Molecular Recognition of Metal Complex Ions by Lyotropic Liquid Crystals

为了完成这一主题，我研究了两个小课题：一个是关于某些钴(III)络合物在两亲性向列相液晶溶液中的选择性相互作用；另一个是金属(络合)离子对某些液晶体系相稳定性的影响。在以前的研究中，使用了多核核磁共振谱，发现^&lt；59&gt；Co的四极分裂和化学位移给出了关于钴(III)离子结合的补充信息。研究了改变表面电荷对胶束的影响，以及用一种阳离子表面活性剂取代另一种阳离子表面活性剂或用一种阴离子表面活性剂取代另一种阴离子表面活性剂的效果。对于CO(NH_3)_6，Co(CN)_6^&gt；3-&gt；Co(En)_3^&lt；3+&gt；和Co(NO_2)(NH_3)_5^&lt；2+&gt；现在我要研究…的具体相互作用胆甾型液晶体系中钴(III)络合物较多，其结构可能在很大程度上取决于电解质的组成，如金属络合物。在后一项研究中，我用差示扫描量热仪(DSC)和核磁共振光谱观察了二丁基碱性磷酸盐类液晶从液晶相到各向同性相的转变过程；借助这一助剂得到的DSC给出了二丁基碱性磷酸盐类液晶的转变热。热变的大小顺序为钠盐、钾盐和铯盐，与转变温度的顺序一致。水分子的~2H核磁共振谱表明，水分子的行为是由钠盐对碱性离子的水合作用决定的，而对钾和铯盐的水合作用则由磷酸根的水合作用决定。较少

In order to accomplish the main subject I have approached two small subjects ; the one is concerning selective interactions of some cobalt(III)complexes in amphiphilic nematic liquid crystalline solutions and the other is the effects of metal(complex)ions on the phase stability of some liquid crystalline systems. In the former study multinuclear NMR spectroscopy has been used and it was revealed that the ^<59>Co quadrupole splittings and chemical shifts gave complementary information concerning the binding of the cobalt(III)ions. The effects of changing surface charge on the micelles were investigated, as were the effects of replacing either one cationic surigctant with another or one anionic surfactant with another. For CO(NH_3)_6, ^<3+> Co(CN)_6^<3-> Co(en)_3^<3+>, and Co(NO_2)(NH_3)_5^<2+> the electrostatic force was pdominant to interact with amphiphiles, while hydrophobic interaction was important for Co(acac)_3 and Co(phen)_3^<3+>. Now I'm going to study specific interactions of … More cobalt(III)complexes in cholesteric liquid crystalline system whose structure may largely depend on compositions of electrolytes such as metal complexes. We can thus expect to relate the structure of the cholesteric liquid crystals with specific interactions between the metal complexes and the head groups.In the latter study, I have observed the process of transition from a liquid crystal phase to an isotropic one for dibutyl alkali phosphates by use of a DSC(differential scanning calorimeter)as well as NMR spectroscopy ; the DSC which has been got with the aid of this Grant-in-Aid gave the transition enthalpies for liquid crystals of the dibutyl alkali phosphates. The enthalpy change was in the order sodium salt>potassium salt> cesium salt which was consistent with the order of the transition temperatures. The ^2H NMR of water molecules showed that the behavior of water molecules is governed by hydration to the alkali ions for sodium salt, while to the phsophate head group for the potassium and cesium salts. Less