DEVELOPMENT OF HIGHLY EFFICIENT SEPARATION SYSTEM BY USING MOLECULAR AND ION RECOGNITION BY CALIXARENE COMPOUNDS

合成了对叔辛基杯[4]芳烃及其单体类似物，考察并比较了它们对各种金属离子的萃取行为，特别是对铅离子的萃取行为。前者用铁(III)选择性地萃取铅，后者用铁(III)试剂则相反。从萃取不同金属离子的各种实验结果可以看出，杯[4]芳烃羧酸盐的单位分子萃取了两个铅离子，萃取铅离子前后的核磁共振氢谱的化学位移证实了这一点。给出了与有机磷、杯芳烃类化合物和水配体配位的稀土配合物的分子力力场。配体-金属-配体(L-M-L)的弯曲相互作用用1，3-非键相互作用来模拟，伸缩模式采用简谐的M-L伸缩势。观察到的结构参数与计算的结构参数总体上有很好的一致性。…的计算更多的ns还表明，可以得到一个定量结构性质关系(QSPR)，它将稀土离子和La(III)之间的配位应变能差与它们的相对萃取率联系起来。因此，分子力学被发现是设计具有金属离子特定稀土(III)萃取性的有机磷和杯芳烃配体的有效工具。以D2EHPA为萃取剂，在氯仿、己烷和甲苯中对儿茶酚胺类化合物多巴胺、肾上腺素和去甲肾上腺素的萃取进行了基础研究。计算了萃取反应的化学计量关系和平衡常数。通过分子模拟和半经验分子轨道计算，讨论了各有机稀释剂的平衡常数之间的定量结构性质关系。以杯[4]芳烃为单体单元，通过三氧六环进行交联反应，合成了新型杯[4]芳烃羧酸酯树脂。对铅和铁离子有很高的选择性。该树脂对铅的最大吸附容量为2.44mol/kg，与商品螯合树脂的吸附容量基本相同。采用该树脂填充柱，实现了铅与锌的良好相互分离和浓缩。较少

p-tert-octylcalix[4] arene and its monomeric analogue were synthesized to examine and compare their extraction behaviors for various metal ions, especially for lead ion. Lead was selectively extracted over iron(III) with the the former while reverse was the case with the latter reagent. From various experimental result of the extraction of different metal ions, it was elucidated that two lead ions are extracted by unit molecule of calix[4]arene carboxylate, which was confirmed by chemical shifts of H-NMR spectra before and after the extraction of lead ion.A molecular mechanics force field for lanthanoid complexes coordinated to organophosphates and calixarene compounds together with aqua ligands was presented. The ligand-metal-ligand (L-M-L) bending interaction are modeled with 1,3-nonbonded interaction and a harmonic M-L stretching potential was used for the stretching modes. There was good overall agreement between the observed and the calculated structural parameters. The calculatio … More ns also indicated that a quantitative structure property relationship (QSPR) may be obtained, which relates the complexation strain energy difference between the lanthanoid cations and La (III) with their relative extractability. Thus, molecular mechanics was found to be an efficient tool for the molecular design of organophosphorus and calixarene ligands with metal ion specific lanthanoid(III) extractability properties.A basic investigation on solvent extraction of catecholamines such as dopamine, adrenaline and noradrenaline from dilute hydrochloric acid was conducted using D2EHPA in chloriform, hexane and toluene. The stoichiometric relationship and equilibrium constants of the extraction reactions were evaluated. The quantitative structure property relationship of the equilibrium constant for each organic diluent was discussed using molecular modeling with semi-emperical molecular orbital calculations taking account of the diluent effect.New resin of calix[4]arenecarboxylate was synthesized from its monomeric units with no alkyl radicals by crosslinking using trioxane. High selectivity to lead and ferric ions were observed. The maximum adsorption capacity for lead was 2.44 mol/kg, which is nearly the same values of commercial chelating resins. Excellent mutual separation and concentration of lead away from zinc was achieved by using a column packed with this resin. Less