Theoretical Design of New Grafted Molecules d-Glucosamine-Oxyresveratrol-Essential Amino Acids: DFT Evaluation of the Structure-Antioxidant Activity.

In the pursuit of innovative high-performance materials suitable for antioxidant applications, the density functional theory was employed to design a series of compounds derived from small biodegradable organic molecules. This study involved grafting the negatively charged unit d-glucosamine (GleN) and essential amino acids onto the 3 and 4' carbons of the backbone of trans-2,4,3',5'-tetrahydroxystilbene (trans-OXY), respectively. The aim was to prevent trans-OXY degradation into the cis region and enhance its electronic and antioxidant properties. Theoretical calculations using DFT/PW91/TZP in water revealed that the designed biomolecules (GleN-OXY-AA) outperformed both free OXY units and essential amino acids in terms of antioxidant efficacy, as indicated by the bond dissociation energy (BDE) findings. Notably, GleN-OXY-Ile and GleN-OXY-Trp compounds exhibited an average BDE of 66.355 kcal/mol, translating to 1.82 times the activity of t-OXY and 1.55 times the action of ascorbic acid (Vit C). AIM analysis demonstrated that the proposed biomaterials favored the formation of quasi-rings through intramolecular H···O hydrogen bonds, promoting π-electron delocalization and stabilization of radical, cationic, and anionic forms. Quantum calculations revealed the release of hydrogen atoms or electrons from sites of reduced electronegativity, visually identified by MEP maps and estimated by Hirshfeld atomic charges.

Theoretical Exploration of Enhanced Antioxidant Activity in Copper Complexes of Tetrahydroxystilbenes: Insights into Mechanisms and Molecular Interactions.

A theoretical investigation was conducted using DFT/PW91/TZP/DMSO calculations on a complete set of exhaustive lists of 18 compounds resulting from the complexation of trans-2,4,3',5'-tetrahydroxystilbene (T-OXY) and cis-2,4,1',3'-tetrahydroxystilbene (C-OXY) with copper metal cations (Cu+ and Cu2+). The ligand-binding sites are the critical points of Quantum Theory of Atoms in Molecules (QTAIM) analysis on neutral and deprotonated ligands. Various mechanisms, including hydrogen atom transfer (HAT), sequential proton loss electron transfer (SPLET), single electron transfer followed by proton transfer (SET-PT), and bond dissociation energy (BDE(E0)) calculations, were employed to quantify the antioxidant activity. The BDE(E0) mechanism emerged as the most suitable approach for such analyses to evaluate the departure of hydrogen atoms since the results show the HAT mechanism is the most likely occurring. Particularly intriguing were the anionic Cu+ complexes with ligands adopting trans configurations and deprotonated conformations, displaying superior antioxidant activity compared to their counterparts. Remarkably, a single ligand within the Cu+ complex exhibited exceptional antioxidant prowess, yielding a BDE(E0) value of 91.47 kcal/mol. Furthermore, a complex involving two deprotonated ligands demonstrated antioxidant activity of 31.12 kcal/mol, signifying its potential as a potent antiradical agent, surpassing T-OXY by a factor of 3.91 and even surpassing the antioxidant efficiency of Vitamin C.

Multitask Quantum Study of the Curcumin-Based Complex Physicochemical and Biological Properties.

Density functional theory (DFT), time-dependent density functional theory (TDDFT), quantum theory of atoms in molecules (QTAIM), and extended transition state natural orbitals for chemical valence (ETS-NOCV) have all been used to investigate the physicochemical and biological properties of curcumin and three complexes, i.e., Cur-M (M = Ni, Cu, and Mg). Based on DFT calculations, the enolic form (Cur-Enol) is more stable than the anti-diketone form (Cur-Anti diketone) favored for complexation. This enolic form stability was explained by the presence of three intramolecular hydrogen bonds according to the QTAIM analysis. Furthermore, the ETS-NOCV technique revealed that the enolic form had more significant antioxidant activity compared with the anti-diketone form. The calculations from the COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) showed that the dimethyl sulfoxide (DMSO) solvent could dissolve all the curcumin tautomers Cur-Enol, Cur-Anti-diketone and Cur-Cu, Cur-Mg, and Cur-Ni complexes in contrast to benzene, acetone, octanol, ethanol, methanol, and water. Furthermore, except for Cur-Mg, which had a relatively low solubility (14 g/L), all complexes were insoluble in water. Cur-Anti-diketone was considerably more soluble than Cur-Enol in the examined solvents.

A quantum chemistry investigation on the structure of lanthanide triflates Ln(OTf)3 where Ln = La, Ce, Nd, Eu, Gd, Er, Yb and Lu.

Density functional theory has been used to probe the electronic structure, coordination number, optical properties and the vibration spectra of monolanthanide trifluoromethane sulfonate Ln(OTf)(3) complexes where Ln = La, Ce, Nd, Eu, Gd, Er, Yb and Lu. The study reveals that the OTf group is bonded to Ln as a bidentate ligand. TDDFT calculations show that, for La(OTf)(3), MLTC and HOMO-LUMO transitions in the UV-vis are strongly bathochromically shifted compared to those of Lu(OTf)(3.).