Assessing the reliability of density functional methods in the conformational study of polypeptides: The treatment of intraresidue nonbonding interactions

被引:47
作者
Improta, R
Barone, V [1 ]
机构
[1] Univ Naples Federico II, Dipartimento Chim, Complesso Univ Monte S Angelo,Via Cintia, I-80126 Naples, Italy
[2] CNR, Ist Biostrutt & Bioimmagini, I-80134 Naples, Italy
关键词
dipeptide analog; helical conformers; density functionals; noncovalent interactions;
D O I
10.1002/jcc.20062
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
The role of intraresidue interactions in determining the conformational behavior of polypeptides is analyzed by means of density functional and post-Hartree-Fock computations on the alanine dipeptide analog and other model compounds. Our computations show that the accuracy of current density functionals is sufficient for H-bond, electrostatic, inductive, and short-range repulsive interactions, whereas medium-range attractions between electron-rich atoms and/or bonds are underestimated. This leads, in turn, to an underestimation of the stability of helical structures w.r.t. extended or folded conformers involving H-bonds. Those results could pave the route for devising local ad hoc corrections able to significantly improve structural and dynamic predictions for polypeptides issuing from DFT computations. (C) 2004 Wiley Periodicals, Inc.
引用
收藏
页码:1333 / 1341
页数:9
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