An unusual (H(2)O)(20) discrete water cluster in the supramolecular host of a charge transfer platinum(ii) complex: cytotoxicity and DNA cleavage activities.
The chemical reaction of Pt(II)(L(1))Cl(2) [L(1) = N-4-tolylpyridine-2-aldimine] with a bidentate N,S-donor atom ligand, 2-methylthioaniline, (HL(2)) in alkaline methanolic medium yielded a mixed ligand donor-acceptor complex, [Pt(II)(L(1))(L(2))]Cl, [1]Cl. The complex has been characterized by different spectroscopic and electrochemical techniques. The complex showed intense interligand charge transfer (ILCT) transition in the long wavelength region of UV-vis spectrum (>600 nm). The single-crystal X-ray structure of complex, [1]Cl·3.3H(2)O is reported. The cationic complex upon crystallization from aqueous methanol solvent produces an assembly of discrete, three dimensional (H(2)O)(20) guest moiety within the reference Pt-complex host lattice. The water assembly showed a unique type of aggregation of a distorted cube encapsulated by hydrogen bonded network of a twelve-water ring. The complex displayed one reversible cathodic response at -0.75 V and two irreversible anodic responses at 0.42 and 0.79 V versus Ag/AgCl reference electrode. The redox processes are characterized by EPR and spectroelectrochemistry. Density-functional theory calculations were employed to confirm the structural features and to support the spectral and redox properties of the complex. The square-planar complex has been found to intercalate DNA. Fluorescence spectroscopy, circular dichroism, cyclic voltammetry, viscosity measurements, together with DNA melting studies have been employed to characterize the binding of [1]Cl with calf thymus DNA. Agarose gel electrophoresis indicates that the complex cleaves supercoiled (SC) pUC19 plasmid DNA to its nicked circular (NC) form via singlet oxygen. As determined by a MTT assay, [1]Cl exhibits significant cytotoxicity with IC(50) value 58 μM.
Mandal
Sutanuva
S
Department of Inorganic Chemistry, Indian Association for the Cultivation of Science, Kolkata, 700 032, India.
Castiñeiras
Alfonso
A
Mondal
Tapan K
TK
Mondal
Arindam
A
Chattopadhyay
Dhrubajyoti
D
Goswami
Sreebrata
S
D045744:Cell Line, Tumor; D056831:Coordination Complexes / Q000737:chemistry* / Q000633:toxicity; D018360:Crystallography, X-Ray; D053837:DNA Cleavage; D055664:Electrochemical Techniques; D004578:Electron Spin Resonance Spectroscopy; D006801:Humans; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010984:Platinum / Q000737:chemistry*; D026082:Singlet Oxygen / Q000737:chemistry; D013056:Spectrophotometry, Ultraviolet; D013696:Temperature; D014867:Water / Q000737:chemistry*
D056831:Coordination Complexes; D014867:Water; D026082:Singlet Oxygen; D010984:Platinum