Abstract
Thiosemicarbazone metal complexes [Cu(L)(2-benzpy)]ClO4 (1) and [Zn(L)2] (2) [L = 2-benzoylpyridine-N(4)-methyl-3-thiosemicarbazone), 2-benzpy = 2-benzolylpyridine] were synthesized and X-ray crystallographically characterized. The metal centre in compound 1 has a distorted square planar geometry while in compound 2, the metal centre has a distorted octahedral geometry. Both the molecules induce cytotoxic effects on A431 skin carcinoma cell line in 24 h incubation and significantly enhances hypoploid cell population in cell cycle phase distribution below IC50 dose. Application of both the two molecules exhibit apoptotic induction and genotoxic activity in 24 h exposure.
Graphical abstract
Similar content being viewed by others
References
Bisceglie F, Tavone M, Mussi F, Azzoni S, Montalbano S, Franzoni S, et al. 2017 Effects of polar substituents on the biological activity of thiosemicarbazone metal complexes Inorg. Biochem 179 60
Saswati, Adão P, Majumder S, Dash S P, Roy S, Kuznetsov M L, Pessoa B C, Gomes C S B, Hardikar M R, Tiekinkg E R T and Dinda R 2018 Synthesis, structure, solution behavior, reactivity and biological evaluation of oxidovanadium(IV/V) thiosemicarbazone complexes Dalton Trans. 47 11358
Huseynova M, Taslimi P, Medjidov A, Farzaliyev V, Aliyeva M, Gondolova G, et al. 2018 Synthesis, characterization, crystal structure, electrochemical studies and biological evaluation of metal complexes with thiosemicarbazone of glyoxylic acid Polyhedron 155 25
Chellan P, Stringer T, Shokar A, Au A, Tam C, Cheng L W, et al. 2019 Antiprotozoal activity of palladium(II) salicylaldiminato thiosemicarbazone complexes on metronidazole resistant Trichomonas vaginalis Inorg. Chem. Commun. 102 1
Seena E B, Sithambaresan M, Vasudevan S and Kurup M R P 2020 Structural and spectral characterization of Cu(II) complexes of N(4)-substituted thiosemicarbazones derived from 2-hydroxyacetophenone: crystal structure of a dinuclear Cu(II) complex J. Chem. Sci. 132 149
Haque R A and Salam M A 2015 Synthesis, structural characterization and biological activities of organotin(IV) complexes with 5-allyl-2-hydroxy-3-methoxybenzaldehyde-4-thiosemicarbazone J. Chem. Sci. 127 1589
Anjum R, Palanimuthu D, Kalinowski D S, Lewis W, Park K C, Kovacevic Z, et al. 2019 Synthesis, characterization, and in vitro anticancer activity of copper and zinc bis(thiosemicarbazone) complexes Inorg. Chem. 58 13709
Biswas N, Khanra S, Sarkar A, Bhattacharjee S, Mandal D P, Chaudhuri A, et al. 2017 One new azido bridged dinuclear copper(II) thiosemicarbazide 2 complex: synthesis, DNA/protein binding, molecular docking 3 study and cytotoxicity activity New J. Chem. 41 12996
Li M X, Chen C L, Zhang D, Niu J Y and Ji B S 2010 Mn(II), Co(II) and Zn(II) complexes with heterocyclic substituted thiosemicarbazones: synthesis, characterization, X-ray crystal structures and antitumor comparison Eur J. Med. Chem. 45 3169
Lobana T S, Khanna S and Butcher R J 2012 2-benzoylpyridine thiosemicarbazone as a novel reagent for the single pot synthesis of dinuclear CuI-CuII complexes: formation of stable Cu(II)-iodide bonds Dalton Trans. 41 4845
Indoria S, Lobana T S, Singh D, Kumari S, Kumari P, Bala T, et al. 2015 Stabilization of CuII-I bonds using 2-benzoylpyridine thiosemicarbazones - synthesis, structure, spectroscopy, fluorescence, and cyclic voltammetry Eur. J. Inorg. Chem. 2015 5106
Kausal M, Lobana T S, Nim L, Kaur J, Bala R, Hundal G, et al. 2018 Synthesis, structures, antimicrobial activity and biosefty evaluation of pyridine-2-formaldehyde-N-substituted-thiosemicarbazones of copper(II) New J. Chem. 42 15879
Lobana T S, Sharma R, Bawa G and Khanna S 2009 Bonding and structure trends of thiosemicarbazone derivatives of metal − An overview Coord. Chem. Rev. 253 977
Brockman R W, Thomson J R, Bell M J and Skipper H E 1956 Observations on the antileukemic activity of pyridine-2-carboxaldehyde thiosemicarbazone and thiocarbohydrazone Cancer Res. 16 167
Bacher F, Enyedy E A, Nagy N V, Rockenbauer A, Bognár G M, Trondl R, et al. 2013 Copper(II) complexes with highly water-soluble L- and D-proline− thiosemicarbazone conjugates as potential inhibitors of topoisomerase IIα Inorg. Chem. 52 8895
Finch R A, Liu M C, Cory A H, Cory J G and Sartorelli A C 1999 Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone; 3-AP): an inhibitor of ribonucleotide reductase with antineoplastic activity Adv. Enzyme Regul. 39 3
Finch R A, Liu M C, Grill S P, Rose W C, Loomis R, Vasquez K M, et al. 2000 Triapine (3-aminopyridine-2-carboxaldehydethiosemicarbazone): a potent inhibitor of ribonucleotide reductase activity with broad spectrum antitumor activity Biochem. Pharmacol. 59 983
Kowel C R, Trondl R, Heffeter P, Arion V B, Jakupec M A, Roller A, et al. 2009 Impact of metal coordination on cytotoxicity of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone (triapine) and novel insights into terminal dimethylation J. Med. Chem. 52 5032
Popović-Bijelić A, Kowol C R, Lind M E S, Luo J, Himo F, Enyedy É A, et al. 2011 Ribonucleotide reductase inhibition by metal complexes of Triapine (3-aminopyridine-2-carboxaldehyde thiosemicarbazone): a combined experimental and theoretical study J. Inorg. Biochem. 105 1422
Ghosh A K, Yadav H R, Choudhury A R, Duraipandian N, Kiran M S and Ghosh R 2017 Synthesis and crystal structures of pyridine- 2-carboxaldehyde thiosemicarbazone, its mononuclear and cytotoxic Cu(II) and polynuclear Pb(II) complexes: effect of size of metal ion on nucleation of the complexes Indian J. Chem. 56A 616
Bruker, SMART, SAINT and SADABS 2007 Bruker AXS Inc., Madison, Wisconsin, USA.
Sheldrick G M 2015 Crystal structure refinement with SHELXL Acta Cryst. C 71 3
Nakamoto K 2009 Infrared and Raman Spectra of Inorganic and Coordination Compounds, part B: Applications in Coordination, Organometallic, and Bioinorganic Chemistry (John Wiley: New Jersey)
Li M X, Chen C L, Zhang D, Niu J Y and Ji B S 2010 Mn(II), Co(II) and Zn(II) complexes with heterocyclic substituted thiosemicarbazones: synthesis, characterization, X-ray crystal structures and antitumor comparison Eur. J. Med. Chem. 45 3169
Liu Y- H, Li A, Shao J, Song X- Q, Xie C- Z, Bao W- G and Jing-Yuan X 2016 Four Cu(II) complexes based on antitumor chelators: synthesis, structure, DNA binding/damage, HSA interaction and enhanced cytotoxicity Dalton Trans. 45 8036
Acknowledgements
AC is thankful to PURSE Phase II (Govt. of India) for his fellowship. The single crystal X-ray diffraction facility at USIC, Burdwan University is also gratefully acknowledged.
Author information
Authors and Affiliations
Corresponding authors
Ethics declarations
Conflict of interest
The authors declare that they have no competing interests.
Supplementary Information
Below is the link to the electronic supplementary material.
12039_2021_1906_MOESM1_ESM.pdf
CCDC 1962661 and CCDC 1962662 contain the supplementary crystallographic data for 1 and 2, respectively. These data can be obtained free of charge via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; fax: +441223-336-033; or e-mail: deposit@ ccdc.cam.ac.uk. Figures S1–S7 are available at www.ias.ac.in/chemsci. (PDF 562 kb)
Rights and permissions
About this article
Cite this article
Biswas, C., Chatterjee, A., Bhattacharya, S. et al. Synthesis, X-ray structures and cytotoxic effects of a Cu(II)- and a Zn(II) thiosemicarbazones on human epidermoid carcinoma cell A431. J Chem Sci 133, 45 (2021). https://doi.org/10.1007/s12039-021-01906-5
Received:
Revised:
Accepted:
Published:
DOI: https://doi.org/10.1007/s12039-021-01906-5