Kulsing Chadin, Knob Radim, Macka Mirek, Junor Paul, Boysen Reinhard I, Hearn Milton T W
School of Chemistry, Monash University, Melbourne, Victoria, 3800, Australia.
Department of Analytical Chemistry, Palacky University in Olomouc, 17. Listopadu 12, Olomouc 77146, Czech Republic.
J Chromatogr A. 2014 Aug 8;1354:85-91. doi: 10.1016/j.chroma.2014.05.065. Epub 2014 Jun 2.
A new method has been developed for the preparation of molecular imprinted polymers as porous layers in open tubular (MIP-PLOT) capillary column formats for use in chiral separations by capillary liquid chromatography. The synthesis was based on 'in-capillary' ultraviolet (UV) initiated polymerization using light emitting diodes (LEDs) in conjunction with the continuous delivery of the pre-polymerization reagents into the polymerization zone of the capillary using an automated capillary delivery device. The relationships between exposure times, UV-light intensity and polymer layer thickness have been determined, as well as the effects of reagent delivery rate and multiple LED exposures on the layer thickness for various compositions of pre-polymerization mixtures. The polymer surface morphology was investigated by scanning electron microscopy (SEM). The non-steroidal anti-inflammatory drug S-ketoprofen was used as the template for the preparation of the MIP imprinted PLOT coatings. The separation performance with the ketoprofen racemate was investigated by capillary liquid chromatography. In contrast to alternative methods, which require the use of expensive chiral selectors, the described MIP PLOT stationary phases used non-chiral polymer precursors to create enantioselective nano-cavities through molecular self-assembly processes. The described fabrication methods provide a new avenue to tailor-make chiral MIP-PLOT capillary columns for the separation of chiral compounds present in complex or racemic analyte mixtures of chemical and biological origin.
已开发出一种新方法,用于制备作为开管(MIP-PLOT)毛细管柱形式的多孔层的分子印迹聚合物,用于毛细管液相色谱法的手性分离。合成基于“毛细管内”紫外(UV)引发的聚合反应,使用发光二极管(LED)并结合使用自动毛细管输送装置将预聚合试剂连续输送到毛细管的聚合区。已确定曝光时间、紫外光强度与聚合物层厚度之间的关系,以及试剂输送速率和多次LED曝光对不同预聚合混合物组成的层厚度的影响。通过扫描电子显微镜(SEM)研究了聚合物表面形态。非甾体抗炎药S-酮洛芬用作制备MIP印迹PLOT涂层的模板。通过毛细管液相色谱法研究了酮洛芬外消旋体的分离性能。与需要使用昂贵手性选择剂的替代方法相比,所述的MIP PLOT固定相使用非手性聚合物前体通过分子自组装过程创建对映选择性纳米腔。所描述的制造方法为定制手性MIP-PLOT毛细管柱提供了一条新途径,用于分离化学和生物来源的复杂或外消旋分析物混合物中存在的手性化合物。