Domingos Sérgio R, Pérez Cristóbal, Kreienborg Nora M, Merten Christian, Schnell Melanie
Deutsches Elektronen-Synchrotron (DESY), Notkestraße 85, Hamburg, 22607, Germany.
CFisUC, Department of Physics, University of Coimbra, Coimbra, 3004-516, Portugal.
Commun Chem. 2021 Mar 5;4(1):32. doi: 10.1038/s42004-021-00468-4.
Chiral molecular recognition is a pivotal phenomenon in biomolecular science, governed by subtle balances of intermolecular forces that are difficult to quantify. Non-covalent interactions involving aromatic moieties are particularly important in this realm, as recurring motifs in biomolecular aggregation. In this work, we use high-resolution broadband rotational spectroscopy to probe the dynamic conformational landscape enclosing the self-pairing topologies of styrene oxide, a chiral aromatic system. We reach a definite assignment of four homochiral and two heterochiral dimers using auxiliary quantum chemistry calculations as well as structure-solving methods based on experimental isotopic information. A complete picture of the dimer conformational space is obtained, and plausible routes for conformational relaxation are derived. Molecular structures are discussed in terms of conformational flexibility, the concerted effort of weak intermolecular interactions, and their role in the expression of the molecular fit.
手性分子识别是生物分子科学中的一个关键现象，由难以量化的分子间力的微妙平衡所支配。涉及芳香部分的非共价相互作用在这一领域尤为重要，是生物分子聚集的反复出现的基序。在这项工作中，我们使用高分辨率宽带转动光谱来探测围绕氧化苯乙烯（一种手性芳香体系）自配对拓扑结构的动态构象景观。我们通过辅助量子化学计算以及基于实验同位素信息的结构解析方法，明确确定了四个同手性二聚体和两个异手性二聚体。获得了二聚体构象空间的完整图景，并推导了构象弛豫的合理途径。从构象灵活性、弱分子间相互作用的协同作用及其在分子匹配表达中的作用等方面讨论了分子结构。
