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 (NH 2 CH(COOH)CH 2 COOH, aspH 2 ) 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 metalorganic open-framework materials. [3][4][5][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.We have sought to generate porosity by connecting metalaspartate units with suitable bidentate linker molecules. This objective requires a synthetic route that avoids the presence
Post-synthetic derivatisation of a porous material produces a functionalized material that binds the metal complex V(O)acac2, in contrast to the unfunctionalized precursor, which is inactive for complex binding.
Protonation of chiral porous materials introduces a Brønsted acid centre, the structure of which is unique to the heterogeneous phase requiring pore wall confinement for stable isolation.
Physical delivery of anticancer drugs in controlled anatomic locations can complement the advances being made in chemo‐selective therapies. To this end, an optical fiber catheter is coated in a thin layer of metal organic framework UiO‐66 and the anticancer drug 5‐Fluorouracil (5‐FU) is deposited within the pores. Delivery of light of appropriate wavelength through the fiber catheter is found to trigger the release of 5‐FU on demand, offering a new route to localized drug administration. The system exhibits great potential with as much as 110 × 10−6 m of 5‐FU delivered within 1 min from one fiber.
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 (NH 2 CH(COOH)CH 2 COOH, aspH 2 ) 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 metalorganic open-framework materials. [3][4][5][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.We have sought to generate porosity by connecting metalaspartate units with suitable bidentate linker molecules. This objective requires a synthetic route that avoids the presence
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