In the present work, the hydrolysis process of non-classical transplatin(II) with two same planar heterocycle amines has been studied using hybrid density functional theory (B3LYP) and IEF-PCM solvation models. Optimizations were performed at the B3LYP level using a combined basis set of (LanL2DZ+6-31+G(d,p)) with single-point energy evaluations using the B3LYP/6-31++G(3df,2pd) approach in vacuo and in aqueous solution. For the obtained structures of reactants, intermediates, transition states, and products, both thermodynamic (reaction energies and Gibbs energies) and kinetic (reaction barriers) characteristics were estimated. In comparison with cisplatin, decreased activation energies were obtained. The result implies that the non-classical transplatin with two same planar heterocycle amines increases the equatorial steric effect and lowers reaction barriers, which may assist in designing novel Pt-based anticancer drugs.

A systematic quantum chemical characterization of intrinsic structure, energies and spectral properties of all the studied cross-link adducts formed by the novel trans platinum with thiazole ligand has been carried out at B3LYP/6-31G* level of theory with the Lanl2dz pseudo potential basis set for the Pt atom. Special attention has been paid to the relative stability of these complexes and the factors that probably alter the order of the relative stability. The important influence of hydrogen bond on the structures, the energies and the spectral property was revealed. Other factors that contribute to relative stability including solvation effect, entropy and electronic delocalization energy were taken into account. The stability energy of the whole complex, and the interaction energy between two purine bases and the [Pt-(NH₃)thiazole]²⁺ group were adopted to study the interplay among subsystems and their contribution to relative stability of all the studied cross-link model. Finally, basic spectral properties of these complexes including H(8) chemical shifts of all the studied complexes and the VCD (vibrational circular dichroism) spectra of two pairs of GG chelate enantiomers, were provided in order to define the structure of the most possible duplex bearing novel trans platinum drug lesions.

The influence of a series of square planar metal adducts on the protonation ability of adenine has been investigated using ab initio calculation. The results showed that the protonation ability was mainly influenced by the long-range electrostatic effect in gas phase, no strong influence of different metals has been detected for the system studied, and the solvent effect calculations showed that the polar solvent could efficiently compensate for the long-range electrostatic effect dominant in gas phase. The NBO population analysis indicated that the protonation ability was mainly affected by changes of the electron density on selected atoms.

The influence of binding of cisplatin adducts on tautomeric equilibrium of guanine was investigated using quantum chemical method. The monoaqua adduct [Pt(NH₃)₂Cl(H₂O)]⁺ and the diaqua adduct [Pt(NH₃)₂(H₂O)₂]²⁺were chosen for coordination to the N(7) site of guanine tautomers. The results demonstrate that the platinum adducts influence moderately on tautomeric equilibrium, but do not change the relative stability of tautomers whether in gas phase or in aqueous solution. The keto form having H atom at N(1) and N(9) was always the predominant structure when cisplatin adducts were bound to guanine. However, other forms could coexist in water. Meanwhile, our calculations suggest that the tautomeric equilibrium should be via the same intermediate.