Photoimageable Organic Coating Bearing Cyclic Dithiocarbonate for a Multifunctional Surface
Photoimageable Organic Coating Bearing Cyclic Dithiocarbonate for a Multifunctional Surface
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DOI：
10.1021/acsami.1c19559
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发表时间：
2022-01-04
影响因子：
9.5
通讯作者：
Kim，Myungwoong
中科院分区：
文献类型：
--
作者：
An，Sol;Nam，Jieun;Kim，Myungwoong
我们报道了用含活性环二硫代碳酸盐（DTC）的共聚物制备光交联和表面功能化聚合物薄膜。这些材料表面的化学功能在光照下被精确地定义。采用可逆加成-破碎链转移聚合法制备了聚甲基丙烯酸二硫代碳酸酯-随机甲基丙烯酸烷基酯（DTC）共聚物，并对反应动力学进行了深入分析。共聚物通过双功能氨基甲酸乙酯交联剂交联成涂层，该交联剂含有耐光性-硝基苯基，并在暴露于光下释放苯胺。芳香胺的亲核攻击打开DTC基团，形成氨基甲酸酯键并在此过程中生成反应性巯基。通过改变共聚物和交联剂的用量，可以有效地控制未反应DTC和硫醇的表面浓度。甲基丙烯酸共聚体的使用导致通过酸水解产生额外的活性表面功能，如羧酸。在环境条件下，通过顺序亲核开环、巯基和碳二亚胺偶联反应，DTC、巯基和羧基成功转化为不同的官能团，并通过x射线光电子能谱进行了定量证实。所提出的化学物质很容易适应于固定复杂分子，如荧光团和蛋白质在光刻确定的区域，突出了它们在创造有机涂层方面的潜力，这些有机涂层在环境条件下可以具有多个官能团。
We report the fabrication of photocross-linkable and surface-functionalizable polymeric thin films using reactive cyclic dithiocarbonate (DTC)-containing copolymers. The chemical functionalities of these material surfaces were precisely defined with light illumination. The DTC copolymers, namely, poly(dithiocarbonate methylene methacrylate–random-alkyl methacrylate)s, were synthesized via reversible addition–fragmentation chain transfer polymerization, and the reaction kinetics was thoroughly analyzed. The copolymers were cross-linked into a coating using a bifunctional urethane cross-linker that contains a photolabileo-nitrobenzyl group and releases aniline upon exposure to light. The nucleophilic attack of the aromatic amine opens the DTC group, forming a carbamothioate bond and generating a reactive thiol group in the process. The surface concentrations of the unreacted DTC and thiol were effectively controlled by varying the amounts of the copolymer and the cross-linker. The use of methacrylate comonomers led to additional reactive surface functionality such as carboxylic acid via acid hydrolysis. The successful transformations of the resulting DTC, thiol, and carboxylic acid groups to different functionalities via sequential nucleophilic ring opening, thiol–ene, and carbodiimide coupling reactions under ambient conditions were confirmed quantitatively using X-ray photoelectron spectroscopy. The presented chemistries were readily adapted to the immobilization of complex molecules such as a fluorophore and a protein in lithographically defined regions, highlighting their potential in creating organic coatings that can have multiple functional groups under ambient conditions.