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Hidden isolated OH at the charged hydrophobic interface revealed by two-dimensional heterodyne-detected VSFG spectroscopy

DOI:10.1002/anie.202002368 期刊:Angewandte Chemie International Edition 出版年份:2020 更新时间:2025-09-23 15:19:57
摘要: Water around the hydrophobic groups mediates hydrophobic interaction that plays key roles in many chemical and biological processes. Thus, molecular-level elucidation of the properties of the water in the vicinity of the hydrophobic group is important. We report on the structure and dynamics of water at two oppositely charged hydrophobic interfaces, i.e., the tetraphenylborate ion (TPB-)/water and tetraphenylarsonium ion (TPA+)/water interfaces, which are clarified by two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy. The obtained 2D HD-VSFG spectra of anionic TPB- interface reveal the existence of distinct π-hydrogen bonded OH groups in addition to the usual hydrogen bonded OH groups, which is hidden in the steady-state spectrum. In contrast, 2D HD-VSFG spectra of cationic TPA+ interface only show the presence of usual hydrogen bonded OH groups. The present study demonstrates that the sign of the interfacial charge governs the structure and dynamics of water molecules that face the hydrophobic region.
作者: Mohammed Ahmed,Ken-ichi Inoue,Satoshi Nihonyanagi,Tahei Tahara
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To investigate the structure and dynamics of water at oppositely charged hydrophobic interfaces using two-dimensional heterodyne-detected vibrational sum frequency generation (2D HD-VSFG) spectroscopy.

The 2D HD-VSFG study demonstrated that the sign of the interfacial charge significantly affects the structure and dynamics of water at hydrophobic interfaces. At the anionic TPB-/water interface, distinct π-hydrogen bonded OH groups were identified, in addition to usual hydrogen bonded OH groups, which were hidden in the steady-state spectrum. In contrast, the cationic TPA+/water interface only showed the presence of usual hydrogen bonded OH groups. The findings highlight the decisive role of the charge in governing the structure and dynamics of water molecules facing hydrophobic regions.

The study's limitations include the time-resolution (~200 fs) of the present 2D HD-VSFG experiments, which may not directly detect ultrafast hydrogen-bond fluctuation (~60 fs). Additionally, the use of isotopically diluted water, while beneficial for suppressing vibrational couplings, may not fully represent the natural state of water in all environments.

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