规整两亲性梳状共聚物合成及药控释放研究
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摘要
两亲性梳形共聚物是一类链构造比较特殊的高分子聚合物,也是一种有着广泛应用价值的聚合物材料。目前,它已经成为高分子研究领域的一个热门话题。研究者们也通过阴／阳离子聚合、自由基聚合等不同的方法,同时结合活性聚合方法,成功制备出一系列的两亲性梳状共聚物,并将其成功应用于很多领域当中。但是,对于合成高规整度两亲性梳状共聚物的报道却鲜有提及。本文以苯乙烯(St)、对氯甲基苯乙烯(CMS)和甲基丙烯酸二甲基氨基乙酉(?)(DMAEMA)为主要原料,成功的合成了具有高规整度两亲性的梳状共聚物P(St-g-DMAEMA),并考察了其在选择性溶剂中的自组装过程。通过激光粒度仪(DLS)研究了高规整度梳状共聚物胶束的粒径及粒径分布,并采用TEM观察了胶束的形貌。实验证明,胶束不仅能够有效的加载药物,还可以延长药物释放的时间,控制药物释放的速率,使药物的释放速率更平稳、均匀。
1.首先以正丁基锂(nBuLi)为引发剂,以St为原料,通过添加有机金属钡盐构筑双金属阴离子聚合体系,考察了立构规整性聚苯乙烯的制备条件,制得等规度为31%的苯乙烯均聚物,通过FT IR、DSC、XRD、13C-NMR、GPC对均聚物的结构及分子量进行了表征；2.以St和CMS为起始原料,用nBuLi引发其共聚合,合成等规度为45%的St和CMS的共聚物P(St-co-CMS),并通过FT IR、DSC、XRD、13C-NMR、GPC对共聚物的结构和分子量进行了表征；
3.通过原子转移自由基聚合(ATRP)法,将DEAEMA成功接枝到P(St-co-CMS)上,得到了目标产物,也就是具有高规整度两亲性的梳状共聚物P(St-g-DEAEMA),并通过FT IR、DSC、TGA对共聚物的结构及热性能进行表征；
4.考察了高规整度两亲性梳状共聚物在选择性溶剂中的自组装过程,通过DLS考察胶束的粒径及其分布,测试结果表明：胶束粒径约为100nnm,并用TEM观察胶束的形貌为圆球状。在p H 1.4及p H 7.4的缓冲溶液中,模拟人体温度37℃环境下,研究其对螺旋霉素的体外控制释放行为,结果表明,用高规整度两亲性梳状共聚物胶束包覆疏水性药物螺旋霉素粉,测试在26 h内,在p H 1.4的缓冲溶液中的总释药量1.0302mg,p H7.4缓冲溶液中的释药量为1.0989mg,释药率达到100%,且释放速率比较均匀,表现了对疏水性药物良好的控制释放能力。
Amphiphilic and comb-like copolymer is a kind of polymer material which has special chain and is very useful. At present,it has become a hot topic in the field of polymer reseach. The researchers successful synthesis a series of amphiphilic comb copolymer by anionic/ cationic polymerization and radical polymerization methods, they promote appliances where are all kinds of fields.But the synthesis of high isotactic amphiphilic and comb-like copolymer is rarely mentioned. With P(St-co-CMS) and DMAEMA as raw material,we has synthesis to P(St-g-DMAEMA),and it was investigated self-assembly process in selective solvents by DLS.And the morphologies,which was sphere,of the micelles was verified by TEM images. The micelle still exhibited efficiently properties as drug carrier in deionized water from the drug controlled release study.
1) By adding organometallic barium salt in anionic polymerization system, a double metallic system was built.The synthetic conditions about manufacturing stereoregular PS were also investigated.The result is shown that the isotacticity of this product is about 31%. The products were characterized by FT IR,DSC,XRD and 13C-NMR,and their structures and molecular weight had been confirmed.
2) On this basis,with styrene(St) and chloromethylstyrene(CMS) as monomers,their copolymerization was triggered by n-BuLi. It is found that the isotacticity of P(St-co-CMS) is about 45%.By FT IR,DSC,XRD and 13C-NMR,the product was demonstrated.
3) DEAEMA was grafted to the P(St-co-CMS) by atom transfer radical polymerization, high isotactic amphiphilic and comb-like copolymer has obtained.And P(St-g-DMAEMA) was characterized by FT IR、DSC、TGA.
4) The self-assembly of comb-like copolymer was investigated by DLS. The results showed that the size and PDI of the micelles were about 100nm and 0.146.The same time the morphologies,which was sphere,of the micelles was verified by TEM images.At pH1.4 or 7.4, controlled release behavior of SPM was studied and the results showed that The total release volume is 1.0302mg in p H 1.4 buffer solution,and pH 7.4 is 1.0989mg,release drug rate is 100% and uniform,it was demonstrated the micelle had good performance on drug Controlled release.
1.首先以正丁基锂(nBuLi)为引发剂,以St为原料,通过添加有机金属钡盐构筑双金属阴离子聚合体系,考察了立构规整性聚苯乙烯的制备条件,制得等规度为31%的苯乙烯均聚物,通过FT IR、DSC、XRD、13C-NMR、GPC对均聚物的结构及分子量进行了表征；2.以St和CMS为起始原料,用nBuLi引发其共聚合,合成等规度为45%的St和CMS的共聚物P(St-co-CMS),并通过FT IR、DSC、XRD、13C-NMR、GPC对共聚物的结构和分子量进行了表征；
3.通过原子转移自由基聚合(ATRP)法,将DEAEMA成功接枝到P(St-co-CMS)上,得到了目标产物,也就是具有高规整度两亲性的梳状共聚物P(St-g-DEAEMA),并通过FT IR、DSC、TGA对共聚物的结构及热性能进行表征；
4.考察了高规整度两亲性梳状共聚物在选择性溶剂中的自组装过程,通过DLS考察胶束的粒径及其分布,测试结果表明：胶束粒径约为100nnm,并用TEM观察胶束的形貌为圆球状。在p H 1.4及p H 7.4的缓冲溶液中,模拟人体温度37℃环境下,研究其对螺旋霉素的体外控制释放行为,结果表明,用高规整度两亲性梳状共聚物胶束包覆疏水性药物螺旋霉素粉,测试在26 h内,在p H 1.4的缓冲溶液中的总释药量1.0302mg,p H7.4缓冲溶液中的释药量为1.0989mg,释药率达到100%,且释放速率比较均匀,表现了对疏水性药物良好的控制释放能力。
Amphiphilic and comb-like copolymer is a kind of polymer material which has special chain and is very useful. At present,it has become a hot topic in the field of polymer reseach. The researchers successful synthesis a series of amphiphilic comb copolymer by anionic/ cationic polymerization and radical polymerization methods, they promote appliances where are all kinds of fields.But the synthesis of high isotactic amphiphilic and comb-like copolymer is rarely mentioned. With P(St-co-CMS) and DMAEMA as raw material,we has synthesis to P(St-g-DMAEMA),and it was investigated self-assembly process in selective solvents by DLS.And the morphologies,which was sphere,of the micelles was verified by TEM images. The micelle still exhibited efficiently properties as drug carrier in deionized water from the drug controlled release study.
1) By adding organometallic barium salt in anionic polymerization system, a double metallic system was built.The synthetic conditions about manufacturing stereoregular PS were also investigated.The result is shown that the isotacticity of this product is about 31%. The products were characterized by FT IR,DSC,XRD and 13C-NMR,and their structures and molecular weight had been confirmed.
2) On this basis,with styrene(St) and chloromethylstyrene(CMS) as monomers,their copolymerization was triggered by n-BuLi. It is found that the isotacticity of P(St-co-CMS) is about 45%.By FT IR,DSC,XRD and 13C-NMR,the product was demonstrated.
3) DEAEMA was grafted to the P(St-co-CMS) by atom transfer radical polymerization, high isotactic amphiphilic and comb-like copolymer has obtained.And P(St-g-DMAEMA) was characterized by FT IR、DSC、TGA.
4) The self-assembly of comb-like copolymer was investigated by DLS. The results showed that the size and PDI of the micelles were about 100nm and 0.146.The same time the morphologies,which was sphere,of the micelles was verified by TEM images.At pH1.4 or 7.4, controlled release behavior of SPM was studied and the results showed that The total release volume is 1.0302mg in p H 1.4 buffer solution,and pH 7.4 is 1.0989mg,release drug rate is 100% and uniform,it was demonstrated the micelle had good performance on drug Controlled release.
引文
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