Monolithic Silicas in Separation Science

Klaus K. Unger studied chemistry at the Technical University of Darmstadt, Germany, where he also received his PhD. From 1977 to 2001 he was a professor in chemistry at the Johannes-Gutenberg University, Mainz, Germany, before heading a research group in bioseparations at Merck KGaA, Darmstadt, Germany, for eight years. His research interests are the design and synthesis of porous materials as adsorbents and catalysts, surface functionalization and characterization, the development of liquid phase separation methods, and multidimensional liquid chromatography in proteomics. After studying chemistry at Kyoto University, Japan, Nobuo Tanaka carried out postdocs in the USA at Pennsylvania, Washington and Northeastern Universities, before returning to Kyoto at the Kyoto Institute of Technology (KIT). Since April 2009 he has been working for GL Sciences, Inc., while working part time for KIT as Professor Emeritus. He is the editor of a journal and on the editorial board of several others. Professor Tanaka`s research interests include the development of chromatographic columns and stationary phases, particularly monolithic silica-based materials, as well as the separation of isotopes, isomers and environmental contaminants. Egidijus Machtejevas was born in Lithuania where he studied chemistry and biotechnology at Kaunas University of Technology. After gaining his PhD in analytical chemistry in 2001 he worked as a post-doc with Prof Unger at Mainz University. He joined the R&D Department at Merck KgaA in Darmstadt in 2008, where he is currently a product manager for chromatography. Egidijus Machtejevas has twenty scientific papers and six book chapters to his name, and his major research areas include multidimensional liquid chromatography, proteomics and the development of monolithic stationary phases for chromatography.

• PrefaceTHE BASIC IDEA AND THE DRIVERSDefinitionsMonoliths as Heterogeneous CatalystsMonoliths in Chromatographic SeparationsConclusion and Perspectives PART I: Preparation SYNTHESIS CONCEPTS AND PREPARATION OF SILICA MONOLITHSIntroductionBackground and ConceptsSynthesis of Silica MonolithsMonolithic Columns Prepared in the LaboratoryPREPARATION AND PROPERTIES OF VARIOUS TYPES OF MONOLITHIC SILICA STATIONARY PHASES FOR REVERSED-PHASE, HYDROPHILIC INTERACTION, AND ION-EXCHANGE CHROMATOGRAPHY BASED ON POLYMER-COATED MATERIALSStationary Phases for Reversed-Phase ChromatographyStationary Phases for Hydrophilic-Interaction Chromatography SeparationsStationary Phases for Ion-Exchange SeparationsAdvantages of Polymer-Coated Monolithic Silica Columns PART II: Characterization and Modeling CHARACTERIZATION OF THE PORE STRUCTURE OF MONOLITHIC SILICASMonolithic SilicasGeneral Aspects Describing Porous MaterialsCharacterization Methods of the Pore Structure of Monolithic SilicasComparison of the Silica Monolith Mesopore-Characterization DataComparison of the Silica Monolith Flow-Through Pore-Characterization DataMICROSCOPIC CHARACTERIZATIONSIntroductionPreparation of Macroporous Silica MonolithLaser Scanning Confocal Microscope ObservationImage ProcessingFundamental ParametersThree-Dimensional Observation of Deformations in Confined GeometryMODELING CHROMATOGRAPHIC BAND BROADENING IN MONOLITHIC COLUMNSIntroductionThe General Plate-Height ModelUser of the General Plate-Height Model to Predict Band Broadening in TSM StructuresConclusionCOMPARISON OF THE PERFORMANCE OF PARTICLE-PACKED AND MONOLITHIC COLUMNS IN HIGH-PERFORMANCE LIQUID CHROMATOGRAPHYIntroductionBasic Columns PropertiesComparison of the Through-Pore Structures and Related PropertiesThermodynamic PropertiesKinetic Properties and Column EfficiencyConclusions PART III: Applications QUANTITATIVE STRUCTURE-RETENTION RELATIONSHIPS IN STUDIES OF MONOLITHIC MATERIALSFundamentals of Quantitative Structure-Retention Relationships (QSSR)Quantitative Relationships between Analyte Hydrophobicity and Retention on Monolithic ColumnsQSSR Based on Structural Descriptors from Calculation ChemistryLSER on Monolithic ColumnsConcluding RemarksPERFORMANCE OF SILICA MONOLITHS FOR BASIC COMPOUNDS. SILANOL ACTIVITYIntroductionReproducibility of Commercial Monoliths for Analysis of BasesActivity of Monoliths towards Basic SolutesContribution of Overload to Peak Shapes of Basic SolutesVan Deemter Plots for Commercial MonolithsPerformance of Hybrid Capillary Silica Monoliths for Basic CompoundsQUALITY CONTROL OF DRUGSIntroductionAnalysis of PharmaceuticsNatural Products AnalysisAnalysis Speed and PerformanceMethod TransferSeparation of Complex MixturesMonolithic Derivatives and Versatile ApplicationSummary and ConclusionsMONOLITHIC STATIONARY PHASES FOR FAST ION CHROMATOGRAPHYFast Ion ChromatographyHistorical Development of Fast Ion Chromatography3 Advantages of the Bimodal Porous Structure of the Silica Monolith MatrixType and Properties of Silica Monolithic Columns Used in ICModification of Silica Monoliths for IC SeparationsOperational ParametersAnalytical ApplicationsFuture WorkMONOLITHIC CHIRAL STATIONARY PHASES FOR LIQUID-PHASE ENANTIOSEPARATION TECHNIQUESIntroductionOrganic Monolithic Materials for the Separation of EnantiomersSilica-Based Monolithic Materials for the Separation of EnantiomersSummary of the Present State-of-the-Art and Problems to be Solved in the FutureHIGH-SPEED AND HIGH-EFFICIENCY SEPARATIONS BY UTILIZING MONOLITHIC SILICA CAPILLARY COLUMNSIntroductionPreparation of Monolithic Silica Capillary ColumnsProperties of Monolithic Silica Capillary ColumnsMonolithic Silica Capillary Columns for High-Efficiency SeparationsMonolithic Silica Capillary Columns for High-Speed SeparationsFuture ConsiderationsSILICA MONOLITHIC COLUMNS AND MASS SPECTROMETRYIntroductionOffline Chromatography, LC MALDI MSOnline ESI LC/MS/MS for Proteomics and Selected Reaction Monitoring (SRM)Online Reactors and Affinity Columns Coupled to Mass Spectrometry ConclusionSILICA MONOLITHS FOR SMALL-SCALE PURIFICATION OF DRUG-DISCOVERY COMPOUNDSIntroductionInstrumental and Operating ConsiderationsPreparative Separations and Sample LoadingPurification of Drug-Discovery CompoundsConclusionsMONOLITHIC SILICA COLUMNS IN MULTIDIMENSIONAL LC-MS FOR PROTEOMICS AND PEPTIDOMICSIntroductionLiquid Chromatography as a Tool Box for ProteomicsSelectivity of Columns for MD-LCDimensions of Columns in MD-LCMonolithic Silica ColumnsApplications of Monolithic Silica in Proteomics -A Brief SurveySummary and ConclusionsSILICA MONOLITHS IN SOLID-PHASE EXTRACTION AND SOLID-PHASE MICROEXTRACTIONIntroductionExtraction ProcessExtraction PlatformsApplicationsConclusion and Outlook