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Effects of terminal group and chain length on temperature-responsive chromatography utilizing poly(N-isopropylacrylamide) synthesized via RAFT polymerization

机译:端基和链长对RAFT聚合合成聚(N-异丙基丙烯酰胺)的温度响应色谱的影响

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Poly(N-isopropylacrylamide) with two chain lengths (MW: ca. 5000, and ca. 20 000 g mol(-1)) was synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization, using 2-dodecylsulfanylthiocarbonylsulfanyl-2-methyl propionic acid as the chain transfer agent. The derivatization of terminal dodecyl groups to maleimide groups was performed through the reduction of terminal trithiocarbonate moieties. These polymers were grafted onto aminopropyl silica using an activated ester-amine coupling method. Five types of polymer modified silica beads were prepared, i.e., long chain length, short chain length, and mixed chain length functionalized with a dodecyl terminal group, and long chain length and short chain length with a maleimide terminal group. The surface properties of the modified polymer silica beads were evaluated by employing them as the stationary phase in HPLC setups and examining the temperature-dependent elution profiles of five steroids. The retention factor of steroids became smaller when the terminal dodecyl group was substituted with a maleimide group. A hydrophobic dodecyl moiety on the outermost surface strongly affected the retention of steroids, and the retention factor of steroids on short chains was larger than that on long chains below the lower critical solution temperature. These results indicate that the chain length and terminal functional group on the outermost surface of the polymer have a critical effect on the characteristics of polymer modified silica bead interfaces.
机译:通过使用2-十二烷基硫烷基硫代羰基硫烷基-2-可逆加成-断裂链转移(RAFT)聚合合成具有两个链长(MW:约5000和约20000 mol(-1))的聚(N-异丙基丙烯酰胺)甲基丙酸为链转移剂。通过降低末端三硫代碳酸酯部分,将末端十二烷基衍生为马来酰亚胺基。使用活化的酯-胺偶联方法将这些聚合物接枝到氨基丙基二氧化硅上。制备了五种类型的聚合物改性的二氧化硅珠,即长链长度,短链长度和用十二烷基末端基团官能化的混合链长,以及长链长度和短链长度用马来酰亚胺末端基团官能化的。通过在HPLC设置中将改性的聚合物硅胶珠用作固定相并检查五种类固醇的温度依赖性洗脱曲线,可以评估改性的聚合物硅胶珠的表面性能。当末端十二烷基被马来酰亚胺基团取代时,类固醇的保留因子变小。在最低临界溶液温度以下,最外表面的疏水性十二烷基部分强烈影响类固醇的保留,并且短链上的类固醇保留因子大于长链上的类固醇。这些结果表明,聚合物最外表面上的链长和末端官能团对聚合物改性的二氧化硅珠界面的特性具有关键影响。

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