文章基本信息

标题：Halogen bonds in biological molecules
本地全文：下载
作者：Pascal Auffinger ; Franklin A. Hays ; Eric Westhof 等
期刊名称：Proceedings of the National Academy of Sciences
印刷版ISSN：0027-8424
电子版ISSN：1091-6490
出版年度：2004
卷号：101
期号：48
页码：16789-16794
DOI：10.1073/pnas.0407607101
语种：English
出版社：The National Academy of Sciences of the United States of America
摘要：Short oxygen-halogen interactions have been known in organic chemistry since the 1950s and recently have been exploited in the design of supramolecular assemblies. The present survey of protein and nucleic acid structures reveals similar halogen bonds as potentially stabilizing inter- and intramolecular interactions that can affect ligand binding and molecular folding. A halogen bond in biomolecules can be defined as a short C[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">X{middle dot}{middle dot}{middle dot}O[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">Y interaction (C[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">X is a carbon-bonded chlorine, bromine, or iodine, and O[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">Y is a carbonyl, hydroxyl, charged carboxylate, or phosphate group), where the X{middle dot}{middle dot}{middle dot}O distance is less than or equal to the sums of the respective van der Waals radii (3.27 A for Cl{middle dot}{middle dot}{middle dot}O, 3.37A for Br{middle dot}{middle dot}{middle dot}O, and 3.50 A for I{middle dot}{middle dot}{middle dot}O) and can conform to the geometry seen in small molecules, with the C[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">X{middle dot}{middle dot}{middle dot}O angle {approx}165{degrees} (consistent with a strong directional polarization of the halogen) and the X{middle dot}{middle dot}{middle dot}O[IMG]/medium/cjs0807.gif" ALT="{cjs0807}">Y angle {approx}120{degrees}. Alternative geometries can be imposed by the more complex environment found in biomolecules, depending on which of the two types of donor systems are involved in the interaction: (i) the lone pair electrons of oxygen (and, to a lesser extent, nitrogen and sulfur) atoms or (ii) the delocalized {pi} -electrons of peptide bonds or carboxylate or amide groups. Thus, the specific geometry and diversity of the interacting partners of halogen bonds offer new and versatile tools for the design of ligands as drugs and materials in nanotechnology.
关键词：molecular folding ; molecular recognition ; molecular design