Exploring Unusual Confined Chemistry: Excited-State Proton Transfer Reaction in Supported Liquid Membrane with Deep Eutectic Solvents.

IF 2.8 2区化学 Q3 CHEMISTRY, PHYSICAL

The Journal of Physical Chemistry B Pub Date : 2024-10-10 Epub Date: 2024-09-28 DOI:10.1021/acs.jpcb.4c03517

Sangeeta, Arnab Sil, Vikash Singh, Renu Bhati, Biswajit Guchhait

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Abstract

Supported liquid membrane (SLM) incorporating ionic liquids (ILs) or deep eutectic solvents (DESs) offers a promising method for ion and (bio)chemical separations and CO₂ capture. However, a molecular understanding of whether chemical reactions occur in these confined media is crucial. We report excited-state proton transfer (ESPT) reaction of a photoacid, HPTS, in various DES-based SLMs (pore size ∼280 nm) using steady-state and time-resolved fluorescence spectroscopy. Our findings reveal that, while the ESPT is unfavorable in bulk DESs, it occurs substantially in SLM-containing DESs. Time-resolved area normalized emission spectra (TRANES) show that ESPT time ranges from 2.6 to 7.5 ns and is greatly affected by changes in DES constituents. The results suggest that HPTS interacts with ordered DES structures formed by long-range interfacial effects in membrane pores, making it suitable for ESPT. Furthermore, it is found that the dynamics of solvent relaxation in confined DESs are significantly slower than in bulk liquids. This observation, together with a large red-edge excitation shift, supports the impact of long-range interfacial effects on the DES structure inside membrane pores. Given the task-specific properties of DESs, the incorporation of these solvents into SLM pores can be a useful strategy for investigating new chemical processes.

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探索非同寻常的封闭化学：深共晶溶剂支撑液膜中的受激态质子转移反应。

含有离子液体（ILs）或深共晶溶剂（DESs）的支撑液体膜（SLM）为离子和（生物）化学分离以及二氧化碳捕获提供了一种前景广阔的方法。然而，从分子角度了解这些密闭介质中是否会发生化学反应至关重要。我们利用稳态和时间分辨荧光光谱技术，报告了光酸 HPTS 在各种基于 DES 的 SLM（孔径 ∼280 nm）中的激发态质子转移（ESPT）反应。我们的研究结果表明，虽然ESPT在块状DES中是不利的，但在含有SLM的DES中却大量存在。时间分辨区域归一化发射光谱（TRANES）显示，ESPT 时间范围为 2.6 至 7.5 ns，受 DES 成分变化的影响很大。结果表明，HPTS 与膜孔中长程界面效应形成的有序 DES 结构相互作用，使其适用于 ESPT。此外，研究还发现，密闭 DES 中的溶剂松弛动力学明显慢于块状液体。这一观察结果以及较大的红边激发位移支持了长程界面效应对膜孔内 DES 结构的影响。鉴于 DESs 的特定任务特性，将这些溶剂纳入 SLM 孔隙是研究新化学过程的有用策略。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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来源期刊

The Journal of Physical Chemistry B 化学-物理化学

CiteScore

5.80

自引率

9.10%

发文量

965

审稿时长

1.6 months

期刊介绍： An essential criterion for acceptance of research articles in the journal is that they provide new physical insight. Please refer to the New Physical Insights virtual issue on what constitutes new physical insight. Manuscripts that are essentially reporting data or applications of data are, in general, not suitable for publication in JPC B.