Copper Coordinated Congo-Red as a Solvent Assisted Selective Fluorometric and Colorimetric Chemosensor for Determination and Naked-Eye Detection of Multiple Analytes in Nanomolar Scale: A Reversible Fluorescent CN−/CO32− Switch that Works as Keypad Lock

Document Type: Original research article

Authors

Department of Chemistry, Payame Noor University, P.O. BOX, 19395-3697, Tehran, Iran

Abstract

A new diazo based, Congo-Red-Cu , was developed to act as an ‘Off–On’ reversible fluorescent probe for CNdetection. The changes in solvent composition has been shown greatly effective on selectivity of anion sensing through eliminate of sulfite interference. Increasing the amount of ethanol up to 5% (v/v) cause a dramatic development in selectivity of CNvia inhibitory effect on sulfite interferent. The chemosensing behavior of the CR-Cu has been demonstrated through fluorescence, absorption, visual color changes and FT-IR studies. This chemosensor (CR-Cu) has been shown a significant visible color change and displays a remarkable fluorescent switch on in the presence of CN ions. The ‘in situ’ prepared CN complexes of CR-Cu shows high “Turn-Off” selectivity toward CO32− over the other anions. The detection limits for CN were 90 and 20 nM for colorimetric and fluorometric methods respectively, that is far lower than the WHO guideline of 1.9 µM. The complex of CN with CR-Cu also displayed ability to detect up to 15 nM CO32− among other competing anions through a fast response time of less than 30 s which is much lower than most recently reported chemosensor probes. It has been possible to build an INHIBIT logic gate for two binary inputs viz., CN and CO32− by monitoring the fluorescence emission band at 446 nm as output. The development of fluorometric an ‘‘Off–On’’ reversible switch for three chemical inputs Cu2+, CN and CO32− ions and mimics a molecular level keypad lock.

Keywords


[1] E.B. Veale and T. Gunnlaugsson, Fluorescent sensors for ions based on organic structures, Annu. Rep. Prog. Chem. Sect. B Org. Chem. 106 (2010) 376–406.

[2] H.J. Kim, S. Bhuniya, R.K. Mahajan, R. Puri, H. Liu, K.C. Ko, J.Y. Lee and J.S. Kim, Fluorescence turn-on sensors for HSO4−, Chem. Commun. 46 (2009) 7128–7130.

[3] C. Caltagirone and P.A. Gale, Anion receptor chemistry: highlights from 2007, Chem. Soc. Rev. 38 (2009) 520–563.

[4] Guidelines for Drinking-Water Quality, World Health Organization, Geneva (1996).

[5] P.K. Bhattacharya, Metal Ions in Biochemistry, Alpha Science International Ltd. Harrow, U.K. (2005).

[6] J.T. Zhang, S.L. Zhu, L. Valenzano, F.T. Luo and H.Y. Liu, BODIPY-based ratiometric fluorescent probes for the sensitive and selective sensing of cyanide ions, RSC Adv. 3 (2013) 68–72.

[7] D. Marton, A. Tapparo, V.B. Di Marco, C. Repice, C. Giorio and S. Bogialli, Ultratrace determination of total and available cyanides in industrial wastewaters through a rapid headspace-based sample preparation and gas chromatography with nitrogen phosphorous detection analysis, J. Chromatogr. A 1300 (2013) 209–216.

[8] G.J. Park, I.H. Hwang, E.J. Song, H. Kim and C. Kim, A colorimetric and fluorescent sensor for sequential detection of copper ion and cyanide, Tetrahedron 70 (2014) 2822– 2828.

[9] D.G. Themelis, S.C. Karastogianni and P.D. Tzanavaras, Selective determination of
cyanides by gas diffusion-stopped flowsequential injection analysis and an on-line standard addition approach, Anal. Chim. Acta 632 (2009) 93–100.

[10] Y. Tian,; P.K. Dasgupta, S.B. Mahon, J. Ma, M. Brenner, J.H. Wang and R.B. Gerry, A disposable blood cyanide sensor, Anal. Chim. Acta 768 (2013) 129–135.

[11] F. Wang, L. Wang, X. Chen and J. Yoon, Recent progress in the development of fluorometric and colorimetric chemosensors for detection of cyanide ions, J. Chem. Soc. Rev. 43 (2014) 4312–4324.

[12]  J.T. Baker, Material Safety Data Sheet, No. 3242 (1998).

[13]  M.J. Little and P.D. Wentzell, Evaluation of acoustic emission as a means for carbonate determination, Anal. Chim. Acta 309 (1995) 283–292.

[14] X. Su, L. Nie and S. Yao, A novel gasdiffusion/flow-injection system coupled with a bulk acoustic wave impedance sensor for total inorganic carbonate and its application to determination of total inorganic and total organic carbon in waters, Anal. Chim. Acta 349 (1997) 143–151.

[15]  S. Kou, H.N. Lee, D. van Noort, K.M.K. Swamy, S.H. Kim, J.H. Soh, K.M. Lee, S.W. Nam, J. Yoon and S. Park, Fluorescent Molecular Logic Gates Using Microfluidic Devices, Angew. Chem. Int. Ed. 47 (2008) 872–876. 

[16]  U. Pischel, Chemical approaches to molecular logic elements for addition and subtraction, Angew. Chem. Int. Ed. 46 (2007) 4026–4040.

[17]  R. Baron, A. Onopriyenko, E. Katz, O. Lioubashevski, I. Willner, S. Wang and H. Tian, An electrochemical / photochemical information processing system using a monolayer-functionalized electrode, Chem. Commun. 20 (2006) 2147–2149.

[18]  Y. Liu, W. Jiang, H.Y. Zhang and C.J. Li, A multifunctional arithmetical processor model integrated inside a single molecule, J. Phys. Chem. B 110 (2006) 14231–14235.

[19]  D. Margulies, C.E. Felder, G. Melman and A. Shanzer, A molecular keypad lock:  A photochemical device capable of authorizing password entries, J. Am. Chem. Soc. 129 (2007) 347–354.

[20]  B. Schneier, Secrets and Lies Digital Security in a Networked World, John Wiley & Sons Inc., New York (2000).

[21] A. Okamoto, K. Tanaka and I. Saito, DNA logic gates, J. Am. Chem. Soc. 126 (2004) 9458–9463.

[22]  M.S. Han and D.H. Kim, Naked‐Eye Detection of Phosphate Ions in Water at Physiological pH: A Remarkably Selective and Easy‐To‐Assemble Colorimetric Phosphate‐Sensing Probe, Angew. Chem. Int. Ed. 41 (2002) 3809 –3811.

[23]  P. Saluja, N. Kaur, N. Singh and D.O. Jang, A benzimidazole-based fluorescent sensor for Cu2+ and its complex with a phosphate anion formed through a Cu2+ displacement approach, Tetrahedron Lett. 53 (2012) 3292– 3295. 

[24]  H. Tavallali, G. Deilamy-Rad, A. Parhami and E. Abbasiyan, A new application of bromopyrogallol red as a selective and sensitive competition assay for recognition and determination of acetate anion in DMSO/water media, Dyes Pigm. 94 (2012) 541–547.

[25]  H. Tavallali, G. Deilamy-Rad, A. Parhami and E. Abbasiyan, Colorimetric detection of copper and chloride in DMSO/H2O media using bromopyrogallol red as a chemosensor with analytical applications, Spectrochim. Acta: Part A 97 (2012) 60–65.

[26]  H. Tavallali, G. Deilamy-Rad, A. Parhami and E. Abbasiyan, A novel and efficient colorimetric chemosensor for detection and determination of biologically important ions in DMSO/H2O media using bromo pyrogallol red chemosensors with analytical applications, J. Photochem. Photobiol. B 115 (2012) 51–57.

[27]  H. Tavallali, G. Deilamy-Rad, A. Parhami and S.Z. Mousavi, A novel development of dithizone as a dual-analyte colorimetric chemosensor: detection and determination of
cyanide and cobalt (II) ions in dimethyl sulfoxide/water media with biological applications, J. Photochem. Photobiol. B 125 (2013) 121–130.

[28] H. Tavallali, G. Deilamy-Rad, A. Parhami and S. Kiyani, Dithizone as novel and efficient chromogenic probe for cyanide detection in aqueous media through nucleophilic addition into diazenylthione moiety, Spectrochim. Acta, Part A 121 (2014) 139–146.

[29]  H. Tavallali, G. Deilamy-Rad, A. Parhami and 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.

[30] H. Tavallali, M.R. Baezzat, G. Deilamy-Rad, A. Parhami and N. Hasanli, An ultrasensitive and highly selective fluorescent and colorimetric chemosensor for citrate ions based on rhodamineB and its application as the first molecular security keypad lock based on phosphomolybdic acid and citrate inputs, J. Luminescence 160 (2015) 328–336.

[31]  H. Tavallali, G. Deilamy-Rad, A. Parhami and N. Hasanli, An efficient and ultrasensitive rhodamine B-based reversible colorimetric chemosensor for naked-eye recognition of molybdenum and citrate ions in aqueous solution: Sensing behavior and logic operation Spectrochim. Acta, Part A 139 (2015) 253–261.

[32] H. Tavallali, G. Deilamy-Rad, A. Parhami and S. Lohrasbi, A novel and simple fluorescent and colorimetric primary chemosensor based on Congo-Red for sulfite and resultant complex as secondary fluorescent chemosensor towards carbonate ions: Fluorescent probe mimicking INHIBIT logic gate, Talanta 149 (2016) 168–177.

[33]  H.A. Benesi and J.H. Hildebrand, A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons, J. Am. Chem. Soc. 71 (1949) 2703–2707.

[34]  K.G. Casey and E.L. Quitevis, Effect of solvent polarity on nonradiative processes in xanthene dyes: Rhodamine B in normal alcohols, J. Phys. Chem. 92 (1988) 6590– 6594.

[35]  A. Sinicropi, W.M. Nau and M. Olivucci, Excited state quenching via “unsuccessful” chemical reactions, Photochem. Photobiol. Sci. 1 (2002) 537–546.

[36]  M. Kumar, R. Kumar and V. Bhalla, A reversible fluorescent Hg2+/K+ switch that works as keypad lock in the presence of F- ion, Chem. Commun. (2009) 7384–7386.

[37]  Official Journal of the European Union, Commission Directive 2003/40/EC (2003).

[38]  United States Environmental Protection Agency (EPA), Methods for Chemical Analysis of Water and Wastes, Environmental Monitoring and Support Laboratory, Cincinnati, OH (1983).

[39]  J.N. Miller and J.C. Miller, Statistics and Chemometrics for Analytical Chemistry, 5th ed., Pearson Education Limited, Prentice Hall, NY (2005).

[40]  Y. Sun, Y. Liu, M. Chen and W. Guo, A novel fluorescent and chromogenic probe for cyanide detection in water based on the nucleophilic addition of cyanide to imine group, Talanta 80 (2009) 996–1000.

[41]  D. Cacace, H. Ashbaugh, N. Kouri, S. Bledsoe, S. Lancaster and S. Chalk, Spectrophotometric determination of aqueous cyanide using a revised phenolphthalein method, Anal. Chim. Acta 589 (2007) 137– 141.

[42] X. Zhang, C. Li, X. Cheng, X. Wang and B. Zhang, A near-infrared croconium dye based colorimetric chemodosimeter for biological thiols and cyanide anion, Sens. Actuators B: Chem. 129 (2008) 152–157.

[43]  Y. Sun, Y.L. Liu and W. Guo, Fluorescent and chromogenic probes bearing salicylaldehyde hydrazone functionality for cyanide detection in aqueous solution, Sens. Actuators B: Chem. 143 (2009) 171–176.

[44]  A. Hamza, A.S. Bashammakh, A.A. AlSibaai, H.M. Al-Saidi and M.S. El-Shahawi, Dual-wavelength β-correction spectrophotometric determination of trace concentrations of cyanide ions based on the nucleophilic addition of cyanide to imine group of the new reagent 4-hydroxy-3-(2-oxoindolin-3-ylideneamino)- 2-thioxo-2H-1,3-thiazin-6(3H)-one, Anal. Chim. Acta 757 (2010) 69–74.

[45]  F.H. Zelder, Specific colorimetric detection of cyanide triggered by a conformational switch in vitamin B12, Inorg. Chem. 47 (2008) 1264–1266.

[46] S.S.M. Hassan, M.S.A. Hamza and A.E. Kelany, A novel spectrophotometric method for batch and flow injection determination of cyanide in electroplating wastewater, Talanta 71 (2007) 1088–1095.

[47]  A. Afkhami and N. Sarlak, A novel cyanide sensing phase based on immobilization of methyl violet on a triacetylcellulose membrane, Sens. Actuators B: Chem. 122 (2007) 437–441.

[48]  C.M. Zvinowanda, J.O. Okonkwo and R.C. Gurira, Improved derivatisation methods for the determination of free cyanide and cyanate in mine effluent, J. Hazard. Mater. 158 (2008) 196–201.