Development of analytical methods based on specificity of interfaces and their structural and kinetic stulies

在分析反应领域，研究了硅酸盐材料、金和半导体纳米粒子的固-液界面、液-液界面、介孔通道等，通过氢键人工受体获得对分子和离子的高选择性和/或特异性识别。具有分子或离子识别位置的硫代化合物修饰的金纳米粒子。通过在水中添加目标分子或离子，经过化学修饰的金粒子显示出从红色到蓝色的戏剧性变化。利用硫代羧基化合物对纳米半导体粒子进行修饰，并基于光诱导电子转移机理成功地制备了铅离子传感材料。利用液-液界面作识别场，成功地实现了对极亲水阴离子的高选择性传感。在1，2-二氯乙烷-水界面…上研究了硫脲类双官能团受体与碱金属离子和阴离子的离子对络合行为通过动态界面张力计获得更多的表面积。在有机相中加入碱金属盐后，由于有机相中受体的界面吸附作用，使界面张力降低。受体的吸附常数依赖于碱金属盐。结果表明，受体与阴离子之间的氢键形成实际上是在液-液界面上有效的，尽管阴离子水合作用有很大的干扰。液-液界面上受体的一个更重要的性质是与氯化物相比，磷酸二氢的优先结合。这种选择性仅在基于离子载体的化学传感器中观察到，例如离子选择电极，其中选择性主要由分析物阴离子水合自由能的顺序控制。用液滴极谱研究了阴离子从水相到水相的转移，形成氢键的双硫脲能够有效地促进各种亲水性阴离子通过硝基苯-水界面的转移，这表明该受体可能用于安培传感模式的多分析物检测。此外，还研究了离子载体促进的氯离子在硝基苯-水界面上的转移，观察到一个清晰的波，表明离子载体通过形成氢键促进了氯离子在界面上的转移。离子转移极谱分析表明，氯离子转移是以1：1的络合方式进行的，转移过程是可逆的，受控于离子载体从有机相向界面的扩散。尽管基于两点相互作用的简单结合模式，但与四个氢键参与氯离子结合的离子载体相比，单硫脲表现出更强的促进氯离子转移的能力。还用激光光谱仪进行了动力学研究。较少

As to analytical reaction fields, solid-liquid interface, liquid-liquid interface, meso-porous channels of silcate material, gold and semiconductor nano particles are investigated to obtain highly selective and/or specific recognition of molecules and ions using hydrogen bonding artificail receptors. Gold nano-particles modified with thiolated compounds which have molecule or ion recognition sites. The chemically modified gold particles show dramatic color change from red to blue by addition of target molecules or ions in water. Nano-sized semiconductor particles were also modified by thiolated carboxylic compounds, and sensing lead ions was succesfully attained based on photo-induced electron transfer mechanism. Highly selective sensing of very hydrophilic anions was succeeded using liquid-liquid interfaces as recognition fields. Ion-pair complexation behaviors of a thiourea-based bifunctional receptor with alkali metal ions and anions are examined at the 1,2-dichloroethane-water inte … More rface by dynamic interfacial tensiometry. A decrease in the interfacial tension, caused by the interfacial adsorption of the receptor in the organic phase, is promoted when alkali metal salts are added in the aqueous phase. The adsorption constants of the receptor depend on alkali metal salts. The results indicate that hydrogen bonding formation between the receptor and anions is actually effective at the liquid-liquid interface despite the significant interference from anion hydration. A more important property of the receptor at the liquid-liquid interface is the preferential binding of dihydrogen phosephate over chloride. This kind of selectivity has merely observed in ionophore-based chemical sensors such as ion-selective electrodes, where the selectivity is governed predominantly by the order of the free energy of hydration of the analyte anions. Anion transfer from aqueous phase to water phase was also investigated by liquid droplet polarography, A hydrogen bond-forming bis-thiourea was able to effectively facilitate the transfer of various hydrophilic anions across the nitrobenzene-water interface, suggesting possible use of the receptor for multianalyte detection with an amperometric sensing mode. In addition, chloride transfer across the nitrobenzene-water interface facilitated by the ionophore was studied, and a well-defined wave could be observed, indicating that the chloride transfer across the interface was facilitated by the ionophore via formation of hydrogen bonds. The analysis of ion transfer polarograms showed that the chloride transfer was assisted by 1 : 1 complexation between 2 and chloride, and the transfer process was reversible and controlled by diffusion of the ionophore from the bulk organic phase to the interface. Despite its simple binding mode based on two point interactions, mono-thiourea showed a strong ability to facilitate chloride transfer compared with a ionophore in which four hydrogen bonds were involved in the chloride binding. Dyanamical studies were also carried out by laser spectroscopies. Less