Aquino Adélia J A, Tunega Daniel, Haberhauer Georg, Gerzabek Martin H, Lischka Hans
Institute for Theoretical Chemistry and Structural Biology, University of Vienna, Währingerstrasse 17, A-1090 Vienna, Austria.
J Comput Chem. 2003 Nov 30;24(15):1853-63. doi: 10.1002/jcc.10342.
Hydrogen-bonded interactions between local defect structures on broken clay surfaces modeled as molecular clusters and the organic molecules acetic acid, acetate, and N-methylacetamide (NMA) have been investigated. Density functional theory and polarized basis sets have been used for the computation of optimized interaction complexes and formation energies. The activity of the defect structures has been characterized as physical or chemical in terms of the strength of the hydrogen bonds formed. Chemical defects lead to significantly enhanced interactions with stronger hydrogen bonds and larger elongation of OH bonds in comparison to the physical defects. The type of interaction with the defect structure significantly influences the planarity of the model peptide bond in NMA. Both cases, enhancement of the planarity by increase of the CN double bond character and strong deviations from planarity, are observed.
研究了将破碎黏土表面的局部缺陷结构模拟为分子簇时，其与有机分子乙酸、乙酸盐和N-甲基乙酰胺（NMA）之间的氢键相互作用。采用密度泛函理论和极化基组来计算优化后的相互作用复合物和形成能。根据形成的氢键强度，将缺陷结构的活性表征为物理活性或化学活性。与物理缺陷相比，化学缺陷会导致通过更强的氢键和更大的OH键伸长而显著增强的相互作用。与缺陷结构的相互作用类型显著影响NMA中模型肽键的平面性。观察到了两种情况，即通过增加C=N双键特征增强平面性以及与平面性的强烈偏差。
