Abstract
The binding and photo-induced DNA cleavage activity of a binary complex [CuL2](ClO4)2 (1) and the in situ generated ternary complexes [CuLB](ClO4)2 from 1 (B: 1,10-phenanthroline, phen, 2; dipyrido[3,2-d: 2′,3′-f]quinoxaline, dpq, 3) are studied, where L is a N2S-donor tridentate Schiff base 2- (methylthio)ethylpyridine-2-carbaldimine. Complex 1, structurally characterized by X-ray diffraction study, has six-coordinate meridional geometry showing CuN4S2 coordination. The Cu-N bond lengths are in the range of 1·968(3) to 2·158(4) Å. The Cu-S bond lengths of 2·599(2) and 2·705(2) Å are significantly long indicating weak covalent interaction between copper and sulphur atoms. The thiomethyl groups are cis to each other giving S-Cu-S angle of 75·82(5)°. The Cu-N(pyridyl) bond distances are longer than the Cu-N(imine) bonds. The complexes are redox active and display a quasi-reversible cyclic voltammetric response assignable to the Cu(II)/Cu(I) couple near 0·0 V vs SCE in DMF-Tris buffer (1: 4 v/v) using 0·1 M KCl as supporting electrolyte. Electronic spectra of the complexes show a d-d band in the range 630 to 700 nm in DMF along with higher energy charge transfer bands. While complex 1 is a poor binder to DNA, the ternary complexes show good DNA binding propensity. The photo-nuclease activity of 1–3 is studied using UV and visible wavelengths. The DNA cleavage activity at 365 nm follows the order: 3 > 2 > 1. The cleavage reaction involves the formation of singlet oxygen as the reactive species in a type-II process.
Similar content being viewed by others
References
Sigman D S, Mazumdar A and Perrin D M 1993 Chem. Rev. 93 2295
Erkkila K E, Odom D T and Barton J K 1999 Chem. Rev. 99 2777
Pogozelski W K and Tullius T D 1998 Chem. Rev. 98 1089
Burrows C J and Muller J G 1998 Chem. Rev. 98 1109
Armitage B 1998 Chem. Rev. 98 1171
Pratviel G, Bernadou J and Meunier B 1998 Adv. Inorg. Chem. 45 251
Meunier B 1992 Chem. Rev. 92 1411
Pratviel G, Bernadou J and Meunier B 1995 Angew. Chem., Int. Ed. Engl. 34 746
McMillin D R and McNett K M 1998 Chem. Rev. 98 1201
Lippard S J 1999 Chem. Rev. 99 2467
Hegg E L and Burstyn J N 1998 Coord. Chem. Rev. 173 133
Reedijk J 2001 J. Inorg. Biochem. 86 89
Wolkenberg S E and D L Boger 2002 Chem. Rev. 102 2477
Sreedhara A and Cowan J A 2001 J. Biol. Inorg. Chem. 6 337
Ali H and VanLier J E 1999 Chem. Rev. 99 2379
Bonnett R 1995 Chem. Soc. Rev. 24 19
Sessler M C, Hemmi G, Mody T D, Murai T, Burrel A and Young S W 1994 Acc. Chem. Res. 27 43
Ackroyd R, Kelty C, Brown N and Reed M 2001 Photochem. Photobiol. 74 656
De Rosa M C and Crutchley R J 2002 Coord. Chem. Rev. 233/4 351
Sternberg E D, Dolphin D and Brückner C 1998 Tetrahedron 54 4151
Delaney S, Pascaly M, Bhattacharya P K, Han K and Barton J K 2002 Inorg. Chem. 41 1966
Hastings C A and Barton J K 1999 Biochemistry 38 10042
Angeles-Boza A M, Bradley P M, Fu P K-L, Wicke S E, Bacsa J, Dunbar K R and Turro C 2004 Inorg. Chem. 43 8510
Ambroise A and Maiya B G 2000 Inorg. Chem. 39 4264
Sastri C V, Eswaramoorthy D, Giribabu L and Maiya B G 2003 J. Inorg. Biochem. 94 138
Hergueta-Bravo A, Jimenez-Hernandez M E, Montero F, Oliveros E and Orellana G 2002 J. Phys. Chem. B 106 4010
Eppley H J, Lato S M, Ellington A D and Zalesky J M 1999 Chem. Commun. 2405
Dhar S and Chakravarty A R 2003 Inorg. Chem. 42 2483
Dhar S, Senapati D, Das P K, Chattopadhyay P, Nethaji M and Chakravarty A R 2003 J. Am. Chem. Soc. 125 12118
Dhar S, Senapati D, Reddy P A N, Das P K and Chakravarty A R 2003 Chem. Commun. 2452
Reddy P A N, Santra B K, Nethaji M and Chakravarty A R 2004 J. Inorg. Biochem. 98 377
Thomas A M, Nethaji M and Chakravarty A R 2004 J. Inorg. Biochem. 98 1087
Thomas A M, Naik A D, Nethaji M and Chakravarty A R 2004 Inorg. Chim. Acta 357/8 2315
Thomas A M, Naik A D, Nethaji M and Chakravarty A R 2004 Indian J. Chem. A43 691
Patra A K, Dhar S, Nethaji M and Chakravarty A R 2003 Chem. Commun. 1562
Gupta T, Dhar S, Nethaji M and Chakravarty A R 2004 Dalton Trans. 1896
Qian X, Huang T-B, Wei D-Z, Zhu D-H, Fan M-C and Yao W 2000 J. Chem. Soc., Perkin Trans. 2 715
Jakobs A and Piette J 1994 J. Photochem. Photobiol. B22 9
Jakobs A and Piette J 1995 J. Med. Chem. 38 869
Santra B K, Reddy P A N, Neelakanta G, Mahadevan S, Nethaji M and Chakravarty A R 2002 J. Inorg. Biochem. 89 191
Zelenko O, Gallagher J and Sigman D S 1997 Angew. Chem., Int. Ed. Engl. 36 2776
Veal J M, Merchant K and Rill R L 1991 Nucleic Acids Res. 19 3383
Toshima K, Takano R, Ozawa T and Matsumura S 2002 Chem. Commun. 212
Bernadou J, Pratviel G, Bennis F, Girardet M and Meunier B 1989 Biochemistry 28 7268
Kahn O 1993 Molecular magnetism (Weinheim, Germany: VCH)
Sheldrick G M 2001 SADABS, Version 2, Multi-Scan Absorption Correction Program, Universität of Göttingen, Göttingen, Germany
Sheldrick G M 1997 SHELX-97, A Computer Program for Crystal Structure Solution and Refinement, Universität Göttingen, Göttingen, Germany
Johnson C K 1976 ORTEP III Report ORNL-5138, Oak Ridge National Laboratory: Oak Ridge, Tennessee, USA
Marmur J 1961 J. Mol. Biol. 3 208
Reichmann M E, Rice S A, Thomas C A and Doty P 1954 J. Am. Chem. Soc. 76 3047
Lee M, Rhodes A L, Wyatt M D, Forrow S and Hartley 1993 Biochemistry 32 4237
Santra B K, Reddy P A N, Nethaji M and Chakravarty A R 2001 J. Chem. Soc., Dalton Trans. 3553
Khan A U 1976 J. Phys. Chem. 80 2219
Croke D T, Perrouault L, Sari M A, Battioni J P, Mansuy D, Helene C and Le Doan T 1993 J. Photochem. Photobiol. B18 41
Author information
Authors and Affiliations
Corresponding author
Additional information
Dedicated to the memory of the late Professor Bhaskar G Maiya
Rights and permissions
About this article
Cite this article
Gupta, T., Patra, A.K., Dhar, S. et al. Effect of copper-sulphur bond on the DNA photo-cleavage activity of 2-(methylthio)ethylpyridine-2-carbaldimine copper(II) complexes. J Chem Sci 117, 123–132 (2005). https://doi.org/10.1007/BF03356106
Published:
Issue Date:
DOI: https://doi.org/10.1007/BF03356106