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可逆光控质子化学。

Reversible photo control of proton chemistry.

机构信息

Florida Institute of Technology, 150 W University Blvd, Melbourne, Florida, USA.

出版信息

Phys Chem Chem Phys. 2022 Feb 16;24(7):4116-4124. doi: 10.1039/d1cp05627a.

Abstract

Spatial, temporal, and remote control of proton chemistry can be achieved by using photoacids, which are molecules that transform from weak to strong acids under light. Most of proton chemistry is driven by a high concentration of protons ([H]), which is difficult to obtain using excited-state photoacids. Metastable-stable state photoacids (mPAHs) can reversibly generate a high [H] under visible light with a moderate intensity. It has been widely applied in different fields, fueling dissipative assemblies, driving molecular machines, controlling organic reactions, powering nanoreactors, curing diseases, manipulating DNA and proteins, developing smart materials, capturing carbon dioxide in air This article compares mPAH with excited-state photoacid as well as common acids HCl to explain its advantages. Recent studies on the thermal dynamics, kinetics, and photoreaction of mPAHs are reported. The advantages and disadvantages of the three types of mPAHs, merocyanine, indazole, and TCF mPAHs, are compared with regard to photo-induced [H], switching rate, and other properties. The mechanisms of controlling or driving functional systems, which involve acid-base reactions, acid catalyzed reactions, ionic bonding, coordination bonding, hydrogen bonding, ion exchange, cation-π interaction, solubility, swellability, permeability, and pH change in biosystems, are described. Applications of mPAHs in the chemical, material, energy, biotechnology and biomedical fields published in the past 5 years are reviewed. Prospects in the development and application of mPAHs are discussed.

摘要

光酸可以在空间、时间和远程控制质子化学,光酸是指在光的作用下从弱酸转变为强酸的分子。大多数质子化学是由高浓度质子([H])驱动的,而使用激发态光酸很难获得高浓度质子。亚稳态-稳定态光酸(mPAH)可以在中等强度的可见光下可逆地产生高[H]。它已广泛应用于不同领域,推动耗散组装体、驱动分子机器、控制有机反应、为纳米反应器提供动力、治疗疾病、操纵 DNA 和蛋白质、开发智能材料、捕获空气中的二氧化碳等。本文将 mPAH 与激发态光酸以及常见酸 HCl 进行比较,以解释其优势。报告了 mPAH 的热动力学、动力学和光反应的最新研究。比较了三种 mPAH(变色烯、吲唑和 TCF mPAH)在光诱导[H]、开关速率和其他性质方面的优缺点。描述了涉及酸碱反应、酸催化反应、离子键、配位键、氢键、离子交换、阳离子-π 相互作用、溶解度、溶胀性、渗透性和生物体系中 pH 变化的控制或驱动功能体系的机制。综述了过去 5 年在化学、材料、能源、生物技术和生物医学领域发表的 mPAH 的应用。讨论了 mPAH 的发展和应用前景。

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