Deutsches Elektronen-Synchrotron (DESY), Notkestr. 85, 22607, Hamburg, Germany.
Institute of Organic Chemistry, Justus Liebig University, Heinrich-Buff-Ring 17, 35392, Giessen, Germany.
Chemistry. 2021 Apr 7;27(20):6198-6203. doi: 10.1002/chem.202100078. Epub 2021 Mar 5.
Fluorinated derivatives of biological molecules have proven to be highly efficient at modifying the biological activity of a given protein through changes in the stability and the kind of docking interactions. These interactions can be hindered or facilitated based on the hydrophilic/hydrophobic character of a particular protein region. Diadamantyl ether (C H O) possesses both kinds of docking sites, serving as a good template to model these important contacts with aromatic fluorinated counterparts. In this work, an experimental study on the structures of several complexes between diadamantyl ether and benzene as well as a series of fluorinated benzenes is reported to analyze the effect of H→F substitution on the interaction and structure of the resulting molecular clusters using rotational spectroscopy. All experimentally observed complexes are largely dominated by London dispersion interactions with the hydrogen-terminated surface areas of diadamantyl ether. Already single substitution of one hydrogen atom with fluorine changes the preferred docking site of the complexes. However, the overall contributions of the different intermolecular interactions are similar for the different complexes, contrary to previous studies focusing on the difference in interactions using fluorinated and non-fluorinated molecules.
生物分子的氟化衍生物已被证明在通过改变稳定性和对接相互作用的类型来修饰给定蛋白质的生物活性方面非常有效。这些相互作用可以根据特定蛋白质区域的亲水性/疏水性来阻碍或促进。二金刚烷醚（C H O）具有两种对接位点，可作为与芳香族氟化类似物建模这些重要接触的良好模板。在这项工作中，报道了几项关于二金刚烷醚与苯以及一系列氟化苯之间的复合物结构的实验研究，以使用旋转光谱分析 H→F 取代对所得分子团簇的相互作用和结构的影响。所有实验观察到的复合物主要由伦敦色散相互作用主导，其中二金刚烷醚的氢端表面区域占主导地位。即使仅用一个氟原子取代一个氢原子，也会改变复合物的首选对接位点。然而，与以前的研究不同，这些研究侧重于使用氟化和非氟化分子的相互作用差异，对于不同的复合物，不同分子间相互作用的总体贡献相似。
