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

1)为了开发一种新的具有共价键的层状无机-有机纳米复合材料的合成方法，设计了一种简单的酰胺功能化四价金属膦酸盐的合成路线，并通过模型反应进行了验证。在该反应中，烷基铵离子交换形式的层状(羧乙基)膦酸锆通过热缩合反应转化为酰胺类衍生物。2)我们发现部分膦酸化的羧基乙基膦酸铵对N-烷基胺CnH_2n+1NH_2(n=1-10)的插层反应优先发生在七胺(n=7)上。这是由于客体分子的组装放大了碳数的选择性。因此，我们提出了分子组装识别的新概念，取代了通常应用于单个分子或离子识别的分子识别。3)为了开发与环糊精通过共价键结合的层状主体化合物，尝试通过热酰胺化方法将胺化的环糊精分子连接到无机层上。这项研究目前正在进行中。对该体系的另一项研究表明，α-磷酸锆插层双(二氨基)乙氨基-β-环糊精形成双层插层化合物。与以前获得的化合物相比，该化合物被发现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.