Smith Gregory N, Mears Laura L E, Rogers Sarah E, Armes Steven P
Department of Chemistry , University of Sheffield , Brook Hill , Sheffield , South Yorkshire S3 7HF , UK . Email:
Department of Chemistry , University of Liverpool , Liverpool L69 7ZD , UK.
Chem Sci. 2017 Nov 17;9(4):922-934. doi: 10.1039/c7sc03334f. eCollection 2018 Jan 28.
Cationic diblock copolymer nanoparticles have been prepared in -dodecane polymerization-induced self-assembly (PISA). A previously reported poly(stearyl methacrylate)-poly(benzyl methacrylate) (PSMA-PBzMA) PISA formulation ( 2016, , 5078-5090) was modified by statistically copolymerizing an oil-soluble cationic methacrylic monomer, (2-(methacryloyloxy)ethyl)trimethylammonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate, with either SMA or BzMA, to produce either charged shell or charged core nanoparticles. The electrokinetics were studied as a function of many variables (function of volume function, particle size, solvent viscosity, and number of ions per chain). These data are consistent with electrophoresis controlled by counterion condensation, which is typically observed in salt-free media. However, there are several interesting and unexpected features of interest. In particular, charged shell nanoparticles have a lower electrophoretic mobility than the equivalent charged core nanoparticles, and the magnitude of the electrophoretic mobility increases as the fraction of cationic stabilizer chains in the shell layer is reduced. These results show that cationic PSMA-PBzMA spheres provide an interesting new example of electrophoretic nanoparticles in non-polar solvents. Moreover, they should provide an ideal model system to evaluate new electrokinetic theories.
阳离子双嵌段共聚物纳米粒子已通过在正十二烷中进行聚合诱导自组装（PISA）制备而成。通过将油溶性阳离子甲基丙烯酸单体（2 -（甲基丙烯酰氧基）乙基）三甲基铵四（3,5 - 双（三氟甲基）苯基）硼酸盐与SMA或BzMA进行统计共聚，对先前报道的聚（甲基丙烯酸硬脂酯）-聚（甲基丙烯酸苄酯）（PSMA - PBzMA）PISA配方（2016年，，5078 - 5090）进行了改性，以制备带电荷壳层或带电荷核的纳米粒子。研究了电动现象与许多变量的函数关系（体积函数、粒径、溶剂粘度和每条链上离子数的函数）。这些数据与由抗衡离子凝聚控制的电泳一致，这在无盐介质中通常会观察到。然而，存在几个有趣且意想不到的特征。特别地，带电荷壳层的纳米粒子比等效的带电荷核纳米粒子具有更低的电泳迁移率，并且随着壳层中阳离子稳定剂链的比例降低，电泳迁移率的大小会增加。这些结果表明，阳离子PSMA - PBzMA球体在非极性溶剂中提供了一个有趣的电泳纳米粒子新例子。此外，它们应该为评估新的电动理论提供一个理想的模型系统。
