Diversification of Nucleophile-Intercepted Beckmann Fragmentation Products and Related Density Functional Theory Studies.
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ABSTRACT:
SUBMITTER: Lowder LL
PROVIDER: S-EPMC7485623 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:To induce double-proton transfer (DPT) with guanine in a biological environment, 12 cytosine analogues (Ca) were formed by atomic substitution. The DPT reactions in the Watson-Crick cytosine-guanine model complex (Ca0G) and 12 modified cytosine-guanine complexes (Ca1-12G) were investigated using density functional theory methods at the M06-2X/def2svp level. The intramolecular proton transfers within the analogues are not facile due to high energy barriers. The hydrogen bond lengths of the Ca1-12G complexes are shorter than those in the Ca0G complex, which are conducive to DPT reactions. The DPT energy barriers of Ca1-12G complexes are also lower than that of the Ca0G complex, in particular, the barriers in the Ca7G and Ca11G complexes were reduced to -1.33 and -2.02?kcal/mol, respectively, indicating they are significantly more prone to DPT reactions. The DPT equilibrium constants of Ca1-12G complexes range from 1.60 × 100 to 1.28 × 107, among which the equilibrium constants of Ca7G and Ca11G are over 1.0 × 105, so their DPT reactions may be adequate. The results demonstrate that those cytosine analogues, especially Ca7 and Ca11, are capable of inducing DPT with guanine, and then the guanine tautomer will form mismatches with thymine during DNA replication, which may provide new strategies for gene therapy.
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Project description:Lower chlorinated polychlorinated biphenyls (PCBs) are readily metabolized via hydroxylated metabolites to reactive PCB quinones. Although these PCB metabolites elicit biochemical changes by mechanisms involving cellular target molecules, such as the aryl hydrocarbon receptor, and toxicity by interacting with enzymes like topoisomerases, only few PCB quinones have been synthesized and their conformational properties investigated. Similar to the parent compounds, knowledge of the three-dimensional structure of PCB quinones may therefore be important to assess their fate and risk. To address this gap in our knowledge, the gas phase molecular structure of a series of PCB quinones was predicted using HF/3-21G, B3LYP/6-31G?? and UB3LYP/6-311G?? calculations and compared to the respective solid state structure. All three methods overestimated the Cl-C bond length, but otherwise provided a reasonable approximation of the solid state bond angles and bond lengths. Overall, the UB3LYP/6-311G?? level of theory yielded the best approximation of the molecular structure of PCB quinones in the solid state. Chlorine addition at the ortho position of both rings was found to increase the dihedral angle of the resulting quinone compound, which may have important implications for their interaction with cellular targets and, thus, their toxicity.
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Project description:During the current study, the new aminothiazole Schiff base ligands (S1 ) and (S2 ) were designed by reacting 1,3-thiazol-2-amine and 6-ethoxy-1,3-benzothiazole-2-amine separately with 3-methoxy-2-hydroxybenzaldehyde in good yields (68-73%). The ligands were characterized through various analytical, physical, and spectroscopic (FT-IR, UV-Vis, 1H and 13C NMR, and MS) methods. The ligands were exploited in lieu of chelation with bivalent metal (cobalt, nickel, copper, and zinc) chlorides in a 1:2 (M:L) ratio. The spectral (UV-Vis, FT-IR, and MS), as well as magnetic, results suggested their octahedral geometry. The theoretically optimized geometrical structures were examined using the M06/6-311G+(d,p) function of density function theory. Their bioactive nature was designated by global reactivity parameters containing a high hardness (η) value of 1.34 eV and a lower softness (σ) value of 0.37 eV. Different microbial species were verified for their potency (in vitro), revealing a strong action. The Gram-positive Micrococcus luteus and Gram-negative Escherichia coli gave the highest activities of 20 and 21 mm for compounds (8) and (7), respectively. The antifungal activity against the Aspergillus niger and Aspergillus terreus species gave the highest activities of 20 and 18 mm for compounds (7) and (6), respectively. The antioxidant activity, evaluated as DPPH and ferric reducing power, gave the highest inhibition (%) as 72.0 ± 0.11% (IC50 = 144 ± 0.11 μL) and 66.3% (IC50 = 132 ± 0.11 μL) for compounds (3) and (8), respectively. All metal complexes were found to be more biocompatible than free ligands due to their chelation phenomenon. The energies of LUMOs had a link with their activities.
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