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Ring opening functionalization of thiolactone homopolymers for ROS scavenging
Journal of Polymer Science ( IF 3.9 ) Pub Date : 2024-04-30 , DOI: 10.1002/pol.20230955
Aaron Priester 1 , Forrest Kievit 2 , Anthony J. Convertine 1
Affiliation  

In this research, we explored the synthesis and application of thiolactone acrylamide (TLA) polymers for neutralizing reactive oxygen species (ROS), produced as a result of traumatic brain injury (TBI). We synthesized well-defined TLA polymers using RAFT (reversible addition-fragmentation chain transfer) polymerization across a range of monomer-to-chain transfer agent ([M]0/[CTA]0) ratios to achieve a range of molar masses. Polymerizations were carried out using a trithiocarbonate CTA (chain transfer agent) with AIBN (azobisisobutyronitrile) as the initiator in N'N-dimethylacetamide (DMAc) at 60 °C. Kinetic studies indicated a linear increase in molar mass with conversion, pseudo-first-order kinetics, and molar mass values that are consistent with theoretical predictions. Furthermore, the polymerizations exhibited a decrease in molar mass dispersity with conversion. We then investigated ring opening of the thiolactone residues with isoserinol (ISOH), which was followed by thiol-ene reactions of the resultant thiol groups with methacrylamide to yield a series of copolymers with different thiol-to-thioether ratios. The resulting polymers demonstrated varying levels of ROS neutralization. Higher thiol concentrations lead to more rapid neutralization while thioether residues provided sustained neutralization activity.

中文翻译:


用于清除 ROS 的硫代内酯均聚物的开环官能化



在这项研究中,我们探索了硫代内酯丙烯酰胺(TLA)聚合物的合成和应用,用于中和因创伤性脑损伤(TBI)而产生的活性氧(ROS)。我们使用 RAFT(可逆加成断裂链转移)聚合方法,在一系列单体到链转移剂 ([M] 0 /[CTA] 0 ) 比率以实现一定范围的摩尔质量。使用三硫代碳酸酯 CTA(链转移剂)和 AIBN(偶氮二异丁腈)作为引发剂,在 N'N-二甲基乙酰胺 (DMAc) 中于 60 °C 下进行聚合。动力学研究表明摩尔质量随着转化而线性增加,伪一级动力学和摩尔质量值与理论预测一致。此外,聚合反应表现出摩尔质量分散度随着转化而降低。然后,我们研究了硫内酯残基与异丝氨醇(ISOH)的开环,随后所得硫醇基团与甲基丙烯酰胺发生硫醇-烯反应,产生一系列具有不同硫醇与硫醚比率的共聚物。所得聚合物表现出不同水平的 ROS 中和作用。较高的硫醇浓度导致更快的中和,而硫醚残基提供持续的中和活性。
更新日期:2024-04-30
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