On the Mechanisms of Ionic Reactions at the Highly Charged Interface

任何带电大分子（线性、交联线性聚合物和离子胶束等）的离子反应，无论是带正电还是带负电，都可以通过假设多离子/支撑电解质体系的两相性质来分析。在本研究项目中，研究了多离子体系中离子反应平衡的新分析方法。统一分析了弱酸性聚电解质（聚丙烯酸和聚甲基丙烯酸）和弱酸性聚电解质（聚n -乙烯基咪唑和聚烯丙胺）的共轭酸的酸解离和金属络合性质。基于donnan的概念解释了平衡对添加盐浓度水平的高敏感性。利用聚酸酸解离平衡的非理想项，正确地评价了静电对带电聚合物体系金属络合平衡的影响，从而可以提取在聚合物表面形成的金属配合物的本征形成常数。多离子体系中的“相分离”概念也被应用于“多电解质分析”的定量。研究了强酸性聚乙烯磺酸盐离子对Fe^<2+>/ [Co (NH_3) _5Cl] ^<2+>电子转移反应的加速作用。解释反应加速所需的多电解质相体积与利用反离子结合平衡数据计算的值一致。在小的阴离子带正电的聚合物体系中，反离子与带电荷的聚合物位点之间存在明显的疏水相互作用。研究了Co^<2+>/SCN^-在聚乙烯苄基三甲基铵离子存在下的络合行为。研究表明，疏水相互作用在很大程度上受支撑阴离子的疏水性影响。

Any ionic reactions of charged macromolecules (linear-, cross-linked linear polymers, and ionic micelles, etc.) , whether they are positively or negatively charged, can be analyzed by assuming a two-phase property of polyion/supporting electrolyte systems. In this reserch project, novel analytical treatments of the equilibria of ionic reactions in polyion systems have been examined. Acid-dissociation and metal complexation properties of weakly acidic polyelectrolytes (polyacrylic acid and polymethacrylic acid) and the conjugate acids of weakly besic polyelectrolytes (poly (N-vinylimidazole) and polyallylamine) , have been analyzed in a unified manner. High sensitivity of the equilibria to the added salt concentration levels was interpreted by a Donnan-based concept. By the use of the non-ideality terms of the acid-dissociation equilibria of the polyacids, the electrostatic effect on the metal complexation equilibria of the charged polymer systems has been evaluated correctly, which made possible to extract the intrinsic formation constants of the metal complexes formed at the polymer surface. This "phase-separation" concept in polyion systems has also been applied to the quantification of "polyelectrolyte eatalysis" . Acceleration of Fe^<2+>/ [Co (NH_3) _5Cl] ^<2+> electron transfer reaction with the addition of strongly acidic polyions, polyvinylsulfonate ions, has been examined. Polyelectrolyte phase volume needed to interpret the reaction acceleration was consistent with the value calculated by the use of counterion binding equilibrium data. Pronounced hydrophobic interaction between counterions and charged polymer sites has been revealed for small anion-positively charged polymer systems. Complexation behavior of Co^<2+>/SCN^- in the presence of polyvinylbenzyltrimethylammonium ions has been investigated. It has been indicated that the hydrophobic interaction is greatly affected by the hydrophobic nature of supporting anions.