One-Pot Synthesis Of Hyperbranched Glycopolymer And Application

Carhobydrates,the main source of energy of organisms and an important part of the process of life activities,are a kind of important biological information molecules.Hyperbranched glycopolymers with three-dimensional globular architecture have attracted significant interesting due to their unique virtues,including low viscosity,numerous terminal groups,interior cavities,low R_g and R_h.Hyperbranched glycopolymers possessing good hydrophilicity,excellent biocompatibility and specific binding protein,are regarded as promising biomaterials for bioapplications,especially in the construction of drug loading and gene delivery systems.In this paper,the synthetic methods of hyperbranched glycopolymers were designed and two novel hyperbranched glycopolymers were synthesized by new methods without the resource to tedious protection-deprotection procedures.The polymerization methods provided a basis for the synthesis of hyperbranched glycopolymers and extended their applications in fluorescence materials and biomedical fields.The main contents are as follows:Chapter ?:The development of hyperbranched glycopolymers is briefly introduced.Chapter ?:The facile preparation of hyperbranched glycopolymers was performed by one-pot reaction of the self-condensing vinyl copolymerization/redox?SCVP/Redox?process using the methyl-6-O-methacryloyl-?-D-glucoside?6-O-MMAGlc?as monomer.The formation of the branching point and linear chain growth were defined to give the degree of branching?DB?from ¹H NMR data.A linear increase of the DB was observed as the concentration of Ce?IV?increased,implying facile control of the DB.The hyperbranched glycopolymers on the amyloid fibrillation of hen egg white lysozyme?HEWL?exhibited a greater inhibition activity than that of the linear analogue.Chapter ?:Hyperbranched poly?6-O-methacryloyl mannose??MaM?was synthesized by Cu?III?and Ce?IV?as the initiators.The ring opening phenomenon existed in hyperbranched poly?MaM?and the ring opening phenomenon of Cu?III?was weaker than one of Ce?IV?.Hence,to explored the different of inidiation mechanisms,hyperbranched poly?6-O-MMAGlc?s were synthesized by Cu?III?.Compared with Ce?IV?,the main intiate center of Cu?III?was located on the hydroxyl groups in C4 position.An increase of the DB was observed as the concentration of Cu?III?increased,the max of DB value reaching 0.32.The obtained hyperbranched glycopolymers on the amyloid fibrillation of hen egg-white lysozyme?HEWL?exhibited a lower inhibition activity than the glycopolymers initiated by Ce?IV?,implying that the-OH groups in C4 position play important roles in this process.The results of cytotoxicity of hyperbranched poly?6-O-MMAGlc?showed that hyperbranched glycopolymer had low cytotoxicity.Chapter ?:A facile strategy of one-pot method,combining free radical polymerization with“click”reaction,is used to synthesize hyperbranched poly?6-O-methacryloyl mannose/2-isocyanatoethyl methacrylate??HPG?MaM-co-IM??.In order to control the single structure parameter of HPG?MaM-co-IM?,the effect of reaction condition on the structure parameters of HPG?MaM-co-IM?were investigated in detail.The molecular weights and DB could be controlled by adjusting a single variable.HPG?MaM-co-IM?could act as an immediate-release carrier for curcumin.HPG?MaM-co-IM?had low cytotoxicity,high inhibition ratio to HEWL fibrillation,and good biodegradability.Chapter ?:The linear poly?6-O-MMAGlc?and hyperbranched poly?6-O-MMAGlc?were grafted with fluorescein derivative?PF?.The graft rate of hyperbranched poly?6-O-MMAGlc?-PF?HPG-PF?was higher than linear poly?6-O-MMAGlc?-PF?LPG-PF?.It was indicated that topological structure of hyperbtanched glycopolymers was helpful to increase the graft ratio of PF.HPG-PF showed good stability in water and had specific responsive to H₂O_2.In addition,the results of cytotoxicity of HPG-PF showed hyperbranched glycopolymer had low cytotoxicity.The fluorescent glycopolymers colocalization studies indicated that HPG-PF was imaging on mitochondria by the different concentration of H₂O₂in cells.