Syntheses of Vinyl Monomers Having Fluorescence Probe Unit and Studies on Polymer Micro-Environments

在9-（4-N，N-二甲氨基苯基）菲（DMA-Phen； DP）中，N，N-二甲苯胺（DMA）和菲（Phen）通过Csp^2-Csp^2键直接连接，显示出强烈的无结构的分子内电荷转移（ICT）荧光。由于该化合物具有较强的溶剂化致色性，我们对其作为一种新型荧光探针感兴趣，并利用其作为分子内荧光探针研究了聚合物微环境。本项目合成了一种具有DP单元的新型乙烯基单体，并利用嵌入到聚合物中的DP探针的荧光研究了一些丙烯酰胺衍生物聚合物在水溶液中的温度诱导相变。本研究的结果如下：1。合成了一种具有DP单元（DP=MMA）的新型甲基丙烯酸甲酯衍生物单体。制备了一些dp标记的丙烯酰胺聚合物，如聚n-异丙基丙烯酰胺（PNIPAM）、聚n-正丙基丙烯酰胺（PNNPAM）和聚n-异丙基甲基丙烯酰胺（PNIPMAM），并利用荧光探针技术研究了它们在水溶液中的温度诱导相变和聚合物微环境。制备了pp标记的PNIPAM与NNPAM和NIPMAM共聚物。NIPAM共聚物的LCST在19-46℃之间，这取决于它们的共聚物成分。它们的温度诱导相变非常明显，NIPAM均聚物的相变也非常明显。热敏PNIPAM水凝胶的荧光标记研究正在进行中。

9-(4-N,N-Dimethylaminophenyl) phenanthrene (DMA-Phen ; DP), in which N,N-dimethylaniline (DMA) and phenanthrene (Phen) are linked directly by a Csp^2-Csp^2 bond, shows an intense and structureless intramolecular charge-transfer (ICT) fluorescence. We have been interedted in this compound DP as a new fluorescence probe because of its strong solvatochromism and studied polymer micro-environments with using DP as an intramolecular fluorescence probe. In this project a new vinyl monomer having DP unit was synthesized and termperature-induced phase transitions of some acrylamide derivative polymers in aqueous solutions have been studied by using the fluorescence of a DP probe incorporated into the polymers. The results in this study are as follows.1. A new methyl methacrylate (MMA) derivative monomer having DP unit (DP=MMA) was synthesized.2. Some DP-labeled acrylamide polymers such as poly(N-isoprophylacrylamide) (PNIPAM), poly(N-n-propylacrylamide) (PNNPAM), and poly(N-isoprophylmethacrylamide) (PNIPMAM) were prepared and their temperature-induced phase transitions and polymer micro-environments in aqueous solutions were studied by fluorescence probe technique.3. DP-labeled PNIPAM copolymers with NNPAM and NIPMAM were prepared. The NIPAM copolymers exhibit their LCST between 19-46ﾟC,depending on their copolymer compositions. And their temperature-induced phase transitions appear to be very sharp as well as that of NIPAM homopolymer.4. Fluorescence label studies of thermosensitive PNIPAM hydrogels are in progress.