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拉曼光谱探究低温对π…H-X氢键的影响
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Abstract:
π…H-X氢键(以下简称π氢键)作为X-H质子供体与π电子体系间的弱相互作用，广泛存在于生物大分子中，在分子识别、超分子组装与生物结构稳定等过程中起到重要作用。本文以费米共振为分子探针，采用拉曼光谱，系统研究低温对π氢键的调控机制。具体研究结果如下：测量了苯–甲醇浓度梯度实验，得到π氢键与费米共振之间的关系：π氢键数量的增加会导致费米共振强度降低。其次对1:1苯–甲醇进行了变温实验，结果表明，通过降温使样品发生相变进而强化氢键作用：约？10℃苯率先凝固，分子有序度提升，费米双峰峰强上升、半高宽变窄并红移；约？90℃甲醇形成共晶，氢键网络更加致密，π氢键对振动非谐性的调控显著增强，进而使费米共振耦合强度进一步降低。
The π…H-X hydrogen bond (hereinafter referred to as π-hydrogen bond) is a weak interaction formed between X-H proton donors and π-electron systems. It widely exists in biomacromolecules and plays a vital role in molecular recognition, supramolecular assembly and biological structural stabilization. Using Fermi resonance as a molecular probe and Raman spectroscopy as the research method, this paper systematically investigates the regulation mechanism of low temperature on π-hydrogen bonds. The main research findings are summarized as follows. Concentration gradient experiments of benzene-methanol mixtures were carried out, revealing the correlation between π-hydrogen bonds and Fermi resonance: an increase in the number of π-hydrogen bonds reduces the intensity of Fermi resonance. Variable-temperature experiments were further performed on benzene-methanol mixtures at a molar ratio of 1:1. The results demonstrate that cooling induces phase transition and strengthens hydrogen bonding interactions. Benzene solidifies first at approximately ？10？C with enhanced molecular orderliness, accompanied by increased intensity, narrowed full width at half maximum and redshift of the Fermi doublet peaks. Methanol forms eutectic crystals at around ？90？C, constructing a denser hydrogen bond network. The regulation effect of π-hydrogen bonds on vibrational anharmonicity is markedly enhanced, which further weakens the coupling strength of Fermi resonance.
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