New Charge Transfer Complexes of K+-Channel-Blocker Drug (Amifampridine; AMFP) for Sensitive Detection; Solution Investigations and DFT Studies.

UV-Vis spectroscopy was used to investigate two new charge transfer (CT) complexes formed between the K+-channel-blocker amifampridine (AMFP) drug and the two π-acceptors 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) and tetracyanoethylene (TCNE) in different solvents. The molecular composition of the new CT complexes was estimated using the continuous variations method and found to be 1:1 for both complexes. The formed CT complexes' electronic spectra data were further employed for calculating the formation constants (KCT), molar extinction coefficients (εCT), and physical parameters at various temperatures, and the results demonstrated the high stability of both complexes. In addition, sensitive spectrophotometric methods for quantifying AMFP in its pure form were proposed and statistically validated. Furthermore, DFT calculations were used to predict the molecular structures of AMFP-DDQ and AMFP-TCNE complexes in CHCl3. TD-DFT calculations were also used to predict the electronic spectra of both complexes. A CT-based transition band (exp. 399 and 417 nm) for the AMFP-TCNE complex was calculated at 411.5 nm (f = 0.105, HOMO-1 → LUMO). The two absorption bands at 459 nm (calc. 426.9 nm, f = 0.054) and 584 nm (calc. 628.1 nm, f = 0.111) of the AMFP-DDQ complex were theoretically assigned to HOMO-1 → LUMO and HOMO → LUMO excitations, respectively.

Synthesis, DNA binding and complex formation reactions of 3-amino-5,6-dimethyl-1,2,4-triazine with Pd(II) and some selected biorelevant ligands.

With the purpose of studying the binding behavior of Pd(II) complexes with DNA as the main biological target, and their ability to penetrate reasonably into tumour cells and destroy their replication ability, Pd(ADT)Cl2 complex was synthesized and characterized, where ADT is 3-amino-5,6-dimethyl-1,2,4-triazine. Stoichiometry and stability constants of the complexes formed between various biologically relevant ligands (amino acids, amides, DNA constituents, and dicarboxylic acids) and [Pd(ADT)(H2O)2](2+) were investigated at 25°C and at constant 0.1moldm(-3) ionic strength. The concentration distribution diagrams of the various species formed are evaluated. Further investigation of the binding properties of the diaqua complex [Pd(ADT)(H2O)2](2+) with calf thymus DNA (CT-DNA) was investigated by UV-vis spectroscopy. The intrinsic binding constants (Kb) calculated from UV-vis absorption studies was calculated to be 2.00×10(3)moldm(-3). The calculated (Kb) value was found to be of lower magnitude than that of the classical intercalator EB (Ethidium bromide) (Kb=1.23(±0.07)×10(5)moldm(-3)) suggesting an electrostatic and/or groove binding mode for the interaction with CT-DNA. Thermal denaturation has been systematically studied by spectrophotometric method and the calculated ΔTm was nearly 5°C, supporting the electrostatic and/or groove binding mode for the interaction between the complex and CT-DNA.