Well-defined AB(2) Y-shaped miktoarm star copolymers of PNIPAM-b-(PZLL)(2) and PNIPAM-b-(PLL)(2) were synthesized through the combination of atom transfer radical polymerization (ATRP), ring-opening polymerization (ROP), and click chemistry, where PNIPAM, PZLL, and PLL arc poly(N-isopropylacrylamide), poly(epsilon-benzyloxycarbonyl-L-lysine), and poly(L-lysine), respectively. Propargyl amine was employed as ROP initiator for the preparation of alkynyl-terminated PZLL. Diazide-terminated PNIPAM was obtained with an azide-containing ATRP initiator. The subsequent click reaction led to the formation of PNIPAM-b-(PZLL)(2). After the removal of the benzyloxycarbonyl group, water-soluble PNIPAM-b-(PLL)(2) was obtained. The core shell micelles of PNIPAM-b-(PLL)(2) were formed above lower critical solution temperature of PNIPAM block. At this temperature, the shell cross-linking was performed through the reaction between glutaraldehyde and the primary amine groups of the PLL shell, affording the micelles with the endurance to temperature and pH changes. These shell-cross-linked micelles were used as drug nanocarriers and the release profile was dually controlled by the solution temperature and the cross-linking degree.
Dual thermo‐ and pH‐sensitive network‐grafted hydrogels formed by macrocrosslinker as drug delivery system
作者:Ting‐Ting Pan、Wei‐Dong He、Li‐Ying Li、Wen‐Xing Jiang、Chen He、Jing Tao
DOI:10.1002/pola.24645
日期:2011.5.15
pH‐sensitive network‐grafted hydrogels made of poly(N,N‐dimethylaminoethyl methacrylate) (PDMAEMA) network and poly(N‐isopropylacrylamide) (PNIPAM) grafting chains were successfully synthesized by the combination of atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chaintransfer (RAFT) polymerization, and click chemistry. PNIPAM having two azide groups at one chain end [PNIPAM‐(N3)2]
通过原子转移自由基聚合的组合成功地合成了由聚甲基丙烯酸N,N-二甲基氨基乙基酯(PDMAEMA)网络和聚N-异丙基丙烯酰胺(PNIPAM)接枝链制成的对温度和pH敏感的双重网络接枝水凝胶。ATRP),可逆加成-断裂链转移(RAFT)聚合和单击化学。具有一个链端[PNIPAM-(N两个叠氮基PNIPAM 3)2用的叠氮化物封端的ATRP引发剂制备] Ñ,ñ -二(β叠氮基乙基)-2- chloropropionylamide。炔未决聚(N,N-二甲基氨基乙基甲基丙烯酸酯共-propargyl丙烯酸酯)[P(DMAEMA-共-ProA)]是通过使用三苄基碳酸二苄酯作为链转移剂的RAFT共聚获得的。随后的点击反应导致网络接枝的水凝胶的形成。从形态学和溶胀/溶胀动力学方面研究了P(DMAEMA- co - ProA)的化学成分对水凝胶性能的影响。在不同温度和pH值下,双重刺激敏感水凝胶均显示出快速