Abstract
A new simple spectrophotometric method for the determination of Cu2+ ion was developed using an thiosemicarbazone compound, 2-{4-[Bis(2-chloroethyl)amino]benzylidene}-N-[(4-methylthio)phenyl]hydrazinecarbothioamide (TSC). A simultaneous color change was observed (from colorless to bright yellow) by the addition of Cu2+ ion to the TSC ligand solution. The maximum absorbance of the TSC ligand measured at 366 nm was decreased by the presence of Cu2+ ion. The graphs of absorbance obtained by means of the Job’s method and the molar-ratio method proposed a complex formation with a 1:2 Cu2+–TSC ligand stoichiometry. The molar-ratio method with emission measurements also confirmed the stoichiometry. The complex stability constant of TSC–Cu2+ complex (K) was evaluated to be 1.76 × 105. The proposed spectrophotometric method was associated with the change in absorbance at 366 nm owing to the interaction between the TSC ligand and Cu2+ ion. From the spectrophotometric titration data, it was pointed out that TSC ligand (1.5 × 10− 5 mol L-1) selectively reacted with Cu2+ ion in DMSO/water (1:1, v/v, citrate buffer at pH = 6.0). The calibration curve for Cu2+ ion was obtained with a good linearity in the range of 0.0191–0.3241 mg L-1. The detection limit for Cu2+ ion was 0.0063 mg L-1. The proposed method was achievemently implemented in real water samples (drink water, tap water and, distilled water). Satisfactory recoveries were confirmed at three different concentrations. The method presented a relative standard deviation (RSD%) of less than 3.08%.
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References
Linder MC, Hazegh-Azam M (1996) Copper biochemistry and molecular biology. Am J Clin Nutr 63:797–811. doi: https://doi.org/10.1093/ajcn/63.5.797
Uauy R, Olivares M, Gonzalez M (1998) Essentiality of copper in humans. Am J Clin Nutr 167:952S–959S. doi: https://doi.org/10.1093/ajcn/67.5.952S
High B, Bruce D, Richter MM (2001) Determining copper ions in water using electrochemiluminescence. Anal Chim Acta 449:17–22. doi: https://doi.org/10.1016/S0003-2670(01)01357-5
Tapia L, Suazo M, Hödar C, Cambiazo V, González M (2003) Copper exposure modifies the content and distribution of trace metals in mammalian cultured cells. Biometals 16:169–174. doi: https://doi.org/10.1023/A:1020766932605
Barranguet C, van den Ende FP, Rutgers M, Breure AM, Greijdanus M et al (2003) Admiraal W. Copper-induced modifications of the trophic relations in riverine algal-bacterial biofilms. Environ Toxicol Chem 22:1340–1349. doi: https://doi.org/10.1002/etc.5620220622
Hahn SH, Tanner MS, Danke DM, Gahl WA (1995) Normal metallothionein synthesis in fibroblasts obtained from children with indian Childhood cirrhosis or Copper-Associated Childhood cirrhosis. Biochem Mol Med 54:142–145. doi: https://doi.org/10.1006/bmme.1995.1021
Zietz BP, de Vergara JD, Dunkelberg H (2003) Copper concentrations in tap water and possible effects on infant’s health—results of a study in Lower Saxony. Ger Environ Res 92:129–138. doi: https://doi.org/10.1016/S0013-9351(03)00037-9
Carter KP, Young AM, Palmer AE (2014) Fluorescent sensors for measuring metalions in living systems. Chem Rev 114:4564–4601. doi: https://doi.org/10.1021/cr400546e
Que EL, Domaille DW, Chang CJ (2008) Metals in neurobiology: probing their chem-istry and biology with molecular imaging. Chem Rev 108:1517–1549. doi: https://doi.org/10.1021/cr078203u
Jia H, Liu W, Li N, Wang J, Song Y (2020) Spectrophotometric determination of copper(II) in Water based on Fluorescein Diacetate. J Anal Chem 2020 75:330–342. doi: https://doi.org/10.1134/S1061934820030089
El-Zomrawy AA (2018) Selective and sensitive spectrophotometric method to determine trace amounts of copper metal ions using Amaranth food dye. Spectrochim Acta Part A Mol Biomol Spectrosc 203:450–454. doi: https://doi.org/10.1016/j.saa.2018.06.014
Karaküçük-İyidoğan A, Mercan Z, Oruç-Emre EE, Taşdemir D, İşler D et al (2014) ; 189: 661–673. doi: https://doi.org/10.1080/10426507.2013.844139
Parrilha GL, Da Silva JG, Gouveia LF, Gasparoto AK, Dias RP et al (2011) Pyridine-derived thiosemicarbazones and their tin (IV) complexes with antifungal activity against Candida spp. Eur J Med Chem 46:1473–1482. doi: https://doi.org/10.1016/j.ejmech.2011.01.041
Ratchanok P, Prachayasittikul SRuchirawat S, Synthesis (2010) Cytotoxic and antimalarial activities of Benzoyl Thiosemicarbazone Analogs of Isoquinoline and Related Compounds. Molecules 15:988–996. doi: https://doi.org/10.3390/molecules15020988
Arion VB, Jakupec MA, Galanski M, Unfried P, Keppler BK (2002) Synthesis, structure, spectroscopic and in vitro antitumor studies of a novel gallium(III) complex with 2-acetylpyridine 4-Ndimethylthiosemicarbazone. J Inorg Biochem 91:298–305. doi: https://doi.org/10.1016/S0162-0134(02)00419-1
Badr SMI (2011) Synthesis and antiinflammatory activity of novel 2,5-disubstituted thiophene derivatives. Turk J Chem 35:131–143. doi: https://doi.org/10.3906/kim-1001-473
Yogeeswari P, Sriram D, Jit LRJS, Kumar SS, Stables JP (2002) Anticonvulsant and neurotoxicity evaluation of some 6-chlorobenzothiazolyl-2-thiosemicarbazones. Eur J Med Chem 37:231–236. doi: https://doi.org/10.1016/S0223-5234(02)01338-7
Padmanabhan P, Khaleefathullah S, Kaveri K, Palani G, Ramanathan G et al (2017) Antiviral activity of Thiosemicarbazones derived from α-amino acids against Dengue virüs. J Med Virol 89:546–552. doi: https://doi.org/10.1002/jmv.24655
Park H, Chang SK (2015) Selective colorimetric and ratiometric signaling of Cu2+ ions bythiosemicarbazone-appended 3-hydroxynaphthalimide. Sens Actuators B 220:376–380. doi: https://doi.org/10.1016/j.snb.2015.05.064
Reddy SA, Reddy KJ, Narayana SL, Reddy AV (2008) Analytical applications of 2,6-diacetylpyridine bis-4-phenyl-3- thiosemicarbazone and determination of Cu(II) in food samples. Food Chem 109:654–659. doi: https://doi.org/10.1016/j.foodchem.2007.12.073
Pourreza N, Hoveizavi R (2005) Simultaneous preconcentration of Cu, Fe and Pb as methylthymol blue complexes on naphthalene adsorbent and flame atomic absorption determination. Anal Chim Acta 549:124–128. doi: https://doi.org/10.1016/j.aca.2005.06.037
Zhong WS, Ren T, Zhao LJ (2016) Determination of lead, cadmium, chromium, copper and nickel in chinese tea with high resolution continuum source graphite furnace atomic absorption spectrometry. J Food Drug Anal 24:46–55. doi: https://doi.org/10.1016/j.jfda.2015.04.010
Behbahani M, Bide Y, Salarian M, Niknezhad M, Bagheri S et al (2014) The use of tetragonal star-like polyaniline nanostructures for efficient solid phase extraction and trace detection of pb(II) and Cu(II) in agricultural products, sea foods and water samples. Food Chem 158:14–19. doi: https://doi.org/10.1016/j.foodchem.2014.02.110
Amlani AM, Turel ZR (1999) Substoichiometric determination of copper by neutron activationanalysis. J Radioanal Nucl Chem 144:27–33. doi: https://doi.org/10.1007/bf02164896
Daugherty KE, Robinson RJ, Mueller JI (1964) X-ray fluorescence spectrometric determination of the copper(II) and mercury(II) complexes of 6-chloro, 2-methoxy-9-thiolacridine. Anal Chem 36:1098–1100. doi: https://doi.org/10.1021/ac60212a043
Hamilton MA, Rode PW, Merchant ME, Sneddon J (2008) Determination and comparison of heavy metals in selected seafood, water, vegetation and sediments byinductively coupled plasma-optical emission spectrometry from an industri-alized and pristine waterway in Southwest Louisiana. Microchem J 88:52–55. doi: https://doi.org/10.1016/j.microc.2007.09.004
Otero-Romani J, Moreda-Pineiro A, Bermejo-Barrera A, Bermejo-Barrera P (2005) Evaluation of commercial C18 cartridges for trace elements solid phase extraction from seawater followed by inductively coupled plasma-optical emission spectrometry determination. Anal Chim Acta 536:213–218. doi: https://doi.org/10.1016/j.aca.2004.12.046
Beni V, Ogurtsov VI, Bakunin NV, Arrigan DWM, Hill M (2005) Development of a portable electroanalytical system for the stripping voltammetry of metals: determination of copper in acetic acid soil extracts. Anal Chim Acta 552:190–200. doi: https://doi.org/10.1016/j.aca.2005.07.058
Gupta VK, Singh AK, Kumawat LK (2013) A novel gadolinium ion-selective membrane electrode based on 2-(4-phenyl-1, 3-thiazol-2-yliminomethyl) phenol. Electrochim Acta 95:132–138. doi: https://doi.org/10.1016/j.electacta.2013.02.053
Prasad S (2005) Kinetic method for determination of nanogram amounts of copper(II) by its catalytic effect on hexacynoferrate(III)-citric acid indicator reaction. Anal Chim Acta 540:173–180. doi: https://doi.org/10.1016/j.aca.2005.03.011
Prasad S, andHalafihi T (2003) Development and validation of catalytic kinetic spectrophotometric method for determination of Cu (II). Microchim Acta 142:237–244. doi: https://doi.org/10.1007/s00604-003-0023-3
Kumar A, Sharma P, Chandel LK, Kalal BL, Kunsagi-Mate S (2008) Synergistic solvent extraction of copper, cobalt, rhodium and iridium into 1, 2-dichloroethane at trace level by newly synthesized 25,26,27,28,tetrahydroxy-5,11,17,23-tetra-[4-(N-hydroxyl-3-phenylprop-2-enimidamido)phenylazo] calyx[4] arene. J Incl Phenom Macrocycl Chem 62:285–292. doi: https://doi.org/10.1007/s10847-008-9469-6
Kamble GS, Kolekar SS, Anuse MA (2011) Synergistic extraction and spectrophotometric determination of copper(II) using1-(2′,4′-dinitro aminophenyl)-4,4,6-trimethyl- 1,4-dihydropyrimidine-2-thiol: analysis of alloys, pharmaceuticals and biological samples. Spectrochim Acta Part A 78:1455–1466. doi: https://doi.org/10.1016/j.saa.2011.01.027
Rao KA, Shivramaiah S, Subudhi KS, Sreevani D, Umamaheswari Y et al (2012) Determination of copper in water, vegetables, foodstuffs and pharmaceuticals by direct and derivative spectrophotometry. Chem Sci Trans 1:590–603. doi: https://doi.org/10.7598/cst2012.241
Wu J, Sheng R, Liu W, Wang P, Ma J et al. Reversible fluorescent probe for highly selective and sensitive detection of mercapto biomolecules, Inorg. Chem. 2011; 50: 6543-6551. doi: 10.1021/ic200181p.
http://water.epa.gov/drink/contaminants/basicinformation/copper.cfm
http://www.who.int/waterSanitationHealth/dwq/chemicals/Copper.PDF
Karaküçük-İyidoğan A, Aydınöz B. Taşkın-Tok T, Oruç-Emre E E, Balzarini J. Synthesis, biological Evaluation and Ligand Based Pharmacophore Modeling of new aromatic thiosemicarbazones as potential anticancer agents. Pharmaceutical Chemistry Journal 2019; 53: 139-149 Russian Original doi: 10.1007/s11094-019-01968-3.
Tnechiu (Deleanu) A C, Kostas I D, Kovala-Demertzi D, Terzis A. Synthesis and characterization of new aromatic aldehyde/ketone 4-(β-d-glucopyranosyl)thiosemicarbazones. Carbohydrate Research 2009; 344: 1352 – 1364. doi: 10.1016/j.carres.2009.05.010.
Pearson R G. Hard and Soft Acids and Bases. J Am Chem Soc 1963; 85: 3533–3539. doi: 10.1021/ja00905a001.
Irving H M N H, Freiser H, West T S, editors. IUPAC compendium of analytical nomenclature, definitive rules 1977. Oxford: Pergamon Press, 1981; pp. 56-222.
Bourson J, Valeur B (1989) Ion-responsive fluorescent compounds. 2. Cation-steered intramolecular charge transfer in a crowned merocyanine. J Phys Chem 93:3871–3876. doi: https://doi.org/10.1021/j100346a099
Benesi HA, Hildebrand JH (1949) A spectrophotometric investigation of the interaction of iodine with aromatic hydrocarbons. J Am Chem Soc 71:2703–2707. doi: https://doi.org/10.1021/ja01176a030
Yuan MJ, Zhou WD, Liu XF, Zhu M, Li JB et al (2008) A multianalyte Chemosensor on a single molecule: promising structure for an Integrated Logic Gate. J Org Chem 73:5008–5014. doi: https://doi.org/10.1021/jo8005683
Bai X, Li Y, Gu H, Hua Z (2015) Selective colorimetric sensing of Co2+ and Cu2+ using 1-(2-pyridylazo)-2-naphthol derivative immobilized polyvinyl alcohol microspheres. RSC Adv 5:77217–77226. doi: https://doi.org/10.1039/C5RA12765C
Hu S, Song J, Zhao F, Meng X, Wu G (2015) Highly sensitive and selective colorimetric naked-eye detection of Cu2+ in aqueous medium using a hydrazone chemosensor. Sens Actuator B Chem 215:241–248. doi: https://doi.org/10.1016/j.snb.2015.03.059
De Lemos LR, Santos IJB, Rodrigues GD, da Silva LH (2012) M, da Silva M C H. Copper recovery from ore by liquid–liquid extraction using aqueous two-phase system. J Hazard Mater 237–238. doi: https://doi.org/10.1016/j.jhazmat.2012.08.028
Jamali MR, Assadi Y, Shemirani F (2007) Homogeneous liquid–liquid extraction and determination of Cobalt, copper, and Nickel in Water samples by Flame Atomic absorption spectrometry. Sep Sci Technol 42:3503–3515. doi: https://doi.org/10.1080/01496390701508784
Acknowledgements
We would like to thank Prof. Dr. Miraç OCAK for his consultancy in the application of fluorescence studies.
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This research was supported by Scientific Research Foundation, Gümüşhane Universty, (19.A0118.02.01).
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Aysel BAŞOĞLU and Ümmühan OCAK designed the study. Ayşegül KARAKÜÇÜK İYİDOĞAN synthesized and characterized the ligand. Aysel BAŞOĞLU prepared the manuscript and, performed all spectrophotometric/spectrofluorimetric measurements and, analysis. All authors read and approved the final manuscript.
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BAŞOĞLU, A., OCAK, Ü. & İYİDOĞAN, A.K. Highly Efficient Spectrophotometric Determination of Cu2+ ion in Aqueous Medium Using a thiosemicarbazone–derivative Ligand. J Fluoresc 33, 1003–1015 (2023). https://doi.org/10.1007/s10895-022-03127-6
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DOI: https://doi.org/10.1007/s10895-022-03127-6