Measurements of Non-Equilibrium State for Reactions at Liquid-Liquid Interfaces and the Analysis of Selective Distribution Behaviors

液-液界面反应非平衡态测量及选择性分布行为分析

基本信息

批准号：
06403015
负责人：
TERAMAE Norio
金额：
$ 24.06万
依托单位：
TOHOKU UNIVERSITY
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (A)
财政年份：
1994
资助国家：
日本
起止时间：
1994 至 1996
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-06403015/
关键词：
Liquid-Liquid Interface Ditribution Reaction at the Interface Non-Linear Laser Spectroscopy Second Harmonic Generation Total Internal Reflection Fluorescence Ion Transfer at the Liquid-Liquid Interface 非線形レーザ分光第二高調波マイクロエマルション非平衡状態 /

项目摘要

As measurement methods for reactions at liquid-liquid interfaces, the resonat second harmonic (RSH) spectroscopy and the time resolved total internal reflection fluorescence spectroscopy (TIRF) were developped and applied to characterize molecules absorbed at liquid-liquid interfaces. In addition, the potential-scan polarography with an electrolyte dropping electrode was developped for the analysis of the complexation kinetics at liquid-liquid interfaces.As for RSH spectroscopy, rhodamine B (Rh-B) is studied as a moleule adsorbed at liquid-liquid interfaces. Rh-B molecules were found to be stabilized at the heptane-water interface compared bulk solutions. Based on the concentration dependence of RSH spectra, it was found that molecules at the interface can exist as a mixture of monomer and dimer when the bulk concentration is high. Molecular orientations of Rh-B were estimated and the orientation angle was almost constant as 65 degree when the concentration is low, and the angle decrea … More sed at higher concentrations.A time resolved TIRF was applied to study the microenvironments of 8-anilino-1-naphthalenesulfonate molecules at the heptane-water interface. By analysing the fluorescence decay profiles, it was found that the fluorophores in the vicinity of the interface are present in two different solvated structures. One of them is located up to a few nanometers from the interface, and the other is located in a relatively wide range twoard the aqueous phase. The former solvated structure is the cause of a long fluorescence lifetime which reflects the low polarity or the extremely high viscosity of the microenvironments.As for chemical reactions at liquid-liquid interfaces, complexation kinetics were examined using 8-quinolinol derivatives and divalent metal ions by measuring dynamic interfacial tension and ion transfer across the interface. As a result, it was found that 5-octyloxymethyl-8-quinolinol showed interface absorptivity and the adorptivity depended on both the counter anion and the organic phase. These dependence was explained by the ion pair formation constant and the distribution coefficient of a chelating reagent. From the measurement of an ion tranfer across the interface, it was suggested that the complexations occured at the interface nearer to the organic phase.As mentioned above, several methods were establishied to analyze reactions at liquid-liquid interfaces, and the reactions at the interface were found to be different from those in bluk solutions. Less

作为液态液体界面反应的测量方法，共鸣二次谐波（RSH）光谱和分解的时间内部反射荧光光谱（TIRF）的时间被开发并应用以表征吸收在液体液体界面上的分子。此外，开发了带有电解质掉落电极的潜在扫描激进学以分析液态液体界面处的络合动力学。作为RSH光谱法，Rhodamine B（Rh-B）是在液体 - 液体界面上的分子吸附的。发现RH-B分子在七烷 - 水界面上进行了稳定。基于RSH光谱的浓度依赖性，发现界面的分子可以作为单体和二聚体的混合物存在，当时大量浓度很高。估计RH-B的分子取向，并且当浓度低时，方向角度几乎恒定为65度，并且角度下降……在较高浓度下更高的SED。将时间分解的TIRF应用于在赫生 - 含Heptean-Water-Water-Water-Water-Water Facterface上研究8- anilino-1-苯甲酸 - 苯甲酸甲酸盐分子的微环境。通过分析，荧光衰减曲线，发现界面附近的荧光团以两个不同的溶液结构表示。其中一个位于界面的最多几纳米，另一个位于相对宽范围的两个水相中。以前的解决结构是导致荧光寿命长的原因，它反映了微环境的极性低或极高的粘度。AS在液体液体界面处的化学反应，使用8-喹啉衍生物和分离金属离子通过测量动态界面界面的动力学界面张力和离子转移来检查络合动力学。结果，发现5-氯辛酰甲基-8-喹诺醇显示出界面吸收，并且具有反应性取决于反阴离子和有机相。这些依赖性通过离子对形成常数和螯合剂的分布系数来解释。从在跨界面的离子转移的测量中，提出络合物发生在距离有机相近的界面处。如上所述，建立了几种方法来分析液体液体界面处的反应，并且在界面上的反应与Bluk Solute中的反应不同。较少的