论文标题
水中生物分子的特异性与非特异性溶剂相互作用
Specific versus Nonspecific Solvent Interactions of a Biomolecule in Water
论文作者
论文摘要
溶剂相互作用，尤其是水合，在化学和生化系统中至关重要。模型系统揭示了此类相互作用的微观细节。我们发现了生物分子构建块吲哚（C $ _8 $ h $ _7 $ n）的特定氢键基序，色氨酸的彩色团，在水中：一个强大的局部$ \ text {n-h} \ cdots \ cdots \ cdots \ cdots \ cdots \ text {oh} _2 _2 _2 $ hydogen bond bydy byd bydy byd bydy byds bydrogen byned bysthosed-broundstructured溶液互动。从水溶液中吲哚的电子结构的合并实验和理论分析中可以揭示出这种见解。我们已经记录了水相吲哚的完整X射线光发射和螺旋谱，并通过\ emph {ab initio}建模来定量解释所有峰。建模价和核心光发射光谱的高效，准确的技术涉及最大重叠法和非平衡极化 - 可触发模型。两个孔电子构图分析定量描述了螺旋钻光谱。用于氮和碳的核心电子结合能突出了N-H组在N-H组和非特异性溶剂相互作用的特定相互作用。
Solvent interactions, particularly hydration, are vital in chemical and biochemical systems. Model systems unveil microscopic details of such interactions. We uncover a specific hydrogen-bonding motif of the biomolecular building block indole (C$_8$H$_7$N), tryptophan's chromophore, in water: a strong localized $\text{N-H}\cdots\text{OH}_2$ hydrogen bond, alongside unstructured solvent interactions. This insight is revealed from a combined experimental and theoretical analysis of indole's electronic structure in aqueous solution. We have recorded the complete X-ray photoemission and Auger spectrum of aqueous-phase indole, quantitatively explaining all peaks through \emph{ab initio} modeling. The efficient and accurate technique for modeling valence and core photoemission spectra involves the maximum-overlap method and the non-equilibrium polarizable-continuum model. A two-hole electron-population analysis quantitatively describes the Auger spectra. Core-electron binding energies for nitrogen and carbon highlight the specific interaction with a hydrogen-bonded water molecule at the N-H group and otherwise nonspecific solvent interactions.
