Interaction of anticancer drug cisplatin with guanine: Density functional theory and surface‐enhanced Raman spectroscopy study

Surface‐enhanced Raman spectroscopy (SERS) in a silver sol assisted by density functional theory (DFT) calculations is shown to be a promising tool in the characterization of platinum complexes and their interaction with nucleic acid bases. This is demonstrated using cisplatin and guanine as a model. The energies and geometric parameters of cisplatin, guanine, and their reaction products are calculated at Becke's nonlocal three parameter exchange and correlation functional and the Lee–Yang–Parr correlation functional level using the 6‐31++G(d,p) basis set on the light elements and the effective core potential by Hay and Wadt on platinum. Available X‐ray crystallography data are mostly in agreement with predictions within the experimental precision level, although PtN bond lengths tend to be systematically overestimated. The normal Raman spectrum of cisplatin is assigned. The SERS spectra of cisplatin and its reaction product with guanine are measured from 10 −6 M aqueous solution. The observed spectral changes in the SERS spectrum of guanine upon cisplatin binding are modeled by DFT calculations. The best agreement between theory and experiment is achieved when the adsorbed reaction product is assumed to be the 1:1 adduct cis ‐Pt(NH 3 ) 2 ClG in which Pt is bound to N7 and guanine is deprotonated at N9. © 2003 Wiley Periodicals, Inc. Biopolymers (Biospectroscopy), 2003