Shining Light on Cyclopentadienone–Norbornadiene Diels–Alder Adducts to Enable Photoinduced Click Chemistry with Cyclopentadiene
Shining Light on Cyclopentadienone–Norbornadiene Diels–Alder Adducts to Enable Photoinduced Click Chemistry with Cyclopentadiene
复制标题
揭示环戊二烯酮 - 降冰片二烯二烯 - 桤木加合物，以实现与环戊二烯的光诱导点击化学
DOI：
10.1021/acsami.1c08670
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发表时间：
2021
影响因子：
9.5
通讯作者：
Read de Alaniz, Javier
中科院分区：
文献类型：
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作者：
Bailey, Sophia J.;Stricker, Friedrich;Hopkins, Erik;Wilson, Maxwell Z.;Read de Alaniz, Javier
提出了一种新的基于Diels-Alder（DA）的光催化脱羰反应平台，该平台利用了环烯酮-降冰片二烯（CPD-NBD）加合物的不可逆光诱导脱羰反应和随后的裂解反应。合成了一系列CPD-NBD加合物，并对其在高分子材料微结构化平台中的应用进行了系统的研究。通过将一个优化的CPD-NBD加合物到聚合物网络中，它表明，环戊二烯可以揭开后365 nm的照射，随后点击各种马来酰亚胺与空间控制下温和的反应条件下，快速的动力学。与目前可用的光诱导Diels-Alder反应不同，该反应依赖于捕获瞬态的光笼化二烯，该平台在照射后引入了持久的但高度反应性的二烯，使得能够使用光敏物质如花青染料进行图案化。为了突出该平台在各种材料应用中的潜在用途，我们展示了两个概念验证：将多种染料图案化缀合成聚丙烯酸酯网络和将链霉亲和素预编程连接成聚（乙二醇）水凝胶。
A new Diels–Alder (DA)-based photopatterning platform is presented, which exploits the irreversible, light-induced decarbonylation and subsequent cleavage of cyclopentadienone–norbornadiene (CPD–NBD) adducts. A series of CPD–NBD adducts have been prepared and systematically studied toward the use in a polymeric material photopatterning platform. By incorporating an optimized CPD–NBD adduct into polymer networks, it is demonstrated that cyclopentadiene may be unveiled upon 365 nm irradiation and subsequently clicked to a variety of maleimides with spatial control under mild reaction conditions and with fast kinetics. Unlike currently available photoinduced Diels–Alder reactions that rely on trapping transient, photocaged dienes, this platform introduces a persistent, yet highly reactive diene after irradiation, enabling the use of photosensitive species such as cyanine dyes to be patterned. To highlight the potential use of this platform in a variety of material applications, we demonstrate two proof-of-concepts: patterned conjugation of multiple dyes into a polyacrylate network and preprogrammed ligation of streptavidin into poly(ethylene glycol) hydrogels.