Probing Molecular Recognition at the Solid–Gas Interface by Sum-Frequency Vibrational Spectroscopy

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• 作者：Arianna Aprile ; Federica Ciuchi ; Roberta Pinalli ; Enrico Dalcanale ; Pasquale Pagliusi
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2016
• 出版时间：August 4, 2016
• 年：2016
• 卷：7
• 期：15
• 页码：3022-3026
• 全文大小：363K
• 年卷期：0
• ISSN：1948-7185

文摘

Molecular recognition is among the most important chemical events in living systems and has been emulated in supramolecular chemistry, driven by chemical and biochemical sensing potential. Identifying host–guest association in situ at the interface, between the substrate-bound receptors and the analyte-containing media, is essential to predict complexation performances in term of the receptor conformation, orientation and organization. Herein, we report the first sum-frequency vibrational spectroscopy study of molecular recognition at the solid–gas interface. The binding capability of tetraquinoxaline cavitands toward volatile aromatic and aliphatic compounds, namely benzonitrile and acetonitrile, is investigated as test system. We prove the selective complexation of the receptors, organized in a solid-supported hybrid bilayer, toward aromatic compounds. Quantitative analysis allows to correlate the average orientations of the guest molecules and the host binding pockets, establishing “on-axis” complexation of benzonitrile within the cavitand cavity. The study is readily applicable to other receptors, molecular architectures, interfaces and analytes.