Synthesis and Self-Assembly of CO2–Temperature Dual Stimuli-Responsive Triblock Copolymers
Synthesis and Self-Assembly of CO2–Temperature Dual Stimuli-Responsive Triblock Copolymers
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DOI：
10.1021/ma5001404
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发表时间：
2014-04
期刊：
影响因子：
5.5
通讯作者：
Bo-wen Liu;Hang Zhou;Si-tong Zhou;Huijuan Zhang;Anchao Feng;Chun-mei Jian;Jin Hu;Weiping Gao
中科院分区：
文献类型：
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作者：
Bo-wen Liu;Hang Zhou;Si-tong Zhou;Huijuan Zhang;Anchao Feng;Chun-mei Jian;Jin Hu;Weiping Gao
采用原子转移自由基聚合法合成了链末端含β-环糊精(β-CD)的聚(N，N-二甲氨基甲基丙烯酸乙酯)(PDMAEMA)，通过开环聚合合成了链末端带有−C═C链段和金刚烷(ADA)基团的聚己内酯(PCL)，通过可逆加成-断链转移聚合(RAFT)合成了链末端带有−链段的聚N-异丙基丙烯酰胺(PNIPAM)，可转化为硫醇基团。通过硫醇烯Michael加成和主客体相互作用，合成了与PNIPAM、PDMAEMA亲水链段和PCL疏水链段具有良好生物相容性的超分子三嵌段刺激响应型共聚物PNIPAM-b-PCL-b-PDMAEMA。这种三嵌段共聚物可以自组装成囊泡，并对二氧化碳(CO2)气体和温度做出可逆响应。在CO2的刺激下，泡囊集合体明显膨胀；当温度从25°升高到40°时，泡囊集合体明显膨胀。
Poly(N,N-dimethylaminoethyl methacrylate) (PDMAEMA) with a β-cyclodextrin (β-CD) at the chain end was synthesized via atom transfer radical polymerization (ATRP); poly(e-caprolactone) (PCL) with a −C═C– segment and an adamantane (Ada) group at two ends, respectively, was prepared through ring-opening polymerization (ROP), and poly(N-isopropylacrylamide) (PNIPAM) with a −S–C(S)–S– segment, which can be converted into a thiol group, was yielded by reversible addition–fragmentation chain transfer polymerization (RAFT). A supramolecular triblock stimuli-responsive copolymer PNIPAM-b-PCL-b-PDMAEMA having good biocompatibility with PNIPAM and PDMAEMA hydrophilic segments and PCL hydrophobic segment was constructed by thiol–ene Michael addition and host–guest interaction. The triblock copolymer could self-assemble into vesicles and respond to carbon dioxide (CO2) gas and temperature reversibly. Under the stimulation of CO2, the vesicular assemblies swelled obviously; while raising the temperature from 25 to 40 °...