DEVELOPMENT OF LAYERED CERAMICS WITH AN ABLITIY OF MOLECULAR AND IONIC RECOGNITION

本课题的主要目的是开发新型层状无机-有机纳米复合材料，利用无机-有机纳米复合材料中两种组分的协同作用，使其具有良好的分子和离子识别能力。1）为了开发一种新的合成具有共价键的层状无机-有机纳米复合材料的方法，设计了一种制备酰胺官能化四价金属膦酸盐的简单途径，并通过模型反应进行了证明，其中烷基铵离子交换形式的层状锆2）发现部分磷酸化的羧乙基膦酸酯对正烷基胺CnH 2n +1 NH 2（n=1-10）的插层优先发生在庚胺（n=7）上，这是由于客体分子的组装增强了碳数选择性。提出了分子组装识别的新概念，取代了通常用于识别单个分子或离子的分子识别。3）为了开发与环糊精共价键合的层状主体化合物，尝试了通过热酰胺化方法将胺化环糊精分子连接到无机层上。这项研究正在进行中。对该系统的另一项研究表明，α-磷酸锆嵌入双（二氨基）乙氨基取代的β-环糊精，产生双层插层化合物。与先前获得的那些相比，发现该化合物具有可用于包括芳香酸分子的多孔结构。

This project was intended to develop new layred inorganic-organic nanocomposite materials which have an excellent ability of molecular and ionic recognition based on the cooperative effect of both components.1) In order to develop a new method for the synthesis of layred inorganic-organic nanocomposite materials with covalent linkages, a simple route to amide-functionalized tetravalent metal phosphonates was designed and demonstrated by a model reaction in which the alkylammonium ion exchanged form of layred zirconium (carboxyethyl) phosphonate is converted into the amide derivative by thermal condensation.2) We found that the intercalation of n-alkylamines CnH2n+1NH2 (n=1-10) by a partially phosphated carboxyethylphosphonate occurs preferentially for heptylamine (n=7), due to the amplification of carbon number selctivity through the assembling of guest molecules. We thus proposed a new concept of molecular assembly recognition, in place of the molecular recognition usually applied to the recognition of a single molecule or ion.3) In order to develop a layred host compound combined with cyclodextrin by covalent bonding, an attempt was made to link aminated cyclodextrin molecules to inorganic layrs by the thermal-amidation method. This research is now in probress. Another study on this system showed that alpha-zirconium phosphate intercalates a bis (diamino) ethylamino-substituted beta-cyclodextrin to yield a bilayred intercalation compound. In contrast to those previously obtained, this compound was found to have a porous structure available for including aromatic acid molecules.