Radical-mediated step-growth: Preparation of hybrid polymer monolithic columns with fine control of nanostructural and chromatographic characteristics

被引:31
作者
Alves, Filipa [1 ]
Nischang, Ivo [1 ]
机构
[1] Johannes Kepler Univ Linz, Inst Polymer Chem, A-4060 Leonding, Austria
基金
奥地利科学基金会;
关键词
Adsorption; Click chemistry; Mass transfer; Network Ideality; Step-growth; Partition; PERFORMANCE LIQUID-CHROMATOGRAPHY; REVERSED-PHASE CHROMATOGRAPHY; SMALL MOLECULES; SEPARATION EFFICIENCY; CLICK POLYMERIZATION; MACROPOROUS POLYMER; POROUS PROPERTIES; STATIONARY-PHASE; SILICA; MORPHOLOGY;
D O I
10.1016/j.chroma.2015.08.019
中图分类号
Q5 [生物化学];
学科分类号
071010 ; 081704 ;
摘要
The currently most successful type of porous polymer monoliths utilized in chromatography is prepared by free-radical cross-linking (co)polymerization in porogenic solvents and a single-step molding process. Though such types of materials are well-recognized in the scientific community, they suffer from their multi-scale heterogeneity originating from the nanoscale through to their microscale and ultimately limited performance on their macroscale. This is in particular true when estimating their performance under equilibrium (i.e. isocratic) elution conditions for retained compounds. In this contribution, we study a new concept in the preparation of porous monolithic hybrid materials based on polyhedral oligomeric vinylsilsesquioxanes which undergo radical mediated step-growth cross-linking with thiol-linkers. Fundamental characterization of this new entry of materials is performed via a variety of characterization approaches including infrared and Raman spectroscopies, thermogravimetric analysis, gel fraction, dry-state surface area analysis, and visualization of the capillary-scale porous structure by scanning electron microscopy. This characterization identifies that a rational choice of experimental conditions in monolith preparation leads to destined and desirable materials' properties, in particular with experimentally accessible near-ideal nanoscale network structures. With the obtained structural informations at hand, we finally evidence the monoliths' tailored chromatographic performance by isocratic elution experiments of structurally similar small molecules under reversed-phase type of chromatographic conditions. This validates the fundamental origin for an improved performance of these types of monolithic materials under solvated conditions that has its foundation established in the creation of near-ideal nanoscale networks of material. This identified ideality is manifested in an enhanced and almost retention-insensitive performance in liquid chromatographic separations of small molecules across wide ranges of retention factors over at least two orders of magnitude and wide ranges of mobile phase compositions. Such experimental observation is explained by a more homogeneous energetic distribution of partition and adsorption sites. A reference analysis of normalized plate height data at varied retention was performed and set in context with data of state-of-the-art silica- and polymer-based monoliths. This analysis clearly identifies the present materials to display performance behavior clearly located in the domain of derivatized silica-based monoliths. (C) 2015 The Authors. Published by Elsevier B.V.
引用
收藏
页码:112 / 125
页数:14
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