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DOI: 10.1002/slct.

201600229 Full Papers

z Organic & Supramolecular Chemistry

Selective Colorimetric Sensor for the Detection of Hg2 +


and H2S in Aqueous Medium and Waste Water Samples
Rahul Kaushik,[a] Ajeet Singh,[b] Amrita Ghosh,[a] and D. Amilan Jose*[a]

Dabsyl based new colorimetric sensor 1 for the selective de- was also explored with good recovery value. The ensemble
tection of environmentally most important cation Hg2 + and bi- 1.Hg2 + , also applicable for the detection of H2S (LOD = 28 mM)
ologically important hydrogen sulfide (H2S) in aqueous medium in water among different bio-thiols and anions. H2S displaces
have been reported. The probe 1 selectively responded to Hg2 + the mercury from 1.Hg2 + via metal displacement approach and
among various cations and shows colour change from yellow regenerates the original probe 1 within few seconds. Regen-
to red with the bathochromic shift in Uv-Vis spectrum via intra- erated receptor 1, further used for the detection of mercury
molecular charge transfer (ICT) mechanism. The limit of de- ion. Receptor 1 incorporated test paper and polymer based
tection for mercury was determined as 80 mM. The possibility of thin films were used as a portable kit for the selective colori-
using 1 to detect mercury in industrial waste water samples metric detection of mercury and H2S in water.

ment of a colorimetric dip test kit that allows the semi-quanti-


Introduction
tative detection of target cations using a color is in high de-
Mercury is one of the well-known environmental pollutants for mand, as it can be evaluated visually without illumination.
several decades[1]. It is a highly toxic heavy metal along with H2S is the third endogenously generated gaseous signaling
lead and cadmium. Generally, very low concentration of mer- molecule along with NO and CO[9]. Much work has been de-
cury could be found in the environment. High concentration of voted to the detection of H2S using fluorescent and colori-
mercury exposure causes serious problems to human health. metric probes based on nucleophilic cyclization[10], reduction[11]
The most well-documented cases of severe mercury poisoning and metal sulfide formation via metal displacement method[12].
are from Minamata Bay, Japan in 1956 (industrial release of Among these, metal displacement approach is advantageous
methylmercury)[2] and the 1971 Iraq poison grain disaster as it has fast response time and reversibility. These probes are
(wheat treated with a methylmercury as a fungicide).[3] mainly composed of fluorogenic/chromogenic units attached
Considering its serious hazardous effect and toxicity, it is to the copper and/or zinc metal complexes of heterocyclic li-
very important to determine and control the level of mercury gands.[13] However, colorimetric probe for H2S based on mer-
in the environment. Although trace levels of mercury have cury complexes is not well explored.[14]
been determined by advanced analytical techniques, a sensi- Herein, in the present work, we report a dabsyl based chro-
tive, selective and easily synthesizable probe which shows col- mogenic probe 1 containing 2-aminothiophenol for the colori-
orimetric change is in high demand to detect mercury in real metric detection of Hg2 + . The probe exhibited high selectivity
samples[4]. Accordingly a variety of Hg2 + sensors based on small and non- interference with other metal ions in aqueous me-
molecules[5], bio-molecules[6], polymers[7], nanoparticles[8] and dium. Interestingly, 1.Hg2 + ensemble can be further used for
micelles[7d] are reported. However, most of them have certain the colorimetric detection of H2S among different biothiols and
limitations, i.e. multistep synthesis, non-aqueous environment, halides.
irreversibility and lack of selectivity in the presence of the other
interference metals like Ag + and Pb2 + because of their similar
Results and Discussion
chemical behavior to Hg2 + .[4a] Colorimetric response remains a
popular technique due to the factors such as low cost, naked Nitrogen and sulfur can act as soft binding sites for metal cati-
eye detection, easy handling and inexpensive consumables. For ons.[15] A probe with adjacent thiol and amine moieties (as a
simplicity and to achieve a low-cost alternative, the develop- binding unit) and a chromophore (as a charge donating unit)
could be an effective receptor for the binding of Hg2 + .[15a] This
has encouraged us to design a new colorimetric probe 1 based
[a] R. Kaushik, Dr. A. Ghosh, Dr. D. A. Jose
Department of Chemistry, NIT-Kurukshetra, Haryana-136119, India on electron donating dimethylamino group and electron with-
Tel: + 91-1744233559 drawing sulfonamide group in conjugation with thiophenol
E-mail: amilanjosenit@nitkkr.ac.in moiety.
[b] Dr. A. Singh
Receptor 1 was synthesized by following a simple one step
Department of Chemistry, University of Allahabad, Allahabad–211002,
India reaction (Scheme 1) and characterized by standard analytical
Supporting information for this article is available on the WWW under and spectroscopic techniques (Supporting information). The
http://dx.doi.org/10.1002/slct.201600229 Uv-Vis absorption spectrum of 1 recorded in HEPES-CH3CN buf-

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to a characteristic red shift accompanied by a color change.
The ICT nature of 1 was confirmed by the bathochromic shifts
of absorption band along with a gradual increase in the solvent
polarity (SI Figure 2B).

Scheme 1. A schematic method for the synthesis of receptor 1. Reagents and


Conditions: (a) Triethyl amine, DCM, N2, 24 hrs, RT. .

fer (6: 4, 10 mmol, pH = 7.4) solution showed an intense ab-


sorption band at 425 nm (19, 540 M-1 cm-1).
Upon addition of mercury perchlorate, the absorption band
at 425 nm was shifted to 460 nm (e = 20, 500 M-1 cm-1) with a
color change from light yellow to red. However, no such spec-
tral change could be observed after the addition of 20 equiv-
Figure 2. Uv-Vis titration of 1 (1 3 10-4 M) with Hg2 + (0 - 2 3 10-3 M) in HEPES-
alents of (5 3 10-4 M) other cations such as Ca2 + , Ni2 + , Zn2 + , CH3CN buffer. (inset) Jobs’ plot of 1 with Hg2 + .
Pb2 + , Cr3 + , Cd2 + , Cu2 + , Sr2 + Ag + , Co2 + , Fe2 + , Mg2 + , Fe3 + , Li + ,
Na + and K + (Figure 1).

The sensitivity of receptor 1 towards Hg2 + was studied by


systematic Uv-Vis absorbance titration in HEPES- CH3CN buffer
(6:4, 10 mmol, pH = 7.4). As shown in Figure 2 upon addition
of Hg2 + (0 - 2 3 10-3 M) to the receptor solution, the initial ab-
sorption at 425 nm gradually red shifted to 460 nm with a color
change. Based on the change in Uv-Vis spectrum the limit of
detection (LOD) for Hg2 + was found out to be 80 mM (3 x s x
slope 1).
The interference of different metal ions with the selective
mercury sensing behavior of 1 was checked with Hg2 + in the
presence of other metal cations such as Co2 + , Ca2 + , Ni2 + , Zn2 + ,
Pb2 + , Cd2 + , Cu2 + , Sr2 + Ag + , Pb2 + , Cr3 + , Fe2 + , Li + , Na + and K +
and Mg2 + (Figure 3). As shown in the Figure 3, copper shows
reasonable interference but other metals did not show any sig-
nificant interference. We have also tested the Hg2 + detection in
a ternary and quaternary mixtures of metals and they did not
show any considerable interference for mercury binding (SI Fig-
ure 4).
In all of the interference experiments color change was
easily detectable via naked eyes (yellow to red) indicate that
the spectral and colorimetric response is not affected by the
Figure 1. (a) Colour changes of 1 in presence and absence of metal ions in other metal cations.
HEPES:CH3CN (6:4, 10 mmol at pH 7.4). (b) Uv-Vis spectral changes of 1 (2.5 In order to understand the binding stoichiometry of 1.Hg2 +
3 10-5 M) with Hg2 + (5 3 10-4 M) and different metals ions (5 3 10-4 M, 20
equivalents). Fe3 + produced a large amount of precipitate; so Uv-Vis spec- complex, the Job plot experiments were carried out and the
trum with Fe3 + is not presented. stoichiometry was found out to be 1:1 complex, wherein the
total concentration of both Hg2 + and the probe is 5 3 10-5 M
and variation in mole fraction of Hg2 + is from 0 to 1 (Figure 2
inset).
The mercury binding with amino and thiol moiety may fa- We have also checked the mercury binding behavior of 1 in
cilitate the intramolecular charge transfer (ICT), which give rise fluorescence spectroscopy methods. Receptor 1 showed an

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rescence and Uv-vis titrations results confirm that the receptor
1 selectively binds with the mercury among different metal cat-
ions in aqueous solution with good detection limit.

DFT calculation
The geometry of receptor 1 and the binding nature of 1.Hg2 +
was further evaluated by DFT studies using pseudo-potential
basis set[16] (LANL2DZ for Hg and 6-31 + G(d) for other atoms)
using Gaussian 09 frontier orbital energy levels[17]. The resulting
computational calculation indicated that in gas phase energy
levels of the free receptor were HOMO (-5.74499 eV) and LUMO
(-2.64881 eV) and mercury complex were HOMO (-5.71860 eV)
and LUMO (-3.93839 eV), respectively. In solvent phase (water)
energy levels of the free receptor HOMO (-5.63805 eV) and
Figure 3. Change in absorbance of 1 (2.5 3 10-5 M) upon the addition of LUMO (-2.77589 eV) and the mercury complex were HOMO
Hg2 + (5 3 10-4 M, 20 equivalents) (red), different metal ions (blue bars) and
the addition of different metal ions (5 3 10-4 M, 20 equivalents) in the pres-
(-4.85053 eV) and LUMO (-2.73861 eV), respectively. The band
ence of Hg2 + (5 3 10-4 M, 20 equivalents) (brown bars) in buffer. gap between the HOMO-LUMO in solvent phase decreased.
HOMO energy of free receptor showed that the delocalized
electron distribution. In contrast, the electron distribution of
HOMO energy in mercury complex was localized in the area of
Hg2 + binding thio phenol area (Figure 5). In solvent phase (wa-

Figure 4. Fluorescence quenching of the receptor 1 (2.5 3 10-5 M) upon addi-


tion of Hg2 + (0–2,5 3 10-3 M) Slit width = 10/10. Excitation wavelength at
260 nm. Inset: Benesi–Hildebrand (B-H) plot of fluorescence decrement of the
probe as a function of the Hg2 + concentration. F0 and F represent the fluo-
rescence intensity of the probe in the absence and presence of different con-
centrations of Hg2 + .

emission maximum at 370 nm (lexc = 260 nm) in HEPES- CH3CN


buffer (6:4, 10 mmol, pH = 7.4). Upon successive addition of
Hg2 + (2.5 3 10-3 M) to the 1 (2.5 3 10-5 M) the fluorescence
emission is completely quenched (Figure 4) due to the for-
mation of 1.Hg2 + ensemble. Mercury is well known as a
quencher of fluorescence intensity through its effective spin-or- Figure 5. Frontier molecular orbitals (HOMO and LUMO) optimized at the
bit coupling[4a]. Except copper, other metal ions such as Co2 + , LANL2DZ for and 6-31G(d) level of theory.

Ca2 + , Ni2 + , Zn2 + , Pb2 + , Cd2 + , Sr2 + Ag + , Pb2 + , Cr3 + , Li + , Na + , K + ,


Fe2 + and Mg2 + did not show significant change in the emission
intensity (supporting information). But copper did not show ter) the free receptor and mercury complex were indicating
any colorimetric response with receptor 1. The association con- that the dielectric continuum model interacts with solute mole-
stant (Ka) for the binding of 1 to Hg2 + was calculated by emis- cule and it stabilizes the ground state of the solute molecule. It
sion titration and value was found to be 52,356 M-1. The fluo- can be demonstrated that both in gas and solvent phase well-

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Table 1. Determination of Hg2 + in some environmental water samples


for real life samples and is suit-
able for application under
Sample[a] Spiked (M) Found (M) Recovery (%) LOD (10-4 M)
physiological conditions.
Sample 1 5x10-4  4.6a 4.8 x 10-4  8.6a 96 1.52b
Sample 2 5x10-4  5.7a 4.75x10-4  9.7a 95 1.58b
Sample 3 5x10-4  5.7a 4.70x10-4  13.7a 94 1.86b Determination of Hg2 +
[a] Value is calculated by taking the average of three independent readings. [b] LOD is calculated by the using the
in industrial waste
standard deviation (SD) and slope of the linear curve using the formula: LOD = 3 3 SD/slope. water samples
Further, the mercury detection
of 1 in waste water sample was
separated charge distribution between HOMO and LUMO in-
dicating substantial charge transfer from 4-dimethylaminophe-
nylazo group (donor) and the thiophenol ring with sulfonamide
moiety (acceptor). The 1:1 complex formation of 1 with Hg2 +
obtained from DFT calculation supports the experimental result
obtained from jobs’ plot. The colorimetric response of mercury
ion may be correlated with the perturbation in the energy of
the frontier orbitals of the donor amine and the acceptor azo
functionality.

Figure 7. The linear relationship of change in absorbance values vs. different


concentrations of Hg2 + ions in three different water samples collected from
an industrial area of Yamuna Nagar, India.

evaluated by three different samples collected from the in-


dustrial area of Yamuna Nagar, Haryana, India. Initially, the sam-
ples were filtered through 0.25 mm membrane to remove the
solid particles and spiked them with different amount of Hg2 +
Figure 6. Effect of pH on mercury binding with receptor 1 (1 3 10-4 M) in the (2.5 3 10-4 -1.75 3 10-3).
presence of Hg2 + (2 3 10-3 M). In Uv-Vis absorption spectrum of the receptor 1 gives a red
shift with the waste water samples along with the colorimetric
change in the solution. Based on the change in the absorption
spectrum, the calculated LOD value for Hg2 + in all the three
water samples were found to be 1.52 x 10-4 M, 1.58 x 10-4 M
Effect of pH
and 1.86 x 10-4 M respectively. The response of 1 increased line-
Mercury sensor must be effective over a wide range of pH since arly along with the increase in the concentration of Hg2 +
in real life the mercury contaminated samples may be obtained spiked water (Figure 7). As shown in Table 1, the recovery ex-
from different sources. Therefore, the influence of pH on 1 with periments using Hg2 + spiked samples came out to be 96%,
mercury binding was studied by using Uv-Vis measurement. 95% and 94% for sample 1, sample 2 and sample 3 respectively
The sensing study of receptor 1 with different pH range 2.0 to (see SI).
14.0, was studied. It was found that the sensor can be quite These experimental results demonstrated that one of the
effective in the range of pH 4.0-8.0 (Figure 6). potential applications of receptor 1 for the detection of mer-
But at  pH 3 the amino and thiol proton cannot be easily cury in industrial waste water samples. High tolerance of re-
abstracted due to common ion effect, whereas  pH 9 predom- ceptor 1 could be used for on-site preliminary screening of
inantly precipitation occurs due to the formation of insoluble Hg2 + in the aqueous samples with fast response. The recovery
metal hydroxides. These results described that the detection of of Hg2 + from the waste water samples was statistically close to
mercury using probe 1 was pH dependent and change in ab- 100%, indicating the validation of the detection of Hg2 + in in-
sorption spectrum with Hg2 + was obtained in the pH range of dustrial water samples. These results also indicated that the
4.0-8.0. This study proves that receptor 1 can be very effective contaminations in the industrial waste water could not affect
the Hg2 + detection of our sensor system.

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Test paper and thin film optical changes of the PVA films. These results demonstrates
selective mercury detection of sensor 1incorporated test paper
Encouraged by the above results, the possibilities of using re- and polymer film.
ceptor 1 in the development of test paper and test films were The detection limit of mercury in test paper and film were
examined. Receptor 1 incorporated test paper strips were pre- found to be 5 x10-4 and 5 x 10-3 M respectively. They are low as
pared by Whatman filter paper was immersed in 1 3 10-4 M sol- compared to solution. Similar type of observation, low de-
ution of 1 in HEPES-CH3CN buffer (6:4, v/v) for 60 minutes, tection limit in test paper was also observer by other reports[19].
which were then allowed to dry at RT for overnight. The pale These results indicated that the sensor 1 can be prepared as a
yellow color test paper was dipped in an aqueous solution of test-paper or test film for the detection of mercury as similar to
Hg2 + . As shown in Figure 8a, the color of the test paper pH paper. It is highly selective and can detect mercury in aque-
ous solutions without any help of spectroscopic in-
strumentation (supporting information). Test stripes based on
polymeric film and paper is suitable for the safe and easy de-
tection of the dangerous mercury ion in industrial waste water.
Receptor 1 for Hg2 + metal ion has been compared with the
previously reported literature. From the Table 2, the proposed
sensor 1 results seem to be good with respect to Limit of de-
tection (LOD) and detection time. Most of the absorption based
mercury probes displayed good LOD either in pure organic me-
dium or by using less % organic solvent along with water. Re-
Figure 8. (a) The test paper-based visual detection of different cations ceptor 1 also displayed higher LOD (6.8 mM) in pure CH3CN (SI
(5 3 10-2 M) with 1 (b) The change in color of the PVA film for probe 1 with Figure 3B).
different metals (5 3 10-2 M).

Selective colorimetric
Table 2. Some of the reported colorimetric probes for the detection mercury. detection of H2S in
Sensor Probe LOD Medium Detection Reference water
time
H2S has been recognized as
[5k]
Benzoylthiourea based probe 1 mM DMSO/H2O (4:1) < 1 min one of the three gaso-
[19a]
Azo-benzene based sensor 20 mM CH3CN < 1 min transmitters along with nitric
Terpyridine Derivatives 25 nM DMSO/Water (3:7) NDa [19b]

1,4-di substituted Azines 52 mM Water/ CH3CN NDa [5l] oxide (NO) and carbon mon-
(3:7) oxide (CO).[9a] A number of
[20]
Rhodamine based thiourea sensor 6.36 mM Water/ CH3CN 60 min chemical sensors for the de-
(99:1) tection of H2S have been devel-
BODIPY based sensor 0.53 mM CH3CN NDa [21]

Thioacetals based probe 0.8 mM THF Rapid [22] oped in last decade.[10-11, 23]
BODIPY based triazole 0.22 mM CH3CN–H2O(4:1) Fast [5j] However, selectivity over com-
[5i]
Rhodamine-thiosemicarbazide based 0.01 mM DMF/Water (1:1) rapid peting biothiols such as gluta-
sensor thione (GSH), cysteine (Cys) and
Sulfonamide based thiol 80 mM Water/CH3CN (6:4) < 30 seconds Present
and Work
homocysteine (Hcy), response
6.8 mM CH3CN time and biocompatibility are
some of the serious limitations.
[a] ND = not determined
The sulfide anion shows strong
intrinsic affinity for transition
metals such as copper (Ksp for
changed to red immediately (< 30 seconds) only with mercury CuS = 6 3 10-36), zinc (Ksp for ZnS = 2 3 10–25) and mercury (Ksp
(5 3 10-2 M). The color change was not obtained with other for HgS = 2 3 10-53). Recently, we have reported Copper and
metals even after keeping for long period of time. Zinc complex based receptors for the selective detection of H2S
Polymers offer a lot of advantages for optical sensor tech- in biological fluids[13b, c]. In this connection, we found that mer-
nologies and polymer films play an essential role in chemical cury-based metal complexes are not well explored for the de-
sensors.[5h, 18] Therefore, we have incorporated receptor 1 into tection of H2S in water[24]. Hg2 + forms HgS with sulfide anions[14]
the polymer poly vinyl alcohol (PVA) by heating the mixture of as like Cu and Zn[13b, c], therefore we have checked the possible
1 and PVA in water and then allowed to dry in a petri dish for a binding behavior of residual ensemble 1.Hg2 + with H2S in
day at RT to make a thin film. Pale yellow in color PVA films aqueous solution (Na2S has been used as a source of H2S).
incorporated with probe 1 was changed to red when the film Upon addition of Na2S (2 x 10-4 M) to the solution of 1.Hg2 +
dipped into the aqueous solution of Hg2 + (5 3 10-2 M). Experi- , the absorption band of ligand at 428 nm has been reappeared
ments with other cations (5 3 10-2 M) such as Ag + , Mg2 + , Cr3 + , with a color change from red to yellow. This is due to the dis-
Ca2 + , Ni2 + , Zn2 + , Cd2 + , Pb2 + and Cu2 + displayed a lack of any placement of Hg2 + ion from 1.Hg2 + complex.

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As shown in Figure 9, the probe checked with the range of
physiological and biological important analytes such as reactive

Figure 10. Visual detection of H2S (2 3 10–3 M) with 1.Hg2 +

Figure 11. Test paper-based visual detection of 1 (0.0001 M) with different


anions (2 3 10–3 M) after dipped in Hg2 +
Figure 9. Test paper-based visual detection of 1 (0.0001 M) with different
anions (2 3 10–3 M) after dipped in Hg2 + .

and synthesized by one-step method. It showed selective color


sulfur species (glutathione, cysteine, and methionine), reactive change from pale yellow to red and on-off fluorescence
nitrogen species (NO) and halides (F-, Cl-, Br-, I- and CN-). changes only with Hg2 + among the representative transition
Except Iodide, other analytes did not cause any significant and heavy metallic cations. The sensor also displayed a se-
change either in color or in the absorption spectra of 1.Hg2 + . lective chromogenic behavior in test paper and polymeric thin
Changes in the absorption spectra and color of 1 in the pres- film, which could be easily observed by naked eye. Additionally,
ence of excess iodide suggest that the formation of a stable this probe takes advantage of surpassing the drawback of low
iodide complex HgI42-.[25] Glutathione shows a little change in solubility in water and dual sensing behavior of most of the re-
the Uv-Vis spectrum may be due to weak binding of the thiol ported mercury sensor[5e, f, 27]. The structures of 1 and its mer-
group with mercury. cury complex were also optimized by DFT calculations. It binds
Real-time detection of H2S are important for the practical Hg2 + in a 1: 1 ratio with an association constant of 52,356 M-1
application, consequently the real-time detection of the 1.Hg2 + and detects Hg2 + as low as 80 mM.
sensing ensemble has the advantage over reaction based en- We see that the probe 1 has number of advantage as listed
semble reported earlier for H2S detection.[10-11] Based on the below. (a) Probe 1 easily synthesizable by single step method
change in absorption spectra the detection limit of H2S calcu- that eliminated the need of multi-step synthesis (b) Naked eye
lated using 1.Hg2 + are 2.84 x 10-5 M, which was comparable to detection only with mercury (c) fast response (< 30 seconds)
other probes reported for H2S, based on metal displacement time with Mercury and H2S (d) Reversible mode colour and
approach.[26] The detection limit was calculated by using earlier spectral change with Mercury and followed by H2S makes re-
reported methods.[13b, c] These results confirm that the higher ceptor 1 as an recyclable probe (f) Suitable for the detection of
selectivity and sensitivity of H2S among other biological im- mercury in environmental waste water samples. The high de-
portant analytes. The reversibility experiments suggest that gree of selectivity in aqueous solution makes receptor 1 attrac-
1.Hg2 + shows the property of reversibility with H2S (Figure 10) tive for potential use in the analysis of sub-micromolar concen-
and could be reused several times. tration ranges of mercury contamination in actual
Further, test papers and thin film obtained from mercury environmental samples. Further, biologically important analyte
solution of 1 (Figure 11), dipped in the solution of different thi- H2S could rapidly react with the mercuric center of residual en-
ols it regains its yellow color only with H2S solution. Thus, col- semble 1.Hg2 + to release the receptor leading to the recovery
orimetric detection of H2S satisfied the trends that observed in of original receptor’s color and fluorescence. It shows high se-
the aqueous media. lectivity and sensitivity for H2S with a detection limit of 28.4
mM. The reversible nature of 1.Hg2 + with H2S makes receptor 1
as a good addition to the club of small molecules based mer-
Conclusions
cury and H2S selective chemosensors.
In Conclusion, a new simple colorimetric and fluorescent sensor
(E)-4-((4-(dimethylamino)phenyl)diazenyl)-N-(2mercaptophe-
nyl)benzenesulfonamide(receptor 1) for mercury was designed

ChemistrySelect 2016, 1, 1533 – 1540 1538  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Supporting information Liu, G. Chang, Y. Zhang, Y. Luo, A. M. Asiri, A. O. Al-Youbi and X. Sun,
Anal. Chem. 2012, 84, 5351-5357; e) F. Zhang, L. Zeng, C. Yang, J. Xin, H.
Wang and A. Wu, Analyst 2011, 136, 2825-2830; f) G. V. Ramesh and T. P.
Procedure for the synthesis of receptor 1, experimental meth- Radhakrishnan, ACS Appl. Mater. Interfaces 2011, 3, 988-994; g) E. Delga-
ods for UV-Visible absorption and emission titration studies can do-Pinar, N. Montoya, M. Galiana, M. T. Albelda, J. C. Frias, H. R. Jimenez,
be found in the supporting information. E. Garcia-Espana and J. Alarcon, New J. Chem. 2010, 34, 567-570.
[9] a) H. Kimura, Mol. Neurobiol. 2002, 26, 13-19; b) J. L. Wallace and R.
Wang, Nat Rev Drug Discov 2015, 14, 329-345.
Acknowledgements [10] N. Kumar, V. Bhalla and M. Kumar, Coord. Chem. Rev. 2013, 257, 2335-
2347.
We acknowledge the Deartment of Chemistry, NIT Kurukshetra for [11] J. Li, C. Yin and F. Huo, RSC Adv. 2015, 5, 2191-2206.
the research facilities. Authors wish to acknowledge Boopathy [12] a) Z. Guo, G. Chen, G. Zeng, Z. Li, A. Chen, J. Wang and L. Jiang, Analyst
2015, 140, 1772-1786; b) Z. Dong, X. Le, P. Zhou, C. Dong and J. Ma, New
Gnanaprakasam, IISER-Pune for his support in the analysis of J. Chem. 2014, 38, 1802-1808.
compounds.DAJ acknowledge the financial support of Depart- [13] a) M. G. Choi, S. Cha, H. Lee, H. L. Jeon and S.-K. Chang, Chem. Commun
ment of Science and Technology (DST) India for the SERB-DST 2009, 7390-7392; b) R. Kaushik, A. Ghosh and D. A. Jose, J. Lumin. 2016,
project grant SB/FT/CS-195/2013. AG thankful to the financial 171, 112-117; c) R. Kaushik, P. Kumar, A. Ghosh, N. Gupta, D. Kaur, S. Ar-
ora and D. A. Jose, RSC Advances 2015, 5, 79309-79316.
support of DST, India for the SERB-DST young scientist research [14] K. M. Vengaian, C. D. Britto, K. Sekar, G. Sivaraman and S. Singaravadivel,
project grants (SB/FT/CS-193/2013). RSC Advances 2016, 6, 7668-7673.
[15] a) V. Tharmaraj and K. Pitchumani, Anal. Chim. Acta 2012, 751, 171-175;
b) E. M. Nolan and S. J. Lippard, Chem. Rev. 2008, 108, 3443-3480; c) M.
Keywords: Chemosensor · Mercury · Hydrogen sulfide · Shellaiah, Y. C. Rajan, P. Balu and A. Murugan, New J. Chem. 2015, 39,
Colorimetric · Test paper 2523-2531.
[16] C. J. Cramer and D. G. Truhlar, Phys. Chem. Chem. Phys. 2009, 11, 10757-
10816.
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ChemistrySelect 2016, 1, 1533 – 1540 1539  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Full Papers
Submitted: March 18, 2016
Accepted: May 11, 2016

ChemistrySelect 2016, 1, 1533 – 1540 1540  2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

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