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

• 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 /

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-液界面反应的测量方法，共振二次谐波光谱（RSH）和时间分辨全内反射荧光光谱（TIRF）被发展并应用于表征分子在液-液界面的吸附。此外，本文还建立了用于液-液界面络合动力学分析的电位扫描极谱法，并研究了罗丹明B（Rh-B）在液-液界面上的吸附行为。Rh-B分子被发现是稳定在庚烷-水界面相比，散装溶液。基于RSH光谱的浓度依赖性，发现当体相浓度较高时，界面处的分子可以作为单体和二聚体的混合物存在。估算了Rh-B的分子取向，浓度较低时，取向角几乎恒定为65度，随着浓度的增加，取向角逐渐减小 ...更多信息 采用时间分辨TIRF技术研究了8-苯胺基-1-萘磺酸盐分子在庚烷-水界面上的微环境.通过分析荧光衰减曲线，发现在界面附近的荧光团存在于两种不同的溶剂化结构中。其中之一是位于几个纳米的界面，另一个是位于一个相对较宽的范围twoard的水相。前者的溶剂化结构是一个长的荧光寿命，反映了低极性或极高的粘度的微environments.As在液-液界面的化学反应，络合动力学研究使用8-羟基喹啉衍生物和二价金属离子通过测量动态界面张力和跨界面的离子转移。结果表明，5-辛氧甲基-8-羟基喹啉具有界面吸附性，吸附性与反阴离子和有机相有关。这些依赖性解释了离子对形成常数和螯合剂的分配系数。通过对界面离子迁移量的测定，认为络合反应发生在离有机相较近的界面上，并建立了几种分析液-液界面反应的方法，发现界面反应不同于蓝溶液中的反应。少

项目成果

K.Bessyo: "Microenvironments of 8-aAilino-1-Naphthalenesulfonate at the Heptane-Water Interface :" Chemistry Physics Letters. Vol.264. 381-386 (1997)

K.Bessyo：“庚烷-水界面上 8-αAilino-1-萘磺酸盐的微环境：”化学物理快报。

K.Bessho: "Collection of Meral(II)-1-(2-Pyridylazo)-2-naphthol Coruplexes in Nonionic Surfactant Assembly Adsonbed on Silica Gel" Chemistry Letters. 577-578 (1995)

K.Bessho：“Meral(II)-1-(2-吡啶偶氮)-2-萘酚复合体在硅胶上非离子表面活性剂组装 Adsonbed 中的集合”化学快报。

T.Shioya: "Complexation Kinetics of 5-Octyloxymethyl-8-Quinolinol with Ni (II) at the Heptane-Water Interface" Chemistry Letters. No.6. 469-470 (1996)

T.Shioya：“5-辛氧基甲基-8-喹啉醇与 Ni (II) 在庚烷-水界面的络合动力学”化学快报。

Koichi Saitoh: "Separation of chlorophyll-C_1 and C_2 by micellar electrokinetic capillary chromatography" Journal of chromatography A. 687. 149-153 (1994)

Koichi Saitoh：“通过胶束电动毛细管色谱法分离叶绿素-C_1 和 C_2”《色谱杂志》A. 687. 149-153 (1994)

A.Yamaguchi: "Resonant Second Harmonic Spectroscopy of Rhodamine B adsorbed onto Fused Silica" Analytical Sciences. (submitted).

A.Yamaguchi：“吸附在熔融石英上的罗丹明 B 的共振二次谐波光谱”分析科学。