Study on Liquid-Liquid Interfacial Dynamics of Molecular Recognition System by Total Reflection Laser-Induced Thermal Lens.

全反射激光热透镜分子识别系统液-液界面动力学研究。

• 批准号: 12640594
• 负责人: KAWAZUMI Hirofumi
• 金额: $ 1.98万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2001
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12640594/
• 关键词: Total Reflection; Thermal Lens; Ion-Association Reaction; Solvent Extraction; Bathophenanthroline; Complex Formation Rate; Calix[4]arene; ファナントロリン; 反応速度; イオン抽出; 分子認識; 液液界面

The microscopic information about liquid-liquid interface is very important in analytical chemistry and separation science. A new interfacial thermal lens (TL) technique has been developed for the study on dynamics of solvent extraction.In this report, this technique applied to an ion-association reaction, the formation of Fe(II) - 4,7-diphenyl-1, 10-phenanthroline (DPP) complex at a benzene - acetate buffer interface. The thin TL effect of the complex adsorbed on the interface could directly present the complex formation by using a combination of total reflection excitation and pump (NdYAG pulse laser) - probe (red diode laser) alignment. At first, an amphiphilic molecule, 10-(1-pyrene) decanoic acid, expanded at a hexane - phosphate buffer solution interface was used to evaluate the specification of this technique. A response is linear to amounts of the expanded molecule and a minimum detectable amount is 1.0 x 10^<-10> mol corresponding about 1/100-monolayer. A time resolution is 0.1 second, which can monitor an initial stage of the complex formation. After the preparation of the interface TL signal increased gradually corresponding to the aging of the interface formation and the complex formation. The interfacial complex formation rate was proportional to the first order of Fe(II) concentration but did not vary with the DPP concentration. Two-step mechanism is proposed ; (1) the interface aging with an adsorption of DPP to the interface up to a constant amount, (2) the interfacial complex formation with Fe(II) from aqueous phase.For further researches, Calix[4]arenas with molecular recognition ability were synthesized and those spectroscopic properties were measured. Analysis of the thermal lens signal is in progress.

液-液界面的微观信息在分析化学和分离科学中具有重要意义。采用界面热透镜（TL）技术研究了Fe（Ⅱ）-4，7-二苯基-1，10-菲咯啉（DPP）在苯-乙酸缓冲溶液界面上的离子缔合反应。采用全反射激发和泵浦（Nd：YAG脉冲激光）-探针（红光二极管激光）对准相结合的方法，可以直接呈现吸附在界面上的络合物的薄热释光效应。首先，使用在己烷-磷酸盐缓冲溶液界面处扩展的两亲性分子10-（1-芘）癸酸来评价该技术的规格。响应与扩展分子的量呈线性关系，最小可检测量为1.0 × 10 - 6 μ <-10>mol，对应于约1/100-单层。时间分辨率为0.1秒，可以监测复杂地层的初始阶段。界面制备完成后，热释光信号逐渐增强，这与界面的老化形成和复合物的形成相对应。界面络合物的形成速率与Fe（II）浓度的一阶成正比，但不随DPP浓度而变化。本文提出了两步机理：（1）DPP在界面上的吸附达到一定量后界面老化;（2）水相中与Fe（II）形成界面络合物。热透镜信号的分析正在进行中。

项目成果

M.Sato: "Acid-Base Equilibrium Constant at the Water Surface and Distribution Coefficients between the Surface and Bulk as Studied by the Laser Two-Photon Ionization Techniques"The Journal of Physical Chemistry B. 104(42). 9873-9877 (2000)

M.Sato：“通过激光双光子电离技术研究的水面酸碱平衡常数以及表面与本体之间的分布系数”物理化学杂志 B. 104(42)。

K. Yoshida, H. Kawazumi, M. Sato, A. Harata, Y. Hatano: "Microscopic chemical imaging for species-selective determination of rhodamine dyes adsorbed on microparticles"Analytical Science. 17(supplement). a313-a316 (2002)

K. Yoshida、H. Kawazumi、M. Sato、A. Harata、Y. Hatano：“用于微粒上吸附的罗丹明染料的物种选择性测定的显微化学成像”分析科学。

H.Kawazumi: "Observation of Fluidic Behavior in a Polymethylmethacrylate-Fabricated Microchannel by a Simple Spectroscopic Analysis"LAB ON A CHIP. 2. 8-10 (2002)

H.Kawazumi：“通过简单的光谱分析观察聚甲基丙烯酸甲酯制造的微通道中的流体行为”芯片实验室。

M. Sato, T. Kaieda, K. Ohmukai, H. Kawazumi, A. Harata: "Acid-base equilibrium constanats at the water surface and distribution coefficients between the surface and the bulk as studied by the laser two-photon ionization technique"J. Chem. Phys.. 104(42).

M. Sato、T. Kaieda、K. Ohmukai、H. Kawazumi、A. Harata：“通过激光双光子电离技术研究了水面的酸碱平衡常数以及表面与本体之间的分配系数”

河済 博文: "近赤外半導体レーザを光源とする光熱変換水分分析"分析化学. 50(12). 911-914 (2001)

Hirofumi Kawase：“使用近红外半导体激光器作为光源的光热转换水分分析”分析化学 50(12) (2001)。