以4-氯-7-硝基-2,1,3-苯并口恶唑（NBD-Cl）为原料,首先合成了荧光单体4-（2-丙烯酸胺乙基酯）-7-硝基-2,1,3-苯并口恶唑（NBDAE）,然后以2-溴异丁酸乙酯（t-EBiB）为引发剂,CuCl/Me6TREN为催化剂,采用原子转移自由基聚合（ATRP）,与温敏性单体N-异丙基丙烯酰胺（NIPAM）共聚,得到水溶性无规共聚物P（NIPAM-co-NBDAE）。对产物进行了1H-NMR,GPC,UV-Vis及荧光光谱仪（FL）表征。结果表明,成功制备了多分散系数小于1.20的窄分布荧光水溶性共聚物,并研究了该聚合物荧光强度随温度的变化。在PNIPAM的相变温度（30℃）以下,该聚合物在水溶液中荧光较弱;而在PNIPAM的相变温度（30℃）以上,该聚合物的荧光强度随PNIPAM疏水转变而显著增强。
Firstly, A monomerized fluorescence molecular 4-（2-acryloyloxy-ethylamino）-7-nitro-2, 1, 3- benzoxadiazole （NBDAE） was prepared with NBD-Cl （4-Chloro-7-nitro-2, 1, 3-benzoxadiazole） as raw material. Then, well-defined thermoresponsive water-soluble random copolymers, poly（N-isopropylacrylamide-co-NBDAE） （P （NIPAM-co-NBDAE））, were prepared by atom transfer radical polymerization （ATRP）, with ethylbutyl-2- bromoiso-butyrate （t-EBiB） as initiator, and CuC1/Me6TREN as catalyst. The thermoresponsive copolymers were characterized by 1H-NMR, GPC, UV-Vis, and fluorescence measurement. The results indicate that the well-defined thermoresponsive hydrophilic copolymers are narrow molecular-weight distribution with the polydispersity index of less than 1.20. The copolymers possess good fluorescence performance. The phase transition temperature of PNIPAM is 30 ~（2. At 〉30 E, The fluorescence emission of hydrophilic copolymers is weak. While at 〈30 ℃, the thermoresponsive hydrophilic copolymers exhibit 2.5 times increased fluorescence intensity. It is observed that temperature induce polymers collapse at elevated temperatures and can be employed as a novel temperature sensor.
参考文献
| [1] | Krzysztof Matyjaszewski;Jianhui Xia .Atom Transfer Radical Polymerization[J].Chemical Reviews,2001(9):2921-2990. |
| [2] | Kaoru Iwai;Yuriko Matsumura;Seiichi Uchiyama;A.Prasanna de Silva .Development of fluorescent microgel thermometers based on thermo-responsive polymers and their modulation of sensitivity range[J].Journal of Materials Chemistry: An Interdisciplinary Journal dealing with Synthesis, Structures, Properties and Applications of Materials, Particulary Those Associated with Advanced Technology,2005(27/28):2796-2800. |
| [3] | Seiichi Uchiyama;Narumi Kawai;A. Prasanna de Silva;Kaoru Iwai .Fluorescent Polymeric AND Logic Gate with Temperature and pH as Inputs[J].Journal of the American Chemical Society,2004(10):3032-3033. |
| [4] | Shiraishi Y;Miyarnoto R;Hirai T .A hemicyanine-conjugated copolymer as a highly sensitive fluorescent thermometer[J].Langmuir: The ACS Journal of Surfaces and Colloids,2008(8):4273-4279. |
| [5] | Onoda M.;Uchiyama S.;Santa T.;Imai K. .A photoinduced electron-transfer reagent for peroxyacetic acid, 4-ethylthioacetylamino-7-phenylsulfonyl-2,1,3-benzoxadiazole, based on the method for predicting the fluorescence quantum yields[J].Analytical chemistry,2002(16):4089-4096. |
| [6] | 赵长稳,庄秀丽,陈学思,景遐斌.温度敏感性PNIPAM-b-PZLL-b-mPEG三嵌段共聚物的合成与自组装研究[J].高分子学报,2008(11):1096-1101. |
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