Free Radical Polymerization Based On Porphyrin Derivative Immobilization/bionic Enzyme

Free radical polymerization is one of the earliest and most in-depth polymerization reactions,it plays an important role in polymer chemistry.But in traditional free radical polymerization,once the reaction starts,the reaction process and the reaction products cannot be controlled.Meanwhile,in the study of free radical polymerization reaction,people often use transition metals or organic dyes as catalysts for the reaction.But neither transition metals nor organic dyes are conducive to the green theme of chemical production.Therefore,how to realize the effective control of free radical polymerization under the circumstance of environmental protection has become a hot research topic.As a renewable resource,light energy has a very wide utilization value in both living and abiotic bodies.Light is used as the reaction condition to control the free radical polymerization,and the reaction is controlled by adjusting the light,so as to realize the pre-design and process control of the reaction product.As we all know,applying solar energy to industrial production including catalysis is our ideal pursuit for scientific research.This paper starts from the idea of molecular assembly,constructs two different catalysts through different assembly methods,and explores the photocatalytic reaction controlled by light as a switch.The specific research results are as follows:1.Porphyrins and aliphatic dipeptides were modified with short peptides to construct functional hybrids,which were assembled by adjusting the proportion of solvents to form a controllable coarse spherical structure.The photosensitive properties of porphyrins are demonstrated by combining amino acid derivatives(or short peptides)with porphyrins to form porphyrins derivatives and self-assemble into stable structures.At the same time,we studied the mechanism of short peptide-porphyrin assembly used to immobilize glucose oxidase and improve the catalytic activity of the enzyme.Porphyrins have the ability of photoinduced electron transfer,which can transfer the photoelectron generated under the light excitation to glucose oxidase,so that glucose oxidase can better catalyze free radical polymerization reaction,thus improving the ability of enzyme to catalyze RAFT free radical polymerization reaction.2.Inspired by the composition of natural enzymes,a series of biomimetic enzymes with controllable size and shape were prepared by using photosensitizer tetraphyphenyl porphyrin(TPP)and bovine serum albumin(BSA)as the building block.The effects of temperature and the addition of metal ion Mn2+ on the catalytic activity of the materials were investigated.It was found that the co-assembled TPP-BSA series of materials had better catalytic activity and the ability of multiple cycles.After 60 heating treatment,the catalytic performance of the material is obviously enhanced.With the addition of metal ion Mn2+,the catalytic activity of the material was further improved and the material still had strong catalytic activity after four cycles of catalytic activity.