Design, Exploitation, and Rational Improvements of Diazirine-Based Universal Polymer Crosslinkers.

IF 16.4 1区 化学 Q1 CHEMISTRY, MULTIDISCIPLINARY Accounts of Chemical Research Pub Date : 2024-10-31 DOI:10.1021/acs.accounts.4c00509
Mathieu L Lepage, Stefania F Musolino, Jeremy E Wulff
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Abstract

ConspectusAddition of new covalent bonds between the chains of thermoplastic polymers (i.e., crosslinking) provides improved mechanical strength and enhanced high-temperature performance while also providing an effective strategy for photopatterning. Traditionally, however, crosslinking of each polymer substrate has required the use of a specific crosslinking technology (hydrosilylation for PDMS, vulcanization for rubber, etc.). The lack of a general solution to the challenge of polymer crosslinking means that there are many thermoplastics (e.g., polypropylene or polyhydroxyalkanoates) that have desirable properties, but which cannot be upgraded by traditional crosslinking technologies.Our lab developed the first universal crosslinkers for aliphatic polymers by leveraging trifluoromethyl aryl diazirine motifs, functional groups that have been widely used in chemical biology for >30 years, but which have seldom been exploited in materials science. These novel reagents work (via C-H insertion) on essentially any commodity polymer that contains aliphatic C-H bonds, including industrial plastics like polypropylene (the crosslinking of which has been an outstanding challenge in the field for >50 years), as well as commercially important elastomers (e.g., polydimethylsiloxane), biodegradable polymers (e.g., polycaprolactone), and green polymer materials derived from biomass (e.g., polyhydroxyalkanoates).Subsequent structure-function work from our group led to crosslinkers that were >10-fold more effective in undergoing C-H insertion with aliphatic substrates. We then developed an improved synthesis of our electronically optimized diazirines and incorporated them into a family of cleavable crosslinker reagents, which permit the on-demand generation of reprocessable thermosets. At the same time, other groups replaced the perfluoropropyl linker in our first-generation crosslinker with a series of dynamic linkages; these permit the ready generation of vitrimeric materials and can be used in the reactive compatibilization of immiscible plastic waste.Since the publication of our initial Science paper in 2019, this burgeoning field of diazirine-based polymer crosslinkers has experienced an explosion of interest. Publications from our lab and others have described the use of these reagents in covalent adhesion, photopatterning of low dielectric materials for microelectronics, and direct optical printing of quantum dots. Our crosslinkers have also been shown to heighten the robustness of ice-phobic coatings and improve the performance of woven ballistic fabric, while─perhaps most unexpectedly─substantially improving the stability of high-performance perovskite solar cells. Electronically optimized diazirines can also be used to covalently link proteins to polymer surfaces, suggesting a broad range of applications in the biocompatibilization of medical devices. This Account will summarize the development of trifluoromethyl aryl diazirine reagents for materials science over the past 5 years. A brief comparison will also be made, in the Summary and Outlook section at the end of the Account, to competing (and often complementary) reagents based upon azide and diazoalkyl motifs. Finally, we have compiled a Frequently Asked Questions list that covers many practical aspects of crosslinker design and application; this is appended as Supporting Information.

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重氮基通用聚合物交联剂的设计、开发和合理改进。
产品简介 在热塑性聚合物链之间添加新的共价键(即交联)可提高机械强度和高温性能,同时也是一种有效的光图案化策略。但传统上,每种聚合物基材的交联都需要使用特定的交联技术(PDMS 的水硅烷化、橡胶的硫化等)。我们的实验室利用三氟甲基芳基二氮杂环基团开发了第一种脂肪族聚合物通用交联剂,这种官能团在化学生物学中广泛使用已有 30 多年,但在材料科学中却鲜有应用。这些新型试剂(通过 C-H 插入)基本上可用于任何含有脂肪族 C-H 键的商品聚合物,包括聚丙烯等工业塑料(其交联是该领域 50 多年来的一项突出挑战),以及具有重要商业价值的弹性体(如:聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷、聚二甲基硅氧烷)、我们小组随后开展的结构-功能研究发现,交联剂在与脂肪族基质发生 C-H 插入反应时的效率提高了 10 倍以上。随后,我们改进了电子优化二氮杂环胺的合成方法,并将其纳入可裂解交联剂试剂系列,从而按需生成了可再加工的热固性塑料。与此同时,其他研究小组用一系列动态连接取代了我们第一代交联剂中的全氟丙基连接体;这些连接体可以随时生成三聚体材料,并可用于不相溶塑料废料的反应性相容。自 2019 年我们的第一篇《科学》论文发表以来,人们对重氮基聚合物交联剂这一新兴领域的兴趣激增。我们实验室和其他实验室发表的论文介绍了这些试剂在共价粘合、微电子低介电材料光图案化和量子点直接光学印刷中的应用。我们的交联剂还被证明可以提高疏冰涂层的坚固性,改善防弹编织物的性能,同时--也许是最出人意料的--大大提高了高性能过氧化物太阳能电池的稳定性。经过电子优化的二氮丙啶还可用于将蛋白质共价连接到聚合物表面,这表明它在医疗设备的生物相容方面有着广泛的应用。本报告将总结过去 5 年中用于材料科学的三氟甲基芳基重氮吖啶试剂的发展情况。在报告结尾的总结与展望部分,我们还将对基于叠氮和重氮烷基基团的竞争试剂(通常是互补试剂)进行简要比较。最后,我们还汇编了一份常见问题清单,涵盖了交联剂设计和应用的许多实际方面;该清单作为附录资料附在后面。
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来源期刊
Accounts of Chemical Research
Accounts of Chemical Research 化学-化学综合
CiteScore
31.40
自引率
1.10%
发文量
312
审稿时长
2 months
期刊介绍: Accounts of Chemical Research presents short, concise and critical articles offering easy-to-read overviews of basic research and applications in all areas of chemistry and biochemistry. These short reviews focus on research from the author’s own laboratory and are designed to teach the reader about a research project. In addition, Accounts of Chemical Research publishes commentaries that give an informed opinion on a current research problem. Special Issues online are devoted to a single topic of unusual activity and significance. Accounts of Chemical Research replaces the traditional article abstract with an article "Conspectus." These entries synopsize the research affording the reader a closer look at the content and significance of an article. Through this provision of a more detailed description of the article contents, the Conspectus enhances the article's discoverability by search engines and the exposure for the research.
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Misfit Layered Compounds: Insights into Chemical, Kinetic, and Thermodynamic Stability of Nanophases. Nickel-Catalyzed Reductive Alkenylation of Enol Derivatives: A Versatile Tool for Alkene Construction Design, Exploitation, and Rational Improvements of Diazirine-Based Universal Polymer Crosslinkers. Revisiting Pyrimidine-Embedded Molecular Frameworks to Probe the Unexplored Chemical Space for Protein–Protein Interactions Surface Structure and Chemistry of CeO2 Powder Catalysts Determined by Surface-Ligand Infrared Spectroscopy (SLIR).
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