Halogen bonds in biological molecules
Halogen bonds in biological molecules
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DOI：
10.1073/pnas.0407607101
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发表时间：
2004-11-30
影响因子：
11.1
通讯作者：
Ho, PS
中科院分区：
文献类型：
--
作者：
Auffinger, P;Hays, FA;Ho, PS
自20世纪50年代以来，在有机化学中已经知道了短氧-卤素相互作用，最近在超分子组装的设计中得到了利用。目前对蛋白质和核酸结构的研究表明，类似的卤素键具有潜在的稳定分子间和分子内相互作用，可以影响配体结合和分子折叠。生物分子中的卤素键可以定义为短的C-(XO)- o -....-Y相互作用（C-X是碳键的氯、溴或碘，O-Y是羰基、羟基、带电羧酸盐或磷酸基），其中X…0距离小于或等于各自的范德华半径之和（(ClO)- o -....为3.27埃）3.37埃…0, 3.50埃= 0 ....O)，可以符合小分子的几何形状，用C-X....O角近似于165度（与卤素的强定向极化一致）和X…O-Y角近似为120度。在生物分子中发现的更复杂的环境可以施加不同的几何形状，这取决于参与相互作用的两种供体系统中的哪一种：(1)氧（以及较小程度上氮和硫）原子的孤对电子或（它）肽键或羧酸或酰胺基团的离域pi电子。因此，卤素键的特殊几何形状和相互作用伙伴的多样性为纳米技术中药物和材料配体的设计提供了新的和通用的工具。
Short oxygen-halogen interactions have been known in organicchemistry 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-(XO)-O-....-Y interaction (C-X is a carbon-bonded chlorine, bromine, or iodine, and O-Y is a carboryl, hydroxyl, charged carboxylate, or phosphate group), where the X.. 0 distance is less than or equal to the sums of the respective van der Waals radii (3.27 Angstrom for (ClO)-O-...., 3.37Angstrom for Br...O, and 3.50 Angstrom for I....O) and can conform to the geometry seen in small molecules, with the C-X....O angle approximate to165degrees (consistent with a strong directional polarization of the halogen) and the X.. O-Y angle approximate to120degrees. 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: (1) the lone pair electrons of oxygen (and, to a lesser extent, nitrogen and sulfur) atoms or (it) 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.