Deng Ziwei, Hu Xiaoxi, Wang Yun, Yin Yanzhen, Peng Bo, Xu Zushun
a School of Materials Science and Engineering , Shaanxi Normal University , Xi'an 710062 , P.R. China.
J Biomater Sci Polym Ed. 2015;26(1):16-31. doi: 10.1080/09205063.2014.979385. Epub 2014 Nov 11.
This paper proposed a simple synthetic strategy towards a novel cationic europium luminescent copolymer, poly(METAC-co-NIPAm-co-Eu(AA)3Phen) (PMNEu), and investigation about their complexation ability with DNA. In this approach, first, Eu(AA)3Phen complex monomer containing Eu(3+), acrylic acid (AA), and 1,10-phenanthroline (Phen) was synthesized, and subsequently, free radical copolymerization of Eu(AA)3Phen complex monomer with other two functional monomers, [2-(methacryloyloxy) ethyl] trimethylammonium chloride (METAC) and N-isopropylarylamide (NIPAm), was carried out in methanol using azodiisobutyronitrile (AIBN) as the initiator. (1)HNMR, GPC, fluorescence spectroscopy, UV-vis spectroscopy, and TEM were used to investigate the chemical structures, molecular weight and molecular weight distribution, fluorescence properties, UV spectra, and morphologies of PMNEu copolymer, respectively. Furthermore, the interaction of PMNEu with DNA was also studied with fluorescence spectroscopy, UV-vis spectroscopy, and agarose gel electrophoresis. These results indicated that PMNEu could interact with DNA via an electrostatic bonding mode and the bonding constant was 2.2 × 10(5) L/mol. Additionally, TEM observation showed that pure PMNEu formed micelles in water solution, while the size-controllable aggregations of PMNEu with DNA were obtained when PMNEu was mixed with DNA at various concentration ratios. A good biocompability of PMNEu was demonstrated through in vitro cytotoxicity assays.
本文提出了一种合成新型阳离子铕发光共聚物聚（甲基丙烯酰氧乙基三甲基氯化铵 - 异丙基丙烯酰胺 - 铕（丙烯酸）₃菲咯啉）（PMNEu）的简单策略，并研究了其与DNA的络合能力。在该方法中，首先合成了包含Eu(3+)、丙烯酸（AA）和1,10 - 菲咯啉（Phen）的Eu(AA)₃Phen络合物单体，随后，以偶氮二异丁腈（AIBN）为引发剂，在甲醇中使Eu(AA)₃Phen络合物单体与另外两种功能单体[2 - （甲基丙烯酰氧基）乙基]三甲基氯化铵（METAC）和N - 异丙基丙烯酰胺（NIPAm）进行自由基共聚。利用¹H NMR、凝胶渗透色谱（GPC）、荧光光谱、紫外 - 可见光谱和透射电子显微镜（TEM）分别研究了PMNEu共聚物的化学结构、分子量及分子量分布、荧光性质、紫外光谱和形态。此外，还通过荧光光谱、紫外 - 可见光谱和琼脂糖凝胶电泳研究了PMNEu与DNA的相互作用。这些结果表明，PMNEu可通过静电结合模式与DNA相互作用，结合常数为2.2×10⁵ L/mol。另外，TEM观察表明，纯PMNEu在水溶液中形成胶束，而当PMNEu与DNA以不同浓度比混合时，可获得尺寸可控的PMNEu与DNA的聚集体。体外细胞毒性试验证明了PMNEu具有良好的生物相容性。
