Yearley Eric J, Zhurova Elizabeth A, Zhurov Vladimir V, Pinkerton A Alan
Department of Chemistry, University of Toledo, Toledo, Ohio 43606, USA.
J Am Chem Soc. 2007 Dec 5;129(48):15013-21. doi: 10.1021/ja075211j. Epub 2007 Nov 10.
In a continuing effort to determine a relationship between the biological function and the electronic properties of steroidal and nonsteroidal estrogens by analysis of the submolecular properties, an experimental charge density study has been pursued on the nonsteroidal phytoestrogen, genistein. X-ray diffraction data were obtained using a Rigaku R-Axis Rapid high-power rotating anode diffractometer with a curved image plate detector at 20(1) K. The total electron density was modeled using the Hansen-Coppens multipole model. Genistein packs in puckered sheets characterized by intra- and intermolecular hydrogen bonds while weaker intermolecular hydrogen bonds (O...H-C) exist between the sheets. A topological analysis of the electron density of genistein was then completed to characterize all covalent bonds, three O...H-O and four O...H-C intermolecular hydrogen bonds. Two O...H-O hydrogen bonds are incipient (partially covalent) type bonds, while the other O...H-O hydrogen bond and O...H-C hydrogen bonds are of the pure closed-shell interaction type. In addition, two intermolecular H...H interactions have also been characterized from the topology of the electron density. The binding of genistein to the estrogen receptor is discussed in terms of the electrostatic potential derived from the electron density distribution.
为了通过分析亚分子性质来确定甾体和非甾体雌激素的生物学功能与电子性质之间的关系，我们持续开展了相关研究，对非甾体植物雌激素染料木黄酮进行了实验电荷密度研究。使用Rigaku R-Axis Rapid高功率旋转阳极衍射仪及弯曲成像板探测器在20(1) K下获得了X射线衍射数据。利用汉森-科彭斯多极模型对总电子密度进行了建模。染料木黄酮堆积成褶皱片层，其特征是分子内和分子间存在氢键，而片层之间存在较弱的分子间氢键（O...H-C）。随后完成了对染料木黄酮电子密度的拓扑分析，以表征所有共价键、三个O...H-O和四个O...H-C分子间氢键。两个O...H-O氢键是初始（部分共价）型键，而另一个O...H-O氢键和O...H-C氢键是纯闭壳相互作用型。此外，还从电子密度拓扑结构中表征了两种分子间H...H相互作用。根据由电子密度分布得出的静电势，讨论了染料木黄酮与雌激素受体的结合情况。
