PS-b-P4VP的制备及其包载富勒烯的研究
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摘要
富勒烯(C_(60))以其独特的结构有着广泛的应用,但由于其在水中溶解性较差限制了它在生物医学等领域的应用。本文通过嵌段共聚物来包载C_(60),使其在水溶液中稳定存在。首先利用可逆加成-裂解转移活性自由基聚合(RAFT)制备出嵌段共聚物聚苯乙烯-b-聚四乙烯基吡啶(PS-b-P4VP),通过核磁共振氢谱(~1H NMR)、傅里叶红外光谱(FT-IR)对聚合物的结构进行了表征。然后用研磨法将C_(60)包载在聚合物上,制备出以疏水链段PS/C_(60)为核,亲水链段P4VP为壳的聚合物胶束。利用动态光散射(DLS)、透射电镜(TEM)、紫外可见吸收光谱(UV-Vis)对胶束粒径及形貌进行了表征。最后将金属卟啉负载在PS-b-P4VP/C_(60)复合胶束上,制备出同时负载C_(60)和金属卟啉的复合胶束,使其在模拟生物体光合作用和制备太阳能电池等方面有着潜在的应用。
Since the discovery of fullerene(C_(60)),it has attracted much attention because of its unique properties.However,the poor solubility of C_(60) in water has significantly hindered medical applications.In this study,theamphiphilic block copolymers,poly(styrene)-block-poly(4-vinylpyridine)(PS-b-P4 VP),was used to helpthe dispersion of C_(60) in water.The PS-b-P4 VP block copolymers were synthesized through reversible addition-fragmentation chain transfer(RAFT) and characterized by nuclear magnetic hydrogen resonance spectroscopy(~1H NMR) and fourier infrared spectrum(FT-IR).Then PS-b-P4 VP was used to encapsulate C_(60) by the grinding method and the micelle comprised with a PS/C_(60) core and a hydrophilic P4 VP shell was formed.The micelle was characterized by dynamic light scattering(DLS),transmission electron microscopy(TEM),and UV-visible spectroscopy(UV-Vis).Finally,the complex micelle was formed by the electrostatic interactions of metalloporphyrin with the surplus P4 VP units in the PS-b-P4 VP/C_(60) micelle.It is expected that the complex micelle of metalloporphyri and C_(60) is suitable for applications in photocatalysis and solar cells.
Since the discovery of fullerene(C_(60)),it has attracted much attention because of its unique properties.However,the poor solubility of C_(60) in water has significantly hindered medical applications.In this study,theamphiphilic block copolymers,poly(styrene)-block-poly(4-vinylpyridine)(PS-b-P4 VP),was used to helpthe dispersion of C_(60) in water.The PS-b-P4 VP block copolymers were synthesized through reversible addition-fragmentation chain transfer(RAFT) and characterized by nuclear magnetic hydrogen resonance spectroscopy(~1H NMR) and fourier infrared spectrum(FT-IR).Then PS-b-P4 VP was used to encapsulate C_(60) by the grinding method and the micelle comprised with a PS/C_(60) core and a hydrophilic P4 VP shell was formed.The micelle was characterized by dynamic light scattering(DLS),transmission electron microscopy(TEM),and UV-visible spectroscopy(UV-Vis).Finally,the complex micelle was formed by the electrostatic interactions of metalloporphyrin with the surplus P4 VP units in the PS-b-P4 VP/C_(60) micelle.It is expected that the complex micelle of metalloporphyri and C_(60) is suitable for applications in photocatalysis and solar cells.
引文
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[6] Saiki Y,Amao Y.Bio-mimetic hydrogen production from polysaccharide using the visible light sensitization of zinc porphyrin [J].Biotechnol Bioeng.,2003,82(6):710-714.
[7] 时宁宁.RAFT合成P4VP基两亲性聚合物及其在溶液中的自组装研究[D].北京化工大学,2012.
[8] 柴志华,李昂,安英丽,史林启.聚乙二醇-b-聚赖氨酸/C60/ZnTPPS胶束及功能化研究[J].高分子学报,2017(2):393-398.
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[2] 张鑫,贺继东,代元坤,姜雪.水溶性C60衍生物在生物医学领域的研究现状[J].高分子通报,2014(4):8-15.
[3] Liu B,Bunker C E,Sun Y P .Preparation and characterization of soluble pendant [60]fullerene-polystyrene polymers[J].Chemical Communications,1996(10):1241.
[4] 刘岩,孙岚,姚红娟,张英鸽.水溶性富勒烯C60的制备及其血液相容性研究[A].现代仪器与医疗,2014,20(4):1-3.
[5] 杨润苗,王延梅.PS-b-P4VP 两嵌段共聚物的合成及其自组装的研究[J].高分子学报,2004(3):401-405.
[6] Saiki Y,Amao Y.Bio-mimetic hydrogen production from polysaccharide using the visible light sensitization of zinc porphyrin [J].Biotechnol Bioeng.,2003,82(6):710-714.
[7] 时宁宁.RAFT合成P4VP基两亲性聚合物及其在溶液中的自组装研究[D].北京化工大学,2012.
[8] 柴志华,李昂,安英丽,史林启.聚乙二醇-b-聚赖氨酸/C60/ZnTPPS胶束及功能化研究[J].高分子学报,2017(2):393-398.
[9] Deguchi S,Alargova R G,Tsujii K.Langmuir[J].2001(17):6013-6017.