Design,Assembly And Application Of Peptide Chiral Metal-organic Porous Materials

Metal-Organic porous material is a kind of crystalline porous solid material which can be assembled by metal ions/clusters and organic bridging ligands through metal coordination bond.Among them,Metal-Organic Frameworks and supramolecular coordination cages are typical.At present,the Metal-Organic porous material is a latest darling in the field of porous materials.Because of its diverse composition and structure,and characterized by regular pores and super-high specific surface area,it has been widely used in gas storage,separation,catalysis,drug delivery,super capacitance and other fields.The organic ligands（linker design）used in the strategic design have been proved to have an important influence on adjusting the structure of metal organic porous materials and realizing the expected functions,and also the most important part of the whole material design process.The design of ligands can directly affect the topology,pore structure and other properties.In the past decade,Metal-Organic porous material is a promising molecular separation material,and the main research focuses on gas storage,separation and other processes.Although the development of metal organic porous materials is very rapid,the design and separation performance development of Metal-Organic porous materials based on single chiral peptide are always unsatisfactory.In this paper,we intend to use the natural chiral amino acids as a single chiral source,through a simple organic synthesis reaction,to complete the synthesis of organic bridging ligands with different pore sizes and coordination modes,and to assemble peptide Metal-Organic porous materials with chiral separation performance by solvothermal method.And through PXRD,TGA and other means to complete the research and exploration of material structure and performance.Firstly,using L-phenylalanine as a single chiral source,a bridge ligand（H₂L）with C₂symmetry was designed and synthesized,and a Zn MOF（material 1）with two-dimensional structure was obtained by solvothermal method with Zn²⁺,using material 1 as chiral solid adsorbent/separator,explored its performance of selective adsorption/separation of two enantiomers of small molecular medicine intermediates（aromatic alcohol,epoxy compounds,etc.）and small molecular medicine（ibuprofen）.Material 1 has a prominent advantage in the process of chiral separation,and can also be used as a potential filling material for chiral column.Secondly,using L-phenylalanine as the starting material,a peptide organic ligand（H₃L）with C₃symmetry was synthesized through four simple chemical reactions,and a Cd-MOF（material 2）with three-dimensional structure was assembled with Cd²⁺.Material 2 was used as the chiral solid adsorption/separation material to explore the selective adsorption of two enantiomers of small molecular aromatic alcohols.The separation performance highlights the strong size selectivity of material 2.Furthermore,the C₃symmetric organic ligand H₃L synthesized by the above design was assembled with metal ion La³⁺,and a single chiral peptide supramolecular coordination cage（material 3）with excellent separation performance was obtained.Moreover,the material showed very high substrate tolerance and scale for a variety of drug molecules（lansoprazole,saridomide,ketoprofen,flurofen,and tebamine）Inch selectivity is a potential excellent chiral solid separation material.Finally,using L-phenylalanine and L-tryptophan as chiral sources,two kinds of chiral ligands p-H₃L and t-H₃L with similar structure and size are obtained by condensation reaction.Two kinds of peptide bonded chiral supramolecular coordination cages（materials 4 and 5）with similar structure and size are obtained by self-assembly with Cu²⁺.Through the study of the structure of hydrophobicity of the two materials,the structure of the two materials is based on the peptide chiral supramolecular.The design of the micro environment of the chiral cavity of the molecular coordination cage provides a new idea.