Experimental and theoretical study on the regioselective bis- or polyalkylation of 6-amino-2-mercapto-3H-pyrimidin-4-one using zeolite nano-gold catalyst and a quantum hybrid computational method.

The synthetic utility of 6-amino-2-mercapto-3H-pyrimidin-4-one 3 as building blocks for new poly (pyrimidine) by alkylation using the bis(halo) compounds and zeolite nano-gold as a catalyst was investigated. Furthermore, the experimental findings by the theoretical Density functional theory (DFT) computations at the DFT/B3LYP level of theory, utilizing the 6-311++G (d,p) basis set in the gas phase, were used to investigate the distinct phases for Regio isomer 11a & 12a and 11b & 12b compounds was fair and of good quality. The stability of the 12a and 12b phases is higher than the other Regio isomer 11a and 11b phases, according to DFT modelling. By computing HOMO and LUMO pictures, the electronic parameters: dipole moment of these compounds in the ground state were theoretically investigated. Non-linear optical (NLO) characteristics and quantum chemical parameters were examined using frontier molecular orbital (FMO) analysis. Natural bond orbital analysis was used to characterize the charge transfer of the electron density in the investigated compounds (NBO). The molecular electrostatic potential surfaces (MEPS) plots have been generated, and absorption spectral analysis in different solvents has been theoretically and experimentally examined to better understand the reactivity spots. At the B3LYP/6-311G (d,p) level of theory, thermodynamic properties were also calculated. Finally, DFT calculations were used to connect the structure-activity relationship (SAR) with real antibacterial results for compounds 12a and 12b.

Integrated experimental and theoretical insights for Malachite Green Dye adsorption from wastewater using low cost adsorbent.

Water pollution is one of the problems that threaten humanity, and to confront it with only experimental procedures is not enough. It is necessary to integrate both practical methods and theoretical calculations to achieve decontamination with the most accurate interpretation. Hence, discussing the experimental mechanism study of Malachite Green (MG) dye adsorption with the help of the application of density functional theory (DFT) calculations is the main goal of this article. The experimental results affirmed that the preparation of γ-Al2O3 by precipitation method using (NH4)2CO3 improved the porosity, the surface capability, and the adsorbent capacities (qmax = 210 mg/g) at optimum condition compared with the previous studies. Kinetic and equilibrium studies showed that the adsorption follows the pseudo-second-order model and Freundlich isotherm model, respectively. Also, the calculated and observed thermodynamic parameters exerted positive values of ΔH° and ΔS°, which translates into an endothermic process with increasing disorder of the system. Theoretical calculations at DFT- B3LYP/6-31G (d,P) level of theory were calculated to show the selectivity of using the cationic form of MG in the experimental measurements to find the interaction mechanism. The electronic structure and intramolecular charge transfer of MG, its cationic form and the complex of MG-Al were investigated theoretically at the B3LYP/6-31 G (d,p) level of theory. The equilibrium geometries of MG, its cationic form and the complex of MG-Al were determined, and it was found that these geometries are non-planar. The EHOMO and ELUMO energies can be used to calculate the global properties; chemical hardness (η), softness (S) and electronegativity (χ). The calculated non-linear optical parameters (NLO) of the studied compounds, the electronic dipole moment (µ), first-order hyperpolarizability (ß), the hyper-Rayleigh scattering (ßHRS) and the depolarization ratio (DR), showed promising optical properties. Finally, the computational and the experimental results indicated that the adsorption efficiency of MG from wastewater was directly associated with the dye electrophilicity power.