title: Tuning preparation conditions towards optimized separation performance of thermally polymerized organo-silica monolithic columns in capillary liquid chromatography.
abstract: Tuning of preparation conditions, such as variations in the amount of a porogen, concentration of an aqueous acid catalyst, and adjustment in polymerization temperature and time, towards optimized chromatographic performance of thermally polymerized monolithic capillaries prepared from 3-(methacryloyloxy)propyltrimethoxysilane has been carried out. Performance of capillary columns in reversed-phase liquid chromatography was assessed utilizing various sets of solutes. Results describing hydrophobicity, steric selectivity, and extent of hydrogen bonding enabled comparison of performance of hybrid monolithic columns prepared under thermal (TSG) and photopolymerized (PSG) conditions. Reduced amounts of porogen in the polymerization mixture, and prolonged reaction times were necessary for the preparation of monolithic columns with enhanced retention and column efficiency that reached to 111,000 plates/m for alkylbenzenes with shorter alkyl chains. Both increased concentration of catalyst and higher temperature resulted in faster polymerization but inevitably in insufficient time for pore formation. Thermally polymerized monoliths produced surfaces, which were slightly more hydrophobic (a methylene selectivity of 1.28±0.002 TSG vs 1.20±0.002 PSG), with reduced number of residual silanols (a caffeine/phenol selectivity of 0.13±0.001 TSG vs 0.17±0.003 PSG). However, steric selectivity of 1.70±0.01 was the same for both types of columns. The batch-to-batch repeatability was better using thermal initiation compared to monolithic columns prepared under photopolymerized conditions. RSD for retention factor of benzene was 3.7% for TSG capillaries (n=42) vs. 6.6% for PSG capillaries (n=18). A similar trend was observed for columns prepared within the same batch.
authors.affiliation: Department of Physical Sciences, Barry University, Miami Shores, FL 33161, USA.
authors.forename: Deepa
authors.initials: D
authors.lastname: Gharbharan
authors.affiliation: Department of Physical Sciences, Barry University, Miami Shores, FL 33161, USA.
authors.forename: Denae
authors.initials: D
authors.lastname: Britsch
authors.affiliation: Department of Physical Sciences, Barry University, Miami Shores, FL 33161, USA.
authors.forename: Gabriela
authors.initials: G
authors.lastname: Soto
authors.affiliation: Department of Physical Sciences, Barry University, Miami Shores, FL 33161, USA.
authors.forename: Anna-Marie Karen
authors.initials: AM
authors.lastname: Weed
authors.affiliation: The Molecular Foundry, E. O. Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA.
authors.forename: Frantisek
authors.initials: F
authors.lastname: Svec
authors.affiliation: Department of Physical Sciences, Barry University, Miami Shores, FL 33161, USA. Electronic address: ZZajickova@barry.edu.
authors.forename: Zuzana
authors.initials: Z
authors.lastname: Zajickova
mesh_terms: D001554:Benzene; D056148:Chromatography, Reverse-Phase / Q000295:instrumentation* / Q000379:methods; D002911:Chrysenes / Q000032:analysis; D006358:Hot Temperature; D057927:Hydrophobic and Hydrophilic Interactions; D008689:Methacrylates / Q000737:chemistry*; D058105:Polymerization; D012821:Silanes / Q000737:chemistry*; D013237:Stereoisomerism; D013730:Terphenyl Compounds / Q000032:analysis
chemical_list: D002911:Chrysenes; D008689:Methacrylates; D012821:Silanes; D013730:Terphenyl Compounds; C492568:propyltrimethoxysilane; C009590:triphenylene; C017492:methacryloxypropyltrimethoxysilane; D001554:Benzene
keywords: Hybrid; Monolith; Organo-silica; Photo-polymerization; Sol–gel; Thermal polymerization