A Study of Excited -State-Proton-Transfer Reaction

激发态质子转移反应的研究

• 批准号: 09640610
• 负责人: NAGAOKA Shin-ichi
• 金额: $ 1.98万
• 依托单位: Ehime University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 1997
• 资助国家: 日本
• 起止时间: 1997 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-09640610/
• 关键词: Excited State; Proton Transfer; Salicylaldehyde; Vitamin E; Excited-State Dependence; Node; Intramolecular Hydrogen Bond; Antioxidant Reaction; 置換基効果

Proton transfer is a very simple chemical process readily accessible to both accurate measurement and quantitative theoretical analysis. We have constructed a simple theoretical model of the excited-state-proton-transfer, a model based on the nodal pattern of the wave function. In this project we have studied the application of our nodal-plane model to the following three problems.1. The substituent effect and the electronic-state dependence in the excited-state-intramolecular-proton-transfer (ESIPT) of o-hydroxybenzladehydes.2. The substituent-position effect in ESIPT of 2-(o-hydroxyaryl)benzazoles : Although both 2-(2-hydroxy- 3-aryl)benzazole and 2-(1-hydroxy- 2-aryl)benzazole consist of an aryl moiety, a benzazol-2-yl group, and an Oil group, their emission properties are very different.3. The substituent and solvent effects in ESIPT of aminoanthraquinones : The singlet-triplet energy-gap of the proton-transferred form is much less than that in the normal form.The experimental results obtained on the above three problems strongly support our nodal-plane model.Furthermore, we synthesized a bridged molecule of vitamin E and quinones, and studied the radical scavenging reaction of vitamin E.It is interesting that the microscopic electron behavior could manifest itself in the macroscopic vital-function.Although our nodal-plane model is a qualitative one, it allows us to recognize the important features of ESIPT immediately and provides useful information about the reaction mechanisms. Our nodal-plane model is applicable to photochemical reactions in various excited states of various molecules. Many chemists have cited it, and the usefulness of our explanation is recognized by many researchers.

质子转移是一个非常简单的化学过程，易于精确测量和定量理论分析。我们已经建立了一个简单的理论模型的激发态质子转移，模型的波函数的节图案的基础上。在这个项目中，我们研究了我们的平面模型在以下三个问题中的应用.邻羟基苯甲醛激发态分子内质子转移（ESIPT）中的取代基效应和电子态依赖性。2-（邻羟基芳基）苯并唑ESIPT的取代基位置效应：虽然2-（2-羟基-3-芳基）苯并唑和2-（1-羟基-2-芳基）苯并唑都由芳基、苯并唑基和油基组成，但它们的发光性质有很大的不同.氨基蒽醌ESIPT中的取代基和溶剂效应：质子转移形式的单重态-三重态能隙远小于标准形式的单重态-三重态能隙.对上述三个问题的实验结果都有力地支持了我们的双平面模型.此外，我们还合成了一个维生素E和醌的桥联分子，有趣的是，微观电子行为可以体现在宏观的生命函数中。虽然我们的电子-平面模型是定性的，它使我们能够立即认识到ESIPT的重要特征，并提供有关反应机理的有用信息。我们的平面模型适用于各种分子在各种激发态下的光化学反应。许多化学家都引用了它，我们的解释的有用性也得到了许多研究人员的认可。

项目成果

K. Mukai: "Stopped-Flow Kinetic Study of the Free-Radical-Scavenging Action of Catechin and Related Compounds in Homogeneous and Micellar Solutions" Phytochemicals and Phytopharmaceuticals. 印刷中

K. Mukai：“均质和胶束溶液中儿茶素和相关化合物的自由基清除作用的停流动力学研究”植物化学物质和植物药物正在出版。

S.Nagaoka: "Electronic-state dependence of intramolecular proton transfer of o-hydroxybenzaldehyde.2.Substituent effect" The Journal of Physical Chemistry. 101 (17). 3061-3065 (1997)

S.Nagaoka：“邻羟基苯甲醛分子内质子转移的电子态依赖性。2.取代基效应”物理化学杂志。

S.Nagaoka: "Intramolecular proton transfer in the triplet state of 1- (acylamino) anthraquinones" Journal of Photochemistry and Photobiology A : Chemistry. 105 (1). 29-33 (1997)

S.Nagaoka：“1-（酰氨基）蒽醌三重态的分子内质子转移”光化学和光生物学杂志 A：化学。

K.Mukai: "Kinetic Study of Free-Radical-Scavenging Action of Flavonoids in Homogeneous and Aqueous Triton X-100 Micellar Solutions" The Journal of Physical Chemistry A. 101. 3746-3753 (1997)

K.Mukai：“均质 Triton X-100 胶束水溶液中黄酮类化合物自由基清除作用的动力学研究”物理化学杂志 A. 101. 3746-3753 (1997)

T.Koga: "Anomalous triplet mechanism spin polarization induced by the addition of hydrochloric acid in the photochemical system of xanthone in alcohol." The Journal of Physical Chemistry. 101 (43). 8021-8025 (1997)

T.Koga：“在酒精中的氧杂蒽酮光化学系统中添加盐酸引起的异常三重态机制自旋极化。”