A family of nanoporous materials based on an amino acid backbone

A family of nanoporous materials based on an amino acid backbone
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DOI:
10.1002/anie.200602242
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发表时间:
2006-01-01
影响因子:
16.6
通讯作者:
Rosseinsky, Matthew J.
Rosseinsky, Matthew J.
中科院分区:
化学1区
文献类型:
--
作者:
Vaidhyanathan, Ramanathan;Bradshaw, Darren;Rosseinsky, Matthew J.

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由于生物分子能够为底物分子产生合适的受体位点,因此生物分子与底物的相互作用具有极高的精确度和(立体)化学选择性。这些位点在它们的键合能力方面具有足够的多样性,以允许分子几何形状之间的细微差异。因此,在制备具有该功能的合成材料方面存在相当大的兴趣。[1]一种方法是在组装此类材料时使用生物衍生成分。氨基酸残基是许多扩展生物结构的功能特性和高选择性底物结合能力的来源,因此是用于制备生物类似物材料的手性构建块的有吸引力的选择。在此,我们报告了一类合成结晶纳米多孔材料,其中内表面由氨基酸天冬氨酸提供。天冬氨酸(NH 2CH(COOH)CH 2COOH,aspH 2)是一种具有一个胺基和两个羧酸基的酸性氨基酸,它的分子量分布与客体分子中官能团的空间分布密切相关。由于这些官能团中的每一个都能够与金属中心结合,因此天冬氨酸阴离子具有多种配位模式。[2]这种多功能性使其成为构建多孔金属-有机开放骨架材料的合适有机节点。[3-6]最近有报道基于金属螯合物的扩展框架;[2]然而,这些框架中的结构基序太密集而不能产生客人可访问的体积。乳酸根[7]和酒石酸根[8]阴离子也被用于金属有机框架的构建。
Biological molecules interact with substrates with exquisite precision and (stereo) chemical selectivity, because of their ability to generate suitable receptor sites for substrate molecules. These sites have sufficient diversity in their bonding capabilities to allow subtle differentiation between molecular geometries. There is, thus, considerable interest in the preparation of synthetic materials with aspects of this function.[1] One approach is to use biologically derived components in the assembly of such materials. Amino acid residues are the origin for the functional properties and highly selective substrate-binding ability of many extended biological structures, and so are an attractive option as chiral building blocks for the preparation of bio-analogous materials. Herein, we report a family of synthetic crystalline nanoporous materials in which the internal surface is provided by the amino acid aspartic acid. These materials display enantioselective sorption that is strongly dependent on the spatial distribution of functional groups within the guest molecule.Aspartic acid (NH2CH (COOH) CH2COOH, aspH2) is an acidic amino acid with one amine and two carboxylic acid groups. As each of these functional groups is capable of binding to metal centers, the aspartate anion has a variety of coordination modes.[2] This polyfunctionality makes it a suitable organic node for the construction of porous metal–organic open-framework materials.[3–6] Extended frameworks based on metal aspartates have recently been reported;[2] however, the structural motifs in these frameworks are too dense to generate guest-accessible volume. The lactate [7] and tartrate [8] anions have also been used in the construction of metal–organic frameworks.