Chemical Engineering Department, Hacettepe University, 06800 Ankara, Turkey; Institute of Pharmaceutical Sciences, Pharmaceutical (Bio-)Analysis, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany.
Institute of Pharmaceutical Sciences, Pharmaceutical (Bio-)Analysis, University of Tübingen, Auf der Morgenstelle 8, 72076 Tübingen, Germany.
Talanta. 2019 Jun 1;198:330-336. doi: 10.1016/j.talanta.2019.01.116. Epub 2019 Feb 6.
In this study, polyhedral oligomeric silsesquioxane (POSS)-based capillary monoliths with short alkyl chain ligand in the form of butyl (C4) were synthesized via two different polymerization routes, namely UV-initiated free radical copolymerization of methacrylate-derivatized POSS (POSS-MA) with butylmethacrylate (BMA) and UV-initiated thiol-methacrylate copolymerization of POSS-MA with butanethiol (BT). An organosilicon monolith with a pore size distribution lying on both mesoporous and macroporous scales, a lower mean pore size and a higher specific surface area was obtained with UV-initiated thiol-methacrylate polymerization. Both monoliths were then comparatively evaluated for gradient separation of proteins under reversed phase conditions in nano-liquid chromatography. The chromatographic performance was defined in terms of peak-resolution and peak capacity. Four carbon (C4) functionalized-poly(POSS-MA) monolith produced by UV-initiated thiol-methacrylate polymerization exhibited better separation performance with higher peak resolutions and peak capacities. Both, the morphological characterization of monoliths and the results of gradient separation of proteins showed that thiol-methacrylate polymerization was more suitable for the synthesis of C4 functionalized organosilicon based stationary phases for reversed-phase protein separation. The monolith prepared by thiol-methacrylate polymerization was also successfully applied for impurity analysis of two important hormones, namely insulin and genotropin. A comparison with a commercial poly(styrene-co-divinylbenzene) monolith documented the good chromatographic performance of the new BT-attached poly(POSS-MA) monolith.
在这项研究中，通过两种不同的聚合途径合成了具有短链烷基配体丁基（C4）的多面体低聚倍半硅氧烷（POSS）基毛细管整体柱：甲基丙烯酸酯衍生的 POSS（POSS-MA）与丁基甲基丙烯酸酯（BMA）的 UV 引发自由基共聚和 POSS-MA 与丁硫醇（BT）的 UV 引发巯基-甲基丙烯酸酯共聚。通过 UV 引发的巯基-甲基丙烯酸酯聚合，得到了一种具有介孔和大孔尺度的孔分布、更小的平均孔径和更高的比表面积的有机硅整体柱。然后，在反相条件下的纳流液相色谱中，对两种整体柱进行了蛋白质梯度分离的比较评估。色谱性能用峰分辨率和峰容量来定义。通过 UV 引发的巯基-甲基丙烯酸酯聚合生成的四个碳（C4）功能化聚（POSS-MA）整体柱具有更好的分离性能，具有更高的峰分辨率和峰容量。整体柱的形态特征和蛋白质的梯度分离结果表明，巯基-甲基丙烯酸酯聚合更适合用于合成用于反相蛋白质分离的 C4 功能化有机硅固定相。通过巯基-甲基丙烯酸酯聚合制备的整体柱还成功地应用于两种重要激素胰岛素和生长激素的杂质分析。与商业的聚苯乙烯-二乙烯基苯整体柱的比较证明了新的 BT 键合聚（POSS-MA）整体柱具有良好的色谱性能。
