Fesenmeier Daniel J, Park Sungwan, Kim Seyoung, Won You-Yeon
Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA.
Davidson School of Chemical Engineering, Purdue University, West Lafayette, IN 47907, USA; Purdue University Center for Cancer Research, West Lafayette, IN 47906, USA.
J Colloid Interface Sci. 2022 Jul;617:764-777. doi: 10.1016/j.jcis.2022.03.008. Epub 2022 Mar 14.
The surface mechanical properties of poly(styrene)-poly(ethylene glycol) (PS-PEG) micelles are influenced by the PEG corona structure. Changes in micelle aggregation number as well as changes in the PEG end group and linking group chemistry of the PS-PEG block copolymer are expected to alter PEG corona characteristics and therefore affect surface mechanical properties of the resulting micelle film.
Different sized micelles comprised of PS-PEG block copolymer chains were formulated by equilibrating micelles in different ratios of acetone/water mixtures and subsequently removing acetone using dialysis. Additionally, micelles of a similar size and PS-PEG molecular weight but slightly different chemistry were formulated. The micelles were characterized using dynamic light scattering (DLS), transmission electron microscopy (TEM), H NMR, surface pressure-area isotherms and Brewster angle microscopy (BAM).
The reduction in micelle aggregation number results in the subsequent monolayer having higher compressibility moduli and bending stiffnesses and collapsing at lower surface pressures. Micelle hydrophobicity was shown to improve readsorption of micelles to interface after collapse. Analysis of Brewster angle microscopy images of out-of-plane wrinkle structures which formed upon monolayer collapse indicates the presence of continuous 1 nm thick PEG layer which allows micelle monolayers to bend under high compression.
聚(苯乙烯)-聚(乙二醇)(PS-PEG)胶束的表面机械性能受PEG冠层结构影响。预计PS-PEG嵌段共聚物的胶束聚集数变化以及PEG端基和连接基团化学性质的变化会改变PEG冠层特性,从而影响所得胶束膜的表面机械性能。
通过在不同比例的丙酮/水混合物中平衡胶束,随后用透析法除去丙酮,制备了由PS-PEG嵌段共聚物链组成的不同尺寸胶束。此外,还制备了尺寸和PS-PEG分子量相似但化学性质略有不同的胶束。使用动态光散射(DLS)、透射电子显微镜(TEM)、核磁共振氢谱(¹H NMR)、表面压力-面积等温线和布鲁斯特角显微镜(BAM)对胶束进行表征。
胶束聚集数的减少导致随后的单分子层具有更高的压缩模量和弯曲刚度,并在较低的表面压力下塌陷。研究表明,胶束疏水性可改善胶束塌陷后重新吸附到界面的情况。对单分子层塌陷时形成的面外皱纹结构的布鲁斯特角显微镜图像分析表明,存在连续的1纳米厚PEG层,这使得胶束单分子层在高压缩下能够弯曲。