The First Synthesis of Periodic and Alternating Glycopolymers by RAFT Polymerization: A Novel Synthetic Pathway for Glycosaminoglycan Mimics
The First Synthesis of Periodic and Alternating Glycopolymers by RAFT Polymerization: A Novel Synthetic Pathway for Glycosaminoglycan Mimics
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DOI：
10.3390/polym11010070
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发表时间：
2019-01-01
期刊：
影响因子：
5
通讯作者：
Motoyanagi, Jin
中科院分区：
文献类型：
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作者：
Minoda, Masahiko;Otsubo, Tomomi;Motoyanagi, Jin
本研究通过可逆加成-断裂链转移(RAFT)共聚反应控制合成周期糖共聚物。为此，新合成了麦芽糖和乳糖取代的乙烯基醚(Malve和LacVE)和麦芽糖取代的马来酰亚胺(Malmi)。MALVE与乙基马来酰亚胺(EtMI)的RAFT共聚(单体投料比：MALVE：EtMI=1：1)得到了由交替结构(-(Malve-EtMI)(N)-)的主要部分和EtMI(-EtMI-EtMI-)的一小部分连续序列组成的周期性糖共聚物(Poly(Malve-co-EtMI))。后一种序列的出现是由马来酰亚胺在本聚合条件下的均聚性引起的，通过改变单体投料比成功地抑制了EtMI连续序列的形成。LacVE和EtMI的RAFT共聚也被发现进行，类似地产生了周期性的糖共聚物(聚(LacVE-co-EtMI))。此外，还进行了LacVE/Malmi(单体投料比：LacVE：Malmi=1：1)的RAFT共聚反应，得到了LacVE/Malmi组成比接近36/的共聚物。用刀豆球蛋白A和花生凝集素对所合成的聚(MALVE-co-EtMI)和聚(LacVE-co-EtMI)进行了凝集素结合实验，发现其具有糖簇效应。此外，通过VE和MI共聚得到的这些糖共聚物被发现是无细胞毒性的。
This study concerned the controlled synthesis of periodic glycopolymers by reversible addition-fragmentation chain transfer (RAFT) copolymerization. To this end, maltose- and lactose-substituted vinyl ethers (MalVE and LacVE, respectively) and maltose-substituted maleimide (MalMI) were newly synthesized. RAFT copolymerization of MalVE and ethyl maleimide (EtMI) (monomer feed ratio: MalVE:EtMI = 1:1) afforded periodic glycopolymers (poly(MalVE-co-EtMI)) consisting of major parts of alternating structure (-(MalVE-EtMI)(n)-) and a small part of consecutive sequences of EtMI (-EtMI-EtMI-). Occurrence of the latter sequences was caused by the homopolymerizability of maleimide under the present polymerization condition, and the formation of the consecutive sequences of EtMI was successfully suppressed by varying the monomer feed ratio. RAFT copolymerization of LacVE and EtMI was also found to proceed and similarly yielded periodic glycopolymers (poly(LacVE-co-EtMI)). Moreover, RAFT copolymerization of LacVE and MalMI (monomer feed ratio: LacVE:MalMI = 1:1) was performed to give copolymers (poly(LacVE-co-MalMI)) having composition ratio of LacVE/MalMI approximate to 36/64. The resultant periodic glycopolymers poly(MalVE-co-EtMI) and poly(LacVE-co-EtMI) were subjected to lectin binding assay using concanavalin A and peanut agglutinin, exhibiting the glycocluster effect. Moreover, these glycopolymers obtained from the copolymerization of VE and MI were found to be non-cytotoxic.