Characterization of N-phenylmaleimide-terminated poly(ethylene glycol)s and their application to a tetra-arm poly(ethylene glycol) gel
Characterization of N-phenylmaleimide-terminated poly(ethylene glycol)s and their application to a tetra-arm poly(ethylene glycol) gel
复制标题
N-苯基马来酰亚胺封端聚乙二醇的表征及其在四臂聚乙二醇凝胶中的应用
DOI：
10.1039/d0sm01658f
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发表时间：
2020
期刊：
影响因子：
3.4
通讯作者：
Otsuka Hideyuki
中科院分区：
文献类型：
--
作者：
Takashima Rikito;Ohira Masashi;Yokochi Hirogi;Aoki Daisuke;Li Xiang;Otsuka Hideyuki
四臂聚乙二醇（TetraPEG）凝胶是一种坚韧的材料，其韧性来源于其均匀的网状结构。它们可以通过高转化效率的化学反应将四臂聚合物的末端结合而形成，如Michael加成、使用活性酯基的缩合反应和炔-叠氮化环加成。在这里，我们报道了用在聚合物末端有n -苯基马来酰亚胺基团的四臂聚合物（四- n -芳基MA PEG）作为支架合成四聚乙二醇凝胶。采用对马来酰亚苯基异氰酸酯（PMPI）改性剂对马来酰亚苯基异氰酸酯（PMPI）进行简单的马来酰亚胺化反应，在一锅反应中直接将聚合物末端的羟基转化为活性的n -芳基马来酰亚胺基。利用高效液相色谱（HPLC）、基质辅助激光解吸电离飞行时间质谱和质子核磁共振谱对所得的四n -芳基MA PEG进行了全面表征。高效液相色谱分析不仅证明了四- n -芳基MA PEG的高纯度和羟基的完全转化，而且为n -芳基马来酰亚胺基PEG提供了一种简单的表征方法，使我们能够对不同n -芳基马来酰亚胺数的功能化聚合物进行定量分析。此外，我们通过Michael加成得到的四n -芳基MA和巯基TetraPEG制备了TetraPEG凝胶。因此，本报告提出了四- n -芳基MA PEG作为获得均匀网络结构的有效前驱体的应用及其表征方法；这些结果将为基于均匀网络结构概念的功能分子、软材料和进一步的功能材料的开发提供支持。
Tetra-arm poly(ethylene glycol) (TetraPEG) gels are tough materials whose toughness originates from their uniform network structure. They can be formed by combining the termini of tetra-arm polymers via chemical reactions with high conversion efficiency, such as the Michael addition, condensations using an active ester group, and alkyne–azide cycloadditions. Herein, we report the synthesis of a tetra-PEG gel using a tetra-arm polymer with N-phenylmaleimide moieties at the polymer ends (tetra-N-aryl MA PEG) as a scaffold. Tetra-N-aryl MA PEG can be obtained via a simple maleimidation using the modification agent p-maleimidophenyl isocyanate (PMPI), which directly transforms the hydroxy groups at the polymer ends into reactive N-aryl maleimide groups in a one-pot reaction. The thus-obtained tetra-N-aryl MA PEG was fully characterized using high-performance liquid chromatography (HPLC), matrix-assisted laser desorption ionization time of flight mass spectrometry, and proton nuclear magnetic resonance spectroscopy. HPLC analysis not only demonstrated the high purity of tetra-N-aryl MA PEG and the full conversion of the hydroxy groups, but also provided an effective characterization method for N-aryl maleimide-based PEG using a simple protocol, which enables us quantitative analysis of functionalized polymers with different N-aryl maleimide numbers. Furthermore, we fabricated a TetraPEG gel via Michael addition of the obtained tetra-N-aryl MA and thiol-terminated TetraPEGs. Thus, this report presents the application of tetra-N-aryl MA PEG as an effective precursor to obtain a uniform network structure and a method for its characterization; these results should provide support for the development of functional molecules, soft materials, and further functional materials based on the uniform-network-structure concept.