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层层组装膜可作为狄尔斯-阿尔德反应的强化反应环境。

Layer-by-layer assembled film can serve as an enhanced reaction environment for Diels-Alder reaction.

作者信息

Fujisawa Nanami, Ebara Mitsuhiro

机构信息

Research Center for Macromolecules and Biomaterials, National Institute for Materials Science (NIMS), Tsukuba, Japan.

Graduate School of Pure and Applied Sciences, University of Tsukuba, Tsukuba, Japan.

出版信息

Front Chem. 2024 Dec 12;12:1524096. doi: 10.3389/fchem.2024.1524096. eCollection 2024.

Abstract

Although the Diels-Alder reaction (DA) has garnered significant attention due to its numerous advantages, its long reaction time is a drawback. Herein, we investigated the effects of polarity difference on DA using Layer-by-Layer (LbL) films comprising polycationic polyallylamine hydrochloride and polyanionic poly (styrenesulfonic acid-co-furfuryl methacrylate) [poly (SS--FMA)] as the reaction environment. First, furan composition in poly (SS--FMA) was adjusted to be 19 mol% to achieve good water solubility and layer deposition. The successful formation of LbL films with 8 and 40 layers was confirmed by quartz crystal microbalance. The polarity within films and, consequently, the DA efficiency between furfuryl methacrylate and the maleimide in MAL-PEG-NHS increased with an increasing number of layers up to 40 layers without requiring chemical modification on the reaction site of DA or any catalysts. Furthermore, we employed the LbL coating on the surface of magnetic nanoparticles (MNPs). The retro DA reaction (rDA) was successfully triggered by heating the MNPs by AC magnetic field. We believe that the proposed technology can serve as an enhanced DA reaction environment as well as temporal/spatial control of rDA in various applications.

摘要

尽管狄尔斯-阿尔德反应(DA)因其众多优点而备受关注,但其较长的反应时间是一个缺点。在此,我们使用由聚阳离子聚烯丙胺盐酸盐和聚阴离子聚(苯乙烯磺酸-共-甲基丙烯酸糠酯)[聚(SS--FMA)]组成的逐层(LbL)膜作为反应环境,研究了极性差异对DA反应的影响。首先,将聚(SS--FMA)中的呋喃组成调整为19摩尔%,以实现良好的水溶性和层沉积。通过石英晶体微天平确认成功形成了8层和40层的LbL膜。膜内的极性以及因此甲基丙烯酸糠酯与MAL-PEG-NHS中的马来酰亚胺之间的DA反应效率随着层数增加至40层而增加,而无需对DA反应位点进行化学修饰或添加任何催化剂。此外,我们在磁性纳米颗粒(MNP)表面采用了LbL涂层。通过交流磁场加热MNP成功触发了逆DA反应(rDA)。我们相信,所提出的技术可以作为一种增强的DA反应环境以及在各种应用中对rDA进行时空控制的手段。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/54b0/11672198/93142a234049/fchem-12-1524096-g001.jpg

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