements
The authors are obliged for the financial support from Council of Scientific and Industrial Research
(CSIR, Sanction no. 01(2894)/17/EMR-II), New Delhi and instrumental measurement facilities
from Jadavpur University, Kolkata. S. D. thankful to the Council of Scientific and Industrial
Research (CSIR), Govt. of India for research fellowship.

Journal Pre-proof
13
References
[1] M.E. Moragues, R. Martínez-Máñez, F. Sancenón, Chromogenic and fluorogenic
chemosensors and reagents for anions, Chem. Soc. Rev. 40 (2011) 2593-2643.
[2] M.H. Lee, J.S. Kim, J.L. Sessler, Small molecule-based ratiometric fluorescence probes for
cations, anions, and biomolecules, Chem. Soc. Rev. 44 (2015) 4185-4191.
[3] P.A. Gale, C. Caltagirone, Anion sensing by small molecules and molecular ensembles,
Chem. Soc. Rev. 44 (2015) 4212-4227.
[4] M. Jamkratoke, V. Ruangpornvisuti, G. Tumcharern, T. Tuntulani, B. Tomapatanaget, A-D-
A Sensors Based on Naphthoimidazoledione and Boronic Acid as Turn-On Cyanide Probes
in Water, J. Org. Chem. 74 (2009) 3919-3922.
[5] Z. Xu, X. Chen, H.N. Kim, J. Yoon, Sensors for the optical detection of cyanide ion, Chem.
Soc. Rev. 39 (2010) 127-137.
[6] J. Dziewinski, S. Marczak, E. Nuttall, Y. Chan, X. Huang, T. Asefa, Developing and testing
electrochemical methods for treating metal salts, cyanides and organic compounds in waste
streams, Waste Manage. 18 (1998) 257-263.
[7] T.T. Christison, J.S. Rohrer, Direct determination of free cyanide in drinking water by ion
chromatography with pulsed amperometric detection, J. Chromatogr. A 1155 (2007) 31-39.
[8] A.V.L. Gomez, J.M. Calatayud, Determination of cyanide by a flow injection analysis-atomic
absorption spectrometric method, Analyst 123 (1998) 2103-2107.
[9] A. Panitsiri, S. Tongkhan, W. Radchatawedchakoon, U. Sakee, Synthesis and anion
recognition studies of novel bis(4-hydroxycoumarin) methane azo dyes, J. Mol. Struct. 1107
(2016) 14-18.
[10] N. Yadav, A.K. Singh, Dual anion colorimetric and fluorometric sensing of arsenite and
cyanide ions, RSC Adv. 6 (2016) 100136-100144.

Journal Pre-proof
14
[11] I.J. Kim, M. Ramalingam, Y.A. Son, A reaction based colorimetric chemosensor for the
detection of cyanide ion in aqueous solution, Sensors Actuators B Chem. 246 (2017) 319-
326.
[12] P. Gholamzadeh, G.M. Ziarani, N. Lashgari, A. Badiei, A. Shayesteh, M. Jafari, A simple
colorimetric chemosensor for naked eye detection of cyanide ion, J. Fluoresc. 26 (2016)
1857-1864.
[13] Z. Li, C. Liu, S. Wang, L. Xiao, X. Jing, Visual detection of cyanide ion in aqueous medium
by a new chromogenic azo-azomethine chemosensor, Spectrochimica Acta A 210 (2019)
321-328.
[14] P.M. Reddy, S-R. Hsieh, J-K Chen, C-J Chang, J-Y Kang, C-H Chen, Robust, sensitive and
facile method for detection of F−, CN− and Ac− anions, Spectrochimica Acta A 186 (2017) 8-
16.
[15] P.M. Reddy, S-R Hsieh, M-C Lee, C-J Chang, A. Pundi, Y-S Chen, C-H Lu, J-M Yeh,
Aniline trimer based chemical sensor for dual responsive detection of hazardous CN¯ ions
and pH changes, Dyes Pigments 164 (2019) 327–334.
[16] P.M. Reddy, S-R Hsieh, W-C Wu, C-J Chang, Y-S Chen, M-C Lee, Quinone based
oligomeric sensors as colorimetric probes for cyanide anion: Effects of solvent medium and
substituent on sensing, React. Funct. Polym. 123 (2018) 26-33.
[17] Q. Zou, F. Tao, H. Wu, W. W. Yu, T. Li, Y. Cui, A new carbazole-based colorimetric and
fluorescent sensor with aggregation induced emission for detection of cyanide anion, Dyes
and Pig. 164 (2019) 165-173.

Journal Pre-proof
15
[18] P.R. Lakshmi, P. Jayasudha, K.P. Elango, Selective chromogenic detection of cyanide in
aqueous solution-Spectral, electrochemical and theoretical studies, Spectrochimica Acta A,
213 (2019) 318-323.
[19] P. Madhusudhana Reddy, S.–R. Hsieh, C.–J. Chang, J.–Y. Kang, Detection of cyanide ions
in aqueous solutions using cost effective colorimetric sensor, J. Hazard. Mater. 334 (2017)
93–103.
[20] T. Abdinejad, M.R. Zamanloo, N.O. Mahmoodi, T. Alizadeh, A.N. Shamkhali, Colorimetric
sensing of cyanide ion by pyromellitic diimides synthesized in one step from commercially
available reactants, J. Photochem. Photobiol. A, 371 (2019) 17-24.
[21] H. Tavallali, G. Deilamy-Rad, A. Parhami, N. Hasanli, A novel cyanide-selective
colorimetric and fluorescent chemosensor: First molecular security keypad lock based on
phosphotungstic acid and CN− inputs, J. Hazard. Mater. 266 (2014) 189– 197
[22] Y.M. Chung, B. Raman, D.S. Kim, K.H. Ahn, Fluorescence modulation in anion sensing by
introducing intramolecular H-bonding interactions in host–guest adducts, Chem. Commun.
(2006) 186-188.
[23] D.G. Cho, J.H. Kim, J.L. Sessler, The Benzil−Cyanide Reaction and Its Application to the
Development of a Selective Cyanide Anion Indicator, J. Am. Chem. Soc. 130 (2008) 12163-
12167.
[24] X. Lv, J. Liy, Y. Zhao, M. Chen, P. Wang, W. Guo, A ratiometric fluorescent probe for
cyanide based on FRET, Org. Biomol. Chem. 9 (2011) 4954-4958.

Journal Pre-proof
16
[25] Y. Shiraishi, K. Adachi, M. Itoh, T. Hirai, Spiropyran as a Selective, Sensitive, and
Reproducible Cyanide Anion Receptor, Org. Lett. 11 (2009) 3482-3485.
[26] Y. Shiraishi, S. Sumiya, T. Hirai, Highly sensitive cyanide anion detection with a coumarin–
spiropyran conjugate as a fluorescent receptor, Chem. Commun. 47 (2011) 4953-4955.
[27] X. Lv, J. Liu, Y. Liu, Y. Zhao, Y. Q. Sun, P. Wang, W. Guo, Ratiometric fluorescence
detection of cyanide based on a hybrid coumarin–hemicyanine dye: the large emission shift
and the high selectivity, Chem. Commun. 47 (2011) 12843-12845.
[28] N. Niamnont, A. Promchat, C. Siangma, C. Pramaulpornsatit, M. Sukwattanasinitt, A novel
phenylacetylene-indolium fluorophore for detection of cyanide by the naked eye, RSC Adv.
5 (2015) 64763-64768.
[29] K.Y. Chen, W.C. Lin, A simple 7-azaindole-based ratiometric fluorescent sensor for
detection of cyanide in aqueous media, Dyes Pigm. 123 (2015) 1-7.
[30] R. Badugu, J.R. Lakowicz, C.D. Geddes, Enhanced Fluorescence Cyanide Detection at
Physiologically Lethal Levels:ꢀ Reduced ICT-Based Signal Transduction, J. Am. Chem. Soc.
127 (2005) 3635-3641.
[31] Z. Ekmekci, M.D. Yilmaz, U.D. Akkaya, A Monostyryl-boradiazaindacene (BODIPY)
Derivative as Colorimetric and Fluorescent Probe for Cyanide Ions, Org. Lett. 10 (2008) 461-
464.
[32] J. Zhang, S. Zhu, L. Valenzano, F.T. Luo, H. Liu, BODIPY-based ratiometric fluorescent
probes for the sensitive and selective sensing of cyanide ions, RSC Adv. 3 (2013) 68-72.

Journal Pre-proof
17
[33] B. Zou, H. Liu, J. Mack, S.Wang, J. Tian, H. Lu, Z. Li, Z. Shen, A new aza-BODIPY based
NIR region colorimetric and fluorescent chemodosimeter for fluoride, RSC Adv. 4 (2014)
53864-53869.
[34] X. Wu, B. Xu, H. Tong, L. Wang, Highly Selective and Sensitive Detection of Cyanide by a
Reaction-Based Conjugated Polymer Chemosensor, Macromolecules 44 (2011) 4241-4248.
[35] Z. Liu, X. Wang, Z. Yang, W. He, Rational Design of a Dual Chemosensor for Cyanide
Anion Sensing Based on Dicyanovinyl-Substituted Benzofurazan, J. Org. Chem. 76 (2011)
10286-10290.
[36] X. Cheng, Y. Zhou, J. Qin, Z. Li, Reaction-Based Colorimetric Cyanide Chemosensors:
Rapid Naked-Eye Detection and High Selectivity, ACS Appl. Mater. Interfaces 4 (2012)
2133-2138.
[37] X. Cheng, R. Tang, H. Jia, J. Feng, J. Qin, Z. Li, New Fluorescent and Colorimetric Probe
for Cyanide: Direct Reactivity, High Selectivity, and Bioimaging Application, J. Am. Chem.
Soc. 4 (2012) 4387-4392.
[38] L. Yang, X. Li, J. Yang, Y. Qu, J. Hua, Colorimetric and Ratiometric Near-Infrared
Fluorescent Cyanide Chemodosimeter Based on Phenazine Derivatives, J. Am. Chem. Soc. 5
(2013) 1317-1326.
[39] P.B. Pati, S.S. Zade, Dicyanovinyl terthiophene as a reaction based colorimetric and
ratiometric fluorescence probe for cyanide anions, RSC Adv. 3 (2013) 13457-13462.

Journal Pre-proof
18
[40] W.C. Lin, S.K. Fang, J.W. Hu, H.Y. Tsai, K. Y. Chen, Ratiometric Fluorescent/Colorimetric
Cyanide-Selective Sensor Based on Excited-State Intramolecular Charge Transfer−Excited-
State Intramolecular Proton Transfer Switching, Anal. Chem. 86 (2014) 4648-4652.
[41] K.S. Lee, S.J. Kim, J.H. Kim, I. Shin, J.I. Hong, Fluorescent Chemodosimeter for Selective
Detection of Cyanide in Water, Org. Lett., 2008, 10, 49-51.
[42] J. Jo, D. Lee, Turn-On Fluorescence Detection of Cyanide in Water: Activation of Latent
Fluorophores through Remote Hydrogen Bonds That Mimic Peptide β-Turn Motif, J. Am.
Chem. Soc. 131 (2009) 16283-16291.
[43] N. Niamnont, A. Khumsri, A. Promchat, G. Tumcharern, M. Sukwattanasinitt, Novel
salicylaldehyde derivatives as fluorescence turn-on sensors for cyanide ion, J. Hazard. Mater.
280 (2014) 458-463.
[44] K. Prakash, P.R. Sahoo, S. Kumar, A substituted spiropyran for highly sensitive and
selective colorimetric detection of cyanide ions, Sensors Actuators B Chem. 237 (3016) 856-
864.
[45] M.J. Kim, R. Manivannan, I.J. Kim, Y.A. Son, A colorimetric and fluorometric
chemosensor for the selective detection of cyanide ion in both the aqueous and solid phase,
Sensors Actuators B Chem. 253 (2017) 942-948.
[46] P.M. Reddy, S.R. Hsieh, C.J. Chang, J.Y. Chang, Detection of cyanide ions in aqueous
solutions using cost effective colorimetric sensor, J. Hazard. Mater. 334 (2017) 93-103.
[47] Y.W. Liu, M.X. Kao, A.T. Wu, Discriminating detection between F− and CN− by naked eye
from Schiff base sensor, Sensors Actuators B Chem. 208 (2015) 429-435.

Journal Pre-proof
19
[48] Y. Wang, Q. Zhao, L. Zang, C. Liang, S. Jiang, Discriminating detection of multiple
analytes (F− and CN−) by a single probe through colorimetric and fluorescent dual channels,
Dyes Pigments 123 (2015) 166-175.
[49] L. Chen, H. Nie, G. Zhang, F. Gong, F. Yang, C. Gong, Q. Tang, Cyanide ion colorimetric
chemosensor based on protonated merocyanine in EtOH, Tet. Lett. 55 (2014) 3017-3023.
[50] S. Bhardwaj, A.K. Singh, Visual & reversible sensing of cyanide in real samples by an
effective ratiometric colorimetric probe & logic gate application, J. Hazard. Mater. 296
(2015) 54–60
[51] R. Purkait, C. Patra, A. Dasmahapatra, D. Chattopadhyay, C. Sinha, A visible light excitable
chromone appended hydrazide chemosensor for sequential sensing of Al+3 and F- in aqueous
medium and in Vero cells, Sensor Actuat. B-Chem. 257 (2018) 545-552.
[52] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman, G.
Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P.
Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M. Hada, M. Ehara, K.
Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T.
Vreven, J.A. Montgomery Jr, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers,
K.N. Kudin, V.N. Staroverov, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J.C.
Burant, S.S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B.
Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J.
Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G.
Zakrzewski, G.A. Voth, P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas,
J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian 09, Revision D.01, Gaussian
Inc, Wallingford, CT (2009).

Journal Pre-proof
20
[53] A.D. Becke, Density‐functional thermochemistry. III. The role of exact exchange, J. Chem.
Phys. 98 (1993) 5648-5652.
[54] M. Cossi, V. Barone, Time-dependent density functional theory for molecules in liquid
solutions, J. Chem. Phys. 115 (2001) 4708-4717.
[55] M. Cossi, N. Rega, G. Scalmani, V. Barone, Energies, structures, and electronic properties
of molecules in solution with the C-PCM solvation model, J. Comput. Chem. 24 (2003) 669-
681.
[56] N.M. O'Boyle, A.L. Tenderholt, K.M. Langner, cclib: a library for package-independent
computational chemistry algorithms, J. Comput. Chem. 29 (2008) 839-845.
[57] A.R. Surleva, G. Drochioiu, Visualizing Smoking Hazard: A Simple Spectrophotometric
Determination of Hydrogen Cyanide in Cigarette Smoke and Filters, J. Chem. Educ., 90
(2013) 1654–1657.
[58] Y. Ding, T. Li, W. Zhu, Y. Xie, Highly selective colorimetric sensing of cyanide based on
formation of dipyrrin adducts. Org. Biomol. Chem. 10 (2012) 4201-4207.
[59] O.K. Koc, H. Ozay, A simple azoquinoline based highly selective colorimetric Sensor for
CN- anion in aqueous media. Canadian J. Chem. 95 (2017) 771-777.
[60] R.M.F. Batista, E. Oliveira, S.P.G. Costa, C. Lodeiro, M.M.M. Raposo, Cyanide and
fluoride colorimetric sensing by novel imidazo-anthraquinones functionalised with indole
and carbazole. Supramol. Chem. 26 (2014) 71-80.

Journal Pre-proof
21
[61] J. Mondal, A.K. Manna, G.K. Patra, Highly selective hydrazone based reversible
colorimetric chemosensorsfor expeditious detection of CN- in aqueous media. Inorg. Chim.
Acta 474 (2018) 22-29.

Journal Pre-proof
22
Chromogenichydrazide Schiffbasereagent:spectrophotometricdetermination
ofCN- ion
Sunanda Dey, Chandana Sen, Chittaranjan Sinha*

Journal Pre-proof
23
Highlights
 A simple hydrazide Schiff base has been developed using condensation method.
 CN- ion can be determined from the reflected spectrophotometric response and the
proposed method seems to be very simple, fast, sensitive and selective for CN-.
 This cost-effective, useful technique has been successfully applied as a sensor by simple
test paper strip.