A photo–thermal dual-regulated latent monomer strategy for sequence control of polymers,Polymer Chemistry

当前位置： X-MOL 学术 › Polym. Chem. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

A photo–thermal dual-regulated latent monomer strategy for sequence control of polymers
Polymer Chemistry ( IF 4.1 ) Pub Date : 2021-08-12 , DOI: 10.1039/d1py00961c
Liuqiao Zhang ₁ , Yuyang Song ₁ , Yuhang Cao ₁ , Zhen Wang ₁ , Zhihao Huang ₁ , Sunting Xuan ₁ , Zhengbiao Zhang _{1,

2}

Affiliation

Sequence-control, widely found in biopolymers (e.g., DNA), remains a significant challenge in polymer synthesis. Here, the concept of the photo–thermal dual-regulated release of the methyl maleimide (MMI) monomer in RAFT copolymerizations is presented, aiming to enrich the current methodologies of polymer sequence control. Photo-sensitive dithienylfuran-protected methyl maleimide (DTFMMI) was used as a latent monomer in which the dithienyl groups were in the “ring-closed” form under ultraviolet irradiation. This rigid structure significantly reduced its activity towards the retro Diels–Alder (rDA) reaction and the monomer remained dormant at a high temperature. However, the dithienyl group transformed to its “ring-open” analogue with the irradiation of visible light and triggered the rDA reaction of DTFMMI, allowing the release of active MMI and its gradual incorporation into the growing polymer chains. As a result, the structural isomerization of DTFMMI and the onset release of MMI could be well controlled by light and temperature, collectively, to regulate the polymer sequence in a more facile and non-invasive way. This proof-of-concept study sheds light on the development of synthetic methods for the construction of more advanced sequence-controlled polymers.

中文翻译：

用于聚合物序列控制的光热双重调节潜在单体策略

序列控制，广泛存在于生物聚合物中（例如, DNA)，仍然是聚合物合成中的一个重大挑战。在这里，提出了 RAFT 共聚中甲基马来酰亚胺 (MMI) 单体的光热双重调节释放的概念，旨在丰富当前的聚合物序列控制方法。使用光敏二噻吩基呋喃保护的甲基马来酰亚胺（DTFMMI）作为潜在单体，其中二噻吩基在紫外线照射下呈“闭环”形式。这种刚性结构显着降低了其对逆狄尔斯-阿尔德 (rDA) 反应的活性，并且单体在高温下保持休眠状态。然而，二噻吩基在可见光的照射下转变为其“开环”类似物并触发了DTFMMI的rDA反应，允许释放活性 MMI 并将其逐渐结合到不断增长的聚合物链中。因此，DTFMMI 的结构异构化和 MMI 的起始释放可以很好地受到光和温度的共同控制，从而以更容易和非侵入性的方式调节聚合物序列。这项概念验证研究揭示了用于构建更先进的序列控制聚合物的合成方法的发展。

更新日期：2021-08-25

点击分享查看原文

点击收藏

阅读更多本刊最新论文本刊介绍/投稿指南11