Gitsov Ivan, Zhu Chao
Michael M. Szwarc Polymer Research Institute and Department of Chemistry, College of Environmental Science and Forestry, State University of New York, Syracuse, New York 13210, USA.
J Am Chem Soc. 2003 Sep 17;125(37):11228-34. doi: 10.1021/ja0345625.
This paper describes the synthesis of amphiphilic pseudo-semi-interpenetrating polymer networks (pseudo-semi-IPNs) containing linear poly(styrene) and poly(ethylene glycol) (PEG) cross-linked through monodendritic fragments. A unique feature of the synthetic strategy is the permanent attachment of the linear segment to the PEG network by a transesterification reaction between the hydroxyl groups at both ends of the PEG and peripheral ethyl ester moieties in the monodendron portion of a linear poly(styrene)-dendritic poly(benzyl ether) AB block copolymer. The proceeding of the reaction is monitored by (1)H NMR and size exclusion chromatography (SEC). The formation of an interlock structure between the linear block and the network matrix in the pseudo-semi-IPN is evidenced by the results from spectroscopic analyses and differential scanning calorimetry measurements. The accessibility of functional centers in the grafted semi-IPN is confirmed by model reactions with fluorescent markers, fluorescence spectroscopy, and NMR techniques and shows the potential of these novel materials as sequestering reagents for resin capture-release applications in parallel synthesis, combinatorial chemistry, and advanced drug design.
本文描述了一种两亲性伪半互穿聚合物网络(伪半互穿网络)的合成方法,该网络包含通过单枝状片段交联的线性聚苯乙烯和聚乙二醇(PEG)。合成策略的一个独特之处在于,通过PEG两端的羟基与线性聚苯乙烯-树枝状聚苄基醚AB嵌段共聚物单枝部分的外围乙酯基团之间的酯交换反应,将线性链段永久连接到PEG网络上。通过¹H NMR和尺寸排阻色谱法(SEC)监测反应进程。光谱分析和差示扫描量热法测量结果证明了伪半互穿网络中线性嵌段与网络基质之间形成了互锁结构。通过与荧光标记物的模型反应、荧光光谱法和NMR技术证实了接枝半互穿网络中功能中心的可及性,这表明这些新型材料作为螯合试剂在平行合成、组合化学和先进药物设计中的树脂捕获-释放应用具有潜力。