Computer-Aided Drug Design Center, Department of Pharmaceutical Sciences, School of Pharmacy, University of Maryland , Baltimore, Maryland 21201, United States.
J Phys Chem B. 2017 Jul 20;121(28):6813-6821. doi: 10.1021/acs.jpcb.7b04198. Epub 2017 Jul 11.
Halogens are present in a significant number of drugs, contributing favorably to ligand-protein binding. Currently, the contribution of halogens, most notably chlorine and bromine, is largely attributed to halogen bonds involving favorable interactions with hydrogen bond acceptors. However, we show that halogens acting as hydrogen bond acceptors potentially make a more favorable contribution to ligand binding than halogen bonds based on quantum mechanical calculations. In addition, bioinformatics analysis of ligand-protein crystal structures shows the presence of significant numbers of such interactions. It is shown that interactions between halogens and hydrogen bond donors (HBDs) are dominated by perpendicular C-X···HBD orientations. Notably, the orientation dependence of the halogen-HBD (X-HBD) interactions is minimal over greater than 100° with favorable interaction energies ranging from -2 to -14 kcal/mol. This contrasts halogen bonds in that X-HBD interactions are substantially more favorable, being comparable to canonical hydrogen bonds, with a smaller orientation dependence, such that they make significant, favorable contributions to ligand-protein binding and, therefore, should be actively considered during rational ligand design.
卤素存在于大量药物中,有利于配体-蛋白质结合。目前,卤素(尤其是氯和溴)的贡献主要归因于涉及与氢键受体有利相互作用的卤素键。然而,我们通过量子力学计算表明,卤素作为氢键受体可能对配体结合做出更有利的贡献,而不是卤素键。此外,配体-蛋白质晶体结构的生物信息学分析表明存在大量此类相互作用。结果表明,卤素与氢键供体(HBD)之间的相互作用主要由垂直的 C-X···HBD 取向主导。值得注意的是,卤素-HBD(X-HBD)相互作用的取向依赖性在超过 100°时最小,其相互作用能范围为-2 至-14 kcal/mol。这与卤素键形成鲜明对比,因为 X-HBD 相互作用更为有利,可与典型氢键相媲美,其取向依赖性更小,因此它们对配体-蛋白质结合做出了重要的有利贡献,因此在合理的配体设计中应积极考虑它们。