End-functionalized polymers and junction-functionalized diblock copolymers via RAFT chain extension with maleimido monomers.
End-functionalized polymers and junction-functionalized diblock copolymers via RAFT chain extension with maleimido monomers.
复制标题
DOI：
10.1021/bc800426d
复制
发表时间：
2009-06
影响因子：
4.7
通讯作者：
Stayton PS
中科院分区：
文献类型：
--
作者：
Henry SM;Convertine AJ;Benoit DS;Hoffman AS;Stayton PS
描述了一种新的策略，用于官能化通过可逆加成-断裂链转移（RAFT）聚合合成的聚合物的ω-末端，该聚合物提供空间控制的生物缀合位点。制备ω-官能聚合物的传统方法需要还原RAFT链转移剂以产生低反应性的仲硫醇或叔硫醇或合成含有反应性基团的新型链转移剂。作为另外的策略，N-取代的马来酰亚胺单体已被用于改性嵌段聚合中，以几乎定量的效率将单个马来酰亚胺单元添加到RAFT聚合物上。N-取代基中所含的独特反应性基团由此被添加到聚合物的ω-末端，并且随后可用于缀合反应。该技术已经使用N-（2-氨基乙基）马来酰亚胺三氟乙酸盐将单个伯胺引入聚（甲基丙烯酸二甲基-氨基乙酯）和聚（N-异丙基丙烯酰胺）的ω-末端以及用于siRNA递送的专用嵌段共聚物中得到证实。保留的功能RAFT端基的证据是由合成结果，其中扩链的polyDMAEMA（Mn = 10 - 600克/摩尔，Mw/Mn = 1.14）被用作大分子链转移剂的苯乙烯的聚合，产生低多分散性（Mn = 20 - 300克/摩尔，Mw/Mn = 1.11）的二嵌段聚合物。因此，还可以构建具有精确位于两个嵌段之间的连接处的生物缀合位点的二嵌段共聚物。扩链聚合物用胺反应性荧光染料或叶酸分别以86%和94%的缀合效率官能化。本文所述的多功能扩链技术为合成具有生物学和靶向目的的分子的明确定义的聚合物缀合物提供了独特的机会。
A new strategy is described for functionalizing the ω-terminal end of polymers synthesized by reversible addition–fragmentation chain transfer (RAFT) polymerization that provides spatially controlled bioconjugation sites. Traditional methods for preparing ω-functional polymers require the reduction of the RAFT chain-transfer agent to yield secondary or tertiary thiols of low reactivity or the synthesis of novel chain-transfer agents that contain reactive groups. As an additional strategy, N-substituted maleimido monomers have been used in a modified block polymerization to add a single maleimido unit onto the RAFT polymer with nearly quantitative efficiency. Unique reactive groups contained in the N-substituent are thereby added to the ω-terminal end of the polymer and are subsequently available for conjugation reactions. This technique has been demonstrated using N-(2-aminoethyl)maleimide trifluoroacetate to introduce a single primary amine to the ω-terminus of poly(dimethy-laminoethyl methacrylate) and poly(N-isopropyl acrylamide) and to a specialized block copolymer for siRNA delivery. Evidence for retention of functional RAFT endgroups is provided by synthesis results where chain-extended polyDMAEMA (Mn = 10 600 g/mol, Mw/Mn = 1.14) was used as a macro chain transfer agent for the polymerization of styrene, yielding a diblock polymer of low polydispersity (Mn = 20 300 g/mol, Mw/Mn = 1.11). It is thus also possible to construct diblock copolymers with a bioconjugation site precisely located at the junction between the two blocks. The chain-extended polymers are functionalized with an amine-reactive fluorescent dye or folic acid at conjugation efficiencies of 86 and 94%, respectively. The versatile chain-extension technique described here offers unique opportunities for the synthesis of well-defined polymeric conjugates to molecules of biological and targeting interest.
登录
查看更多内容
影响因子：
10.8
作者：
Kyriakides, TR;Cheung, CY;Hoffman, AS
通讯作者：
Hoffman, AS
影响因子：
4.6
作者：
Caulfield, MJ;Solomon, DH
通讯作者：
Solomon, DH
DOI：
10.1163/156856205774472335
发表时间：
2005-01-01
影响因子：
3.6
作者：
Jeong, JH;Kim, SH;Park, TG
通讯作者：
Park, TG
影响因子：
4.7
作者：
Dufresne, MH;Gauthier, MA;Leroux, JC
通讯作者：
Leroux, JC
影响因子：
5.5
作者：
Ganachaud, F;Monteiro, MJ;Rizzardo, E
通讯作者：
Rizzardo, E