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RAFT polymerization of tertiary sulfonium zwitterionic monomer in aqueous media for synthesis of protein stabilizing double hydrophilic block copolymers
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2020-05-28 , DOI: 10.1002/pol.20200158 Ryutaro Imamura 1, 2 , Kazunori Masuko 1 , Hideharu Mori 1
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2020-05-28 , DOI: 10.1002/pol.20200158 Ryutaro Imamura 1, 2 , Kazunori Masuko 1 , Hideharu Mori 1
Affiliation
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The reversible addition‐fragmentation chain‐transfer (RAFT) polymerization of a tertiary sulfonium‐containing zwitterionic monomer (N‐acryloyl‐L‐methionine methyl sulfonium salt: A‐Met[S+]‐OH) was performed in aqueous media in the presence of a water‐soluble chain‐transfer agent (CTA). Several parameters, such as the radical initiator, nature of the salt used as an additive, polymerization temperature, and solvent (water, buffer solution, and mixed solvents), were studied. The polymerization of A‐Met(S+)‐OH in acetate buffer using a trithiocarbonate‐type CTA having two carboxylic acid moieties proceeded in a controlled fashion at 45°C, as confirmed by the low polydispersity of the products (M
w/M
n < 1.1) and pre‐determined molecular weights. Poly(ethylene glycol)‐based macro‐CTA was also employed for the polymerization of A‐Met(S+)‐OH in mixed solvents (H2O/EtOH and H2O/DMF = 70/30 vol%) to afford novel nonionic‐zwitterionic double hydrophilic block copolymers. The chain extension of the hydrophilic poly(N,N‐dimethylacrylamide) macro‐CTA with A‐Met(S+)‐OH was well controlled in pure water under the appropriate conditions, resulting in the formation of block copolymers with “as‐designed” chain structures and relatively low dispersities (M
w/M
n < 1.3). The resulting sulfonium‐containing double hydrophilic block copolymers having optimal nonionic/zwitterionic balance were efficient protein‐stabilizing agents.
中文翻译：
叔sulf两性离子单体在水性介质中的RAFT聚合反应，用于合成蛋白质稳定的双亲水嵌段共聚物
含叔sulf的两性离子单体（N-丙烯酰基-L-甲硫氨酸甲基salt盐：A-Met [S + ] -OH）的可逆加成-断裂链转移（RAFT）聚合反应是在存在水的介质中进行的水溶性链转移剂（CTA）。研究了一些参数，例如自由基引发剂，用作添加剂的盐的性质，聚合温度和溶剂（水，缓冲液和混合溶剂）。使用具有两个羧酸基团的三硫代碳酸酯型CTA在乙酸盐缓冲液中A-Met（S +）-OH的聚合反应在45°C下以受控方式进行，这证实了产物的低多分散性（M w / M n <1.1）和预定的分子量。在混合溶剂（H 2 O / EtOH和H 2 O / DMF = 70/30 vol％）中，还使用了基于聚乙二醇的大分子CTA聚合A-Met（S +）-OH。新型的非离子-两性离子双亲水嵌段共聚物。在适当的条件下，在纯水中可以很好地控制亲水性聚N， N-二甲基丙烯酰胺大分子CTA与A-Met（S +）-OH的链增长，从而形成具有“按设计要求”的嵌段共聚物。链结构和较低的分散度（ M w / M n <1.3）。具有最佳非离子/两性离子平衡的含sulf双亲水嵌段共聚物是有效的蛋白质稳定剂。
更新日期：2020-05-28
中文翻译：
叔sulf两性离子单体在水性介质中的RAFT聚合反应，用于合成蛋白质稳定的双亲水嵌段共聚物
含叔sulf的两性离子单体（N-丙烯酰基-L-甲硫氨酸甲基salt盐：A-Met [S + ] -OH）的可逆加成-断裂链转移（RAFT）聚合反应是在存在水的介质中进行的水溶性链转移剂（CTA）。研究了一些参数，例如自由基引发剂，用作添加剂的盐的性质，聚合温度和溶剂（水，缓冲液和混合溶剂）。使用具有两个羧酸基团的三硫代碳酸酯型CTA在乙酸盐缓冲液中A-Met（S +）-OH的聚合反应在45°C下以受控方式进行，这证实了产物的低多分散性（M w / M n <1.1）和预定的分子量。在混合溶剂（H 2 O / EtOH和H 2 O / DMF = 70/30 vol％）中，还使用了基于聚乙二醇的大分子CTA聚合A-Met（S +）-OH。新型的非离子-两性离子双亲水嵌段共聚物。在适当的条件下，在纯水中可以很好地控制亲水性聚N， N-二甲基丙烯酰胺大分子CTA与A-Met（S +）-OH的链增长，从而形成具有“按设计要求”的嵌段共聚物。链结构和较低的分散度（ M w / M n <1.3）。具有最佳非离子/两性离子平衡的含sulf双亲水嵌段共聚物是有效的蛋白质稳定剂。
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