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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.
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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).
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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-
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ChemistrySelect 2016, 1, 1533 – 1540 1536 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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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.
ChemistrySelect 2016, 1, 1533 – 1540 1537 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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As shown in Figure 9, the probe checked with the range of
physiological and biological important analytes such as reactive
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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.
[1] W. D. Atchison and M. F. Hare, FASEB J. 1994, 8, 622-629. [17] M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R.
[2] B. Weiss, Toxicol. Sci. 2007, 97, 223-225. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Na-
[3] L. Amin-Zaki, S. Elhassani, M. A. Majeed, T. W. Clarkson, R. A. Doherty and katsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G.
M. Greenwood, Pediatrics 1974, 54, 587-595. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Ha-
[4] a) Z. Yan, M.-F. Yuen, L. Hu, P. Sun and C.-S. Lee, RSC Adv. 2014, 4, 48373- segawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.
48388; b) P. Mahato, S. Saha, P. Das, H. Agarwalla and A. Das, RSC Ad- A. Montgomery Jr. , J. E. Peralta, F. Ogliaro, M. J. Bearpark, J. Heyd, E. N.
vances 2014, 4, 36140-36174; c) U. Reddy G, V. Ramu, S. Roy, N. Taye, S. Brothers, K. N. Kudin, V. N. Staroverov, R. Kobayashi, J. Normand, K. Ra-
Chattopadhyay and A. Das, Chem. Commun. 2014, 50, 14421-14424. ghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N.
[5] a) M. Suresh, A. Ghosh and A. Das, Chem. Commun. 2008, 3906-3908; Rega, N. J. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo,
b) M. Suresh, A. Shrivastav, S. Mishra, E. Suresh and A. Das, Org. Lett. J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cam-
2008, 10, 3013-3016; c) M. Suresh, S. Mishra, S. K. Mishra, E. Suresh, A. K. mi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzew-
Mandal, A. Shrivastav and A. Das, Org. Lett. 2009, 11, 2740-2743; d) M. ski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels,
Suresh, A. K. Mandal, S. Saha, E. Suresh, A. Mandoli, R. Di Liddo, P. P. . Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski and D. J. Fox in Gaus-
Parnigotto and A. Das, Org. Lett. 2010, 12, 5406-5409; e) P. Mahato, S. sian 09, Vol. Gaussian, Inc., Wallingford, CT, USA, 2009.
Saha, E. Suresh, R. Di Liddo, P. P. Parnigotto, M. T. Conconi, M. K. Ke- [18] a) H. Xu, W. Wu, Y. Chen, T. Qiu and L.-J. Fan, ACS Appl. Mater. Interfaces
sharwani, B. Ganguly and A. Das, Inorg. Chem. 2012, 51, 1769-1777; f) S. 2014, 6, 5041-5049; b) Y. Wu, Y. Dong, J. Li, X. Huang, Y. Cheng and C.
Saha, P. Mahato, U. Reddy G, E. Suresh, A. Chakrabarty, M. Baidya, S. K. Zhu, Chem. - Asian J. 2011, 6, 2725-2729; c) L. Wang, F. Li, X. Liu, G. Wei,
Ghosh and A. Das, Inorg. Chem. 2012, 51, 336-345; g) G. Chen, Z. Guo, G. Y. Cheng and C. Zhu, J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4070-
Zeng and L. Tang, Analyst 2015, 140, 5400-5443; h) J. Li, Y. Wu, F. Song, 4075.
G. Wei, Y. Cheng and C. Zhu, J. Mater. Chem. 2012, 22, 478-482; i) S. An- [19] a) X. Cheng, Q. Li, C. Li, J. Qin and Z. Li, Chem. Eur. J 2011, 17, 7276-7281;
gupillai, J.-Y. Hwang, J.-Y. Lee, B. A. Rao and Y.-A. Son, Sens. Actuators, B b) R. Shunmugam, G. J. Gabriel, C. E. Smith, K. A. Aamer and G. N. Tew,
2015, 214, 101-110; j) M. Vedamalai and S.-P. Wu, Org.Biomol.Chem 2012, Chem. Eur. J 2008, 14, 3904-3907.
10, 5410-5416; k) M. H. Lee, B.-K. Cho, J. Yoon and J. S. Kim, Org. lett. [20] M. Hong, X. Lu, Y. Chen and D. Xu, Sens. Actuators, B 2016, 232, 28-36.
2007, 9, 4515-4518; l) A. Caballero, R. Martnez, V. Lloveras, I. Ratera, J. [21] X. He, J. Zhang, X. Liu, L. Dong, D. Li, H. Qiu and S. Yin, Sens. Actuators, B
Vidal-Gancedo, K. Wurst, A. Trraga, P. Molina and J. Veciana, J. Am. 2014, 192, 29-35.
Chem. Soc 2005, 127, 15666-15667. [22] X. Cheng, Q. Li, J. Qin and Z. Li, ACS Appl. Mater. Interfaces 2010, 2, 1066-
[6] a) S. Yang, C. Wu, H. Tan, Y. Wu, S. Liao, Z. Wu, G. Shen and R. Yu, Anal. 1072.
Chem. 2013, 85, 14-18; b) J. Wang, H. Chen, P. Zhang, Z. Zhang, S. Zhang [23] a) V. S. Lin and C. J. Chang, Curr. Opin. Chem. Biol. 2012, 16, 595-601;
and J. Kong, Talanta 2013, 114, 204-210; c) D. Huang, C. Niu, X. Wang, X. b) M. Strianese, M. Staiano, G. Ruggiero, T. Labella, C. Pellecchia and S.
Lv and G. Zeng, Anal. Chem. 2013, 85, 1164-1170; d) Y. Helwa, N. Dave, R. D’Auria, Methods Mol. Biol. 2012, 875, 193-216; c) C.-X. Duan and Y.-G.
Froidevaux, A. Samadi and J. Liu, ACS Appl. Mater. Interfaces 2012, 4, Liu, Curr. Med. Chem. 2013, 20, 2929-2937; d) A. R. Lippert, J. Inorg. Bio-
2228-2233; e) S.-M. Jia, X.-F. Liu, P. Li, D.-M. Kong and H.-X. Shen, Biosens. chem. 2014, 133, 136-142.
Bioelectron. 2011, 27, 148-152; f) D.-M. Kong, N. Wang, X.-X. Guo and H.- [24] F. Ma, M. Sun, K. Zhang, H. Yu, Z. Wang and S. Wang, Analytica Chimica
X. Shen, Analyst 2010, 135, 545-549. Acta 2015, 879, 104-110.
[7] a) H. Tan, B. Liu and Y. Chen, ACS Nano 2012, 6, 10505-10511; b) E. S. [25] P. Das, A. Ghosh, H. Bhatt and A. Das, RSC Advances 2012, 2, 3714-3721.
Childress, C. A. Roberts, D. Y. Sherwood, C. L. M. LeGuyader and E. J. [26] H. Peng, Y. Cheng, C. Dai, A. L. King, B. L. Predmore, D. J. Lefer and B.
Harbron, Anal. Chem. 2012, 84, 1235-1239; c) C. Ma, F. Zeng, L. Huang Wang, Angewandte Chemie 2011, 123, 9846-9849.
and S. Wu, J. Phys. Chem. B 2011, 115, 874-882; d) J. Hu, C. Li and S. Liu, [27] a) J. Fan, C. Chen, Q. Lin and N. Fu, Sens. Actuators, B 2012, 173, 874-881;
Langmuir 2010, 26, 724-729; e) X. Ren and Q.-H. Xu, Langmuir 2009, 25, b) T. Lou, Z. Chen, Y. Wang and L. Chen, ACS Appl. Mater. Interfaces 2011,
29-31; f) J.-H. Park, N. S. Cho, Y. K. Jung, H.-J. Cho, H.-K. Shim, H. Kim and 3, 1568-1573; c) C.-Y. Lin, C.-J. Yu, Y.-H. Lin and W.-L. Tseng, Anal. Chem.
Y. S. Lee, Org. Electron. 2007, 8, 272-285. 2010, 82, 6830-6837; d) R. Satapathy, Y.-H. Wu and H.-C. Lin, Org. Lett.
[8] a) Y. Hu, L. Meng and Q. Lu, Langmuir 2014, 30, 4458-4464; b) M. Annad- 2012, 14, 2564-2567.
hasan, T. Muthukumarasamyvel, V. R. Sankar Babu and N. Rajendiran,
ACS Sustainable Chem. Eng. 2014, 2, 887-896; c) A. Singh, T. Raj, T. Aree
and N. Singh, Inorg. Chem. 2013, 52, 13830-13832; d) W. Lu, X. Qin, S.
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Submitted: March 18, 2016
Accepted: May 11, 2016
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