Side chain thiol-functionalized poly(ethylene glycol) by post-polymerization modification of hydroxyl groups: synthesis, crosslinking and inkjet printing
Side chain thiol-functionalized poly(ethylene glycol) by post-polymerization modification of hydroxyl groups: synthesis, crosslinking and inkjet printing
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通过羟基后聚合改性的侧链硫醇官能化聚乙二醇：合成、交联和喷墨印刷
DOI：
10.1039/c4py00099d
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发表时间：
2014
影响因子：
4.6
通讯作者：
G.E.M.
中科院分区：
文献类型：
--
作者：
Southan;Schönhaar;Borchers;Müller;G.E.M.
通过羟甲基侧链的后聚合改性，分三步合成了具有聚乙二醇主链和巯甲基侧链的聚合物。作为合成路线的起点，使用环氧乙烷和缩水甘油的线性共聚物，其中缩水甘油重复单元的摩尔含量约为20%、40%、60%、80%和100%。聚合物结合的羟基分三步转化为硫醇基团，包括甲苯磺酰化、引入三苯甲基保护的硫醇和通过酸处理进行硫醇脱保护。硫醇官能化程度由起始材料的官能化程度控制。对于具有约20%和40%缩水甘油重复单元的共聚物，通过1H NMR光谱测定的羟基转化为硫醇基的程度是定量的；对于具有约60%、80%和100%缩水甘油重复单元的共聚物，羟基转化为硫醇基的程度分别为92%、81%和87%。示例性地，通过聚(缩水甘油)转化获得的聚(缩水甘油基硫醇)与聚(乙二醇)二丙烯酸酯(PEG-DA)交联以产生水凝胶，其在细胞接种后48小时支持人成纤维细胞的粘附和增殖。随后通过将聚(缩水甘油硫醇)和PEG-DA溶液喷墨印刷到丙烯酸酯载玻片上来制造空间限定的和表面附着的凝胶结构。
Polymers with a poly(ethylene glycol) backbone and mercaptomethyl side chains were synthesized by post-polymerization modification of hydroxymethyl side chains in three steps. As the starting point of the synthetic route, linear copolymers of ethylene oxide and glycidol with molar contents of glycidol repeating units of approximately 20, 40, 60, 80 and 100% were used. The polymer-bound hydroxyl groups were converted to thiol groups in three steps, comprising tosylation, introduction of a triphenylmethyl protected thiol and thiol deprotection by acid treatment. The degree of thiol-functionalization was controlled by the degree of functionalization of the starting material. The degree of conversion of hydroxyl groups to thiol groups determined by 1H NMR spectroscopy was quantitative for copolymers with approximately 20 and 40% glycidol repeating units and 92, 81 and 87% for copolymers with approximately 60, 80 and 100% glycidol repeating units, respectively. Exemplarily, poly(glycidylthiol) obtained by conversion of poly(glycidol) was crosslinked with poly(ethylene glycol) diacrylate (PEG-DA) to yield hydrogels which supported adhesion and proliferation of human fibroblasts 48 h after cell seeding. Spatially defined and surface attached gel structures were fabricated by subsequent inkjet printing of poly(glycidylthiol) and PEG-DA solutions onto acrylated glass slides.