Analytical Chemical Studies on SoluteーSolvent Interactions and Phase Transfer Reactions

本文的研究成果如下：分析化学反应中的溶质-溶剂相互作用。通过研究(1)溶剂对离子光学氧化电位的影响，(2)溶剂对电化学发光的影响，(3)氢氧离子与电子受体在非水溶剂中的反应，(4)金属高氯酸盐的离子缔合，(5)离子与溶剂分子之间的络合物形成，溶质-溶剂相互作用和相转移反应(溶剂萃取)来评价溶质-溶剂相互作用。(1)应用溶剂变色参数对同多钼酸盐和杂多钼酸盐的溶剂萃取行为进行了系统的研究。(2)大环四胺镍(II)络合物的溶致变色性能够很好地解释溶质-溶剂相互作用。(3)在水和有机溶剂的混合溶剂中合成了钼磷钼硫酸盐配合物，并测定了它们的结构。(4)…从结构上解释了四硫代醚的银(I)络合物的萃取行为。(5)考虑液-液分配模型，估算了金属络合物在反相液相色谱中的容量因子。(6)利用Lewis碱与β-二酮螯合物在不同的溶剂中形成络合物，改进了手性识别。(7)提出了一些新的金属选择性溶剂萃取剂。应用液/液界面离子转移伏安法，阐明(1)离子传感器的原理及其对生化物种的适用性；(2)水/有机溶液界面离子转移与电子转移之间的相互作用。通过测量不同溶剂之间的液结电势，积累了有关溶质-溶剂和溶剂-溶剂相互作用的基础数据。基于溶质-溶剂相互作用的新的分析方法。(1)建立了从非水溶剂中萃取质子测定纸张中质子浓度的方法。(2)根据榄系离子在水介质中的络合能力，提出了其形态分析方法。较少

Results obtained in the present co-operative work are as follows.Solute-solvent interaction in analytical chemical reactions. Solute-solvent interaction was evaluated through the studies on (1) solvent effects on the optical oxidation potentials of an ion, (2) solvent effects on the electrochemiluminescence, (3) reaction of hydroxide ion with electron acceptors in nonaqueous solvents, (4) ion association of metal perchlorates, and (5) complex formation between ion and solvent molecule.Solute-slovent interaction and phase transfer reactions (solvent extraction). (1) Solvent extraction behavior of isopoly and heteropoly molybdates was systematized by applying solvatochromic parameters. (2) The solvatochromism was verified to be powerful for the explanation of solute-solvent interactions using macrocyclic tetramine nickel (II) complex. (3) Molybdophosphonate and molybdosulphate complexes were synthesized in a mixture of water and organic solvents, and their structures were determined. (4) … More Extraction behavior of silvior (I) complexes of tetrathio ethers was explained based on their structure. (5) The capacity factor of metal complexes in reversed phase liquid chromatography was evaluated taking into account the liquid-liquid partition modal. (6) Chirality recognition was improved employing the adduct formation of Lewis bases with beta-diketone chelates in various solvents (7) Some novel reagents were proposed for selective solvent extraction of metals.Electrochemical studies on solute-solvent interaction. Voltammetry for ion transfer at the liquid/liquid interface was applied to elucidate (1) principles of ion sensors and their applicabilities to biochemical species and (2) the interaction between the ion transfer and the electron transfer at an aqueous/organic solution interface. Basic data relative to solute-solvent and solvent-solvent interactions was accumulated through measurements of liquid junction potentials between different solvents.New analytical methods based on solut-solvent interaction. (1) A method for the determination of proton concentration in paper was developed extracting proton into nonaqueous solvent. (2) Method for speciation of actinide ions was proposed based on their complexing ability in aqueous media. Less