Research On Metal Organic Framework Materials Based On Camphor Acid

The separation and preparation of optically pure chiral drugs has also become a hot and difficult point of research.Metal-organic framework materials?MOF?materials are widely used in various fields such as adsorption separation,optics,and drug delivery as a porous material with excellent properties.Chiral metal-organic framework?CMOF?materials have been studied because of their special chiral environment and their potential huge application value in chiral resolution.At present,most applications of chiral MOFin chiral resolution are to use CMOFas the stationary phase of a liquid chromatography column to detect the resolution of chiral molecules.Because MOFis a porous material based on organic ligands,it may collapse due to an increase in column pressure during liquid chromatography testing.And when packing the column,the column efficiency is not good due to the particle size and shape of the material.Therefore,it is very significant to synthesize a uniform and stable CMOFmaterial or a MOFmaterial that has a good resolution effect for chiral molecules at normal temperature and pressure.In this project,four new metal-organic framework materials were designed and synthesized using camphoric acid as a chiral ligand,and their structures were analyzed and their properties in chiral resolution were studied.The main work is as follows:1 Three new metal-organic framework materials were synthesized using [Cu?D-cam?₄?biim-4?₂]_n?MOF2??[Zn?D-cam??biim-4?]_n·4_nH₂O?MOF3?.The structure and properties of the materials were characterized by means of single crystal XRD diffraction,powder XRD diffraction and thermogravimetry.2 The structure analysis of MOF1,MOF2 and MOF3 were performed.MOF1 is a two-dimensional mesh sql topology.MOF2 is a three-dimensional(4¹²·6³)pcu framework.MOF3 is a simple one-dimensional chain structure.It was found in the structural analysis that although MOF1 and MOF2 used a single configuration of camphoric acid as a chiral ligand,they did not exhibit chirality.By analyzing the structure,it was found that camphoric acid had a two-fold disorder phenomenon.We call this disorder disorder.By reviewing the literature,it was found that achiral MOFmaterials based on camphoric acid all appeared disordered racemic.This proves that whether the MOFmaterial based on camphoric acid exhibits chirality is not directly related to the nitrogen-containing auxiliary ligand.3 A polymetallic three-dimensional metal-organic framework material[Cu₆?D-cam?₈?TMDPY?₄Cd₂Na?OH?₄]was synthesized by hydrothermal synthesis using D-camphoric acid,4,4'-?1,3-propanediyl?bispyridine and Cu²⁺ions,Cd²⁺ions,Na⁺ions.The kinetic adsorption behaviors of MOF4 for D-/L-phenylalanine were also studied.And further proved that MOF4 has a chiral resolution effect on racemic phenylalanine.Then by fitting different data into different isothermal adsorption models,it was found that the isothermal adsorption process of phenylalanine by MOF4 is more consistent with the Langmuir isotherm adsorption model.4 By studying the desorption experiments of MOF4 in solution,it was found that only a small amount of phenylalanine was desorbed,which indicates that phenylalanine may chemically adsorb with metal ions on the surface of MOF4.