Analytical-Chemistry Group, University of Amsterdam, van't Hoff Institute for Molecular Sciences , Science Park 904, 1098 XH Amsterdam, The Netherlands.
TI-COAST , Science Park 904, 1098 XH Amsterdam, The Netherlands.
Anal Chem. 2017 Sep 5;89(17):9167-9174. doi: 10.1021/acs.analchem.7b01906. Epub 2017 Aug 8.
Polymeric nanoparticles have become indispensable in modern society with a wide array of applications ranging from waterborne coatings to drug-carrier-delivery systems. While a large range of techniques exist to determine a multitude of properties of these particles, relating physicochemical properties of the particle to the chemical structure of the intrinsic polymers is still challenging. A novel, highly orthogonal separation system based on comprehensive two-dimensional liquid chromatography (LC × LC) has been developed. The system combines hydrodynamic chromatography (HDC) in the first-dimension to separate the particles based on their size, with ultrahigh-performance size-exclusion chromatography (SEC) in the second dimension to separate the constituting polymer molecules according to their hydrodynamic radius for each of 80 to 100 separated fractions. A chip-based mixer is incorporated to transform the sample by dissolving the separated nanoparticles from the first-dimension online in tetrahydrofuran. The polymer bands are then focused using stationary-phase-assisted modulation to enhance sensitivity, and the water from the first-dimension eluent is largely eliminated to allow interaction-free SEC. Using the developed system, the combined two-dimensional distribution of the particle-size and the molecular-size of a mixture of various polystyrene (PS) and polyacrylate (PACR) nanoparticles has been obtained within 60 min.
聚合物纳米粒子在现代社会中不可或缺，其应用范围广泛，从水基涂料到药物载体输送系统。虽然有许多技术可以确定这些粒子的多种性质，但将粒子的物理化学性质与内在聚合物的化学结构联系起来仍然具有挑战性。已经开发出一种新颖的、高度正交的分离系统，基于全面二维液相色谱（LC×LC）。该系统在第一维中结合流体力学色谱（HDC），根据颗粒大小分离颗粒，在第二维中结合超高效尺寸排阻色谱（SEC），根据每个 80 到 100 个分离级分的流体力学半径分离构成聚合物分子。该系统采用基于芯片的混合器，通过在线在四氢呋喃中溶解第一维分离的纳米颗粒来转化样品。然后使用固定相辅助调制聚焦聚合物带以提高灵敏度，并从第一维洗脱液中除去大部分水以允许无相互作用的 SEC。使用所开发的系统，在 60 分钟内获得了各种聚苯乙烯（PS）和聚丙烯酸酯（PACR）纳米粒子混合物的粒径和分子量的二维分布。
