Preparation and self-assembly of pH-sensitive amphiphilic comb-shaped copolymer containing long fluorinated side chains
Preparation and self-assembly of pH-sensitive amphiphilic comb-shaped copolymer containing long fluorinated side chains
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DOI：
10.1080/10601325.2016.1224630
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发表时间：
2016-09
期刊：
影响因子：
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通讯作者：
Jianquan Tan;Weiqu Liu;Zhengfang Wang
中科院分区：
文献类型：
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作者：
Jianquan Tan;Weiqu Liu;Zhengfang Wang
摘要：利用2-（二甲氨基）甲基丙烯酸乙酯（DMAEMA）的自由基聚合，设计并合成了一种新型含长氟侧链的ph敏感型梳状两亲共聚物，该共聚物结合了叔胺悬垂的ph敏感特性、氟化部分独特的疏水和疏氟特性以及聚乙二醇段的亲水性。聚乙二醇甲基丙烯酸甲醚（PEGMA）和自制的含氟大单体（PHFBMA-GMA）。研究了由此制备的聚合物胶束的物理化学性质。通过GPC、FTIR和1H-NMR表征了共聚物的化学结构。用荧光光谱法测定了不同pH值（5.0和7.4）下共聚物的临界胶束浓度（CMC）。在较低的pH条件下，由于DMAEMA的旋旋增强了其亲水性，可以获得较大的cmc。随着PHFBMA-GMA用量和分子量的增加，CMC显著降低。随着pH的降低，聚合物胶束的粒径和zeta电位显著增加，表明聚合物胶束具有明显的pH敏感性。此外，PHFBMA-GMA用量越大，分子量越高，聚合物胶束越大。透射电子显微镜（TEM）显示共聚物的形态为球形胶束。细胞毒性试验表明，梳状共聚物具有极低的细胞毒性。由含有长氟化侧链的两亲性梳状共聚物制备的ph敏感聚合物胶束可能是疏水或疏氟分子和药物载体的纳米罐的潜在候选者，并且易于制备可能适合大规模工业化。
ABSTRACT Novel pH-sensitive amphiphilic comb-shaped copolymers containing long fluorinated side chains, which combined the characteristics of pH-sensitivity from pendent tertiary amine groups, unique hydrophobic and fluorophobic characteristic from the fluorinated moieties and hydrophilicity from the poly (ethylene glycol) segments, were designed and synthesized via radical polymerizaion of 2-(Dimethylamino) ethyl methacrylate (DMAEMA), poly (ethylene glycol) methyl ether methacrylate (PEGMA) and homemade fluorinated macromonomer (PHFBMA-GMA). The physicochemical properties of polymeric micelles prepared therefrom were investigated. The chemical structures of the copolymers were characterized by GPC, FTIR and 1H-NMR. The critical micelle concentrations (CMC) of the copolymers in different pH (5.0 and 7.4) were determined by fluorescence spectroscopy. Larger CMCs could be obtained in lower pH since the pronation of DMAEMA moieties enhanced the hydrophilicity. With increasing the amount, as well as the molecular weight, of PHFBMA-GMA, CMC decreased significantly. As pH decreased, particle size, as well as zeta potential of the polymeric micelles increased significantly, indicating significant pH-sensitivity of the polymeric micelles. Furthermore, larger polymeric micelles were obtained with larger amount, as well as higher molecular weight, of PHFBMA-GMA. Transmission electron microscopy (TEM) showed that the morphological shapes of the copolymers performed spherical micelles. The cytotoxicity test showed that the comb-shaped copolymers performed extremely low cytotoxicity. The pH-sensitive polymeric micelles prepared from the amphiphilic comb-shaped copolymers containing long fluorinated side chains could be potential candidates for nanotanks for hydrophobic or fluorophobic molecules and drug carriers and the facile preparation might fit for large scale industrialization.