Molecular Recognition of Metal Complex Ions by Lyotropic Liquid Crystals

为了完成这个主要课题，我研究了两个小课题，一个是两亲性液晶溶液中某些钴（Ⅲ）配合物的选择性相互作用，另一个是金属（配合物）离子对某些液晶体系相稳定性的影响。在以前的研究中，多核NMR光谱已被使用，它被揭示，^<59>Co四极分裂和化学位移提供了有关钴（III）离子的结合的补充信息。研究了改变胶束表面电荷的影响，以及用另一种阳离子表面活性剂或用另一种阴离子表面活性剂取代一种阳离子表面活性剂的影响。对于CO（NH_3）_6、^&lt;3+&gt; Co（CN）_6、<3->Co（en）_3^&lt;3+&gt;和Co（NO_2）（NH_3）_5^&lt;2+&gt;，静电力对两亲分子的相互作用起主导作用，而疏水力对Co（acac）_3和Co（phen）_3^&lt;3+&gt;起主导作用。现在我要研究的是 ...更多信息 钴（III）络合物，其结构在很大程度上取决于电解质的组成，例如金属络合物。在后一项研究中，我用DSC观察了双碱金属磷酸盐从液晶相到各向同性相的转变过程（差示扫描量热计）以及NMR光谱;利用该资助项目获得的DSC结果给出了三种碱金属磷酸盐液晶的转变曲线。焓变的大小顺序为钠盐&gt;钾盐&gt;铯盐，这与相变温度的大小顺序一致。水分子的^2 H NMR表明，钠盐中的水分子的行为受碱金属离子的水合作用控制，而钾盐和铯盐中的水分子则受磷酸盐头基的水合作用控制。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