Quantitative column liquid chromatography : a survey of chemometric methods

ORGANIZATION 1.1 1.2 1.3 1.4 1.5 1.6 1.7 Introduction Functional Classification of Quantitative Methods Separation Mechanism Solute Properties Chromatogram Components Preview References I X X I 1 1 2 4 6 7 12 13 2. CHEMOMETRICS IN COLUMN LIQUID CHROMATOGRAPHY 14 2.1 2.2 2.3 2.4 2.5 2.6 Introduction Regression 2.2.1 Regression: Chromatographic Applications 2.2.2 Linear Regression 2.2.3 NomLinear Regression Implementing NomLinear Regression 2.3.1 2.3.2 Single-Parameter Search 2.3.3 Multiple-Parameter Search 2.3.4 Constraining the Parameter Values Error Propagation 2.4.1 2.4.2 Evaluating Error Propagation Statistical Experimental Design 2.5.1 2.5.2 Description and Assessment of Statistical Experimental Design Factor Analysis 2.6.1 Formulation of the Objective Function Error Types and Their Evaluation Applications of Statistical Experimental Design in LC Applications of Factor Analysis in LC2.6.2 Description and Assessment of Factor Analysis 2.7 Pattern Recognition 2.7.1 2.7.2 Applications of Pattern Recognition in LC Description and Assessment of Pattern Recognition 2.8 Conclusions: Chemometrics in LC 2.9 References 3. FRACTIONATION 3.1 3.2 3.3 3.4 3.5 3.6 3.7 3.8 Introduction Defining Acceptable Fractionation 3.2.1 Peak Shape Analysis 3.2.2 Resolution Assessment Mechanisms of Separation Predicting Fractionation 3.4.1 Selectivity Parameters 3.4.2 Solubility Parameters 3.4.3 Hydrophobic Fragmental Constants Selection of the Chromatographic Mode lsocratic Liquid Chromatography 3.6.1 3.6.2 Nomogram 3.6.3 Window Diagrams 3.6.4 Computer Search Methods 3.6.5 Overlapping Resolution Mapping Gradient Column Liquid Chromatography 3.7.1 The Gradient Elution Equation 3.7.2 3.7.3 Selection of Gradients 3.7.4 Conclusions: Fractionation One Variable at a Time Search Determination of the Actual Gradient Selection of lsocratic Conditions Using Gradient Scans3.9 References 4. DETECTION 4.1 Single-Channel Detectors 4.1.1 Characterizing Detector Response 4.1.2 4.1.3 Concentration from Well-Resolved Single-Solute Peaks Concentration from Well-Resolved Multi3olute Peaks 4.2 Multiple Single-Channel Photometric Detectors 4.3 Rapid Scan Spectrophotometers 4.4 Molecular Weight Identification in SEC 4.4.1 Intrinsic Viscosity Detection 4.4.2 Low Angle Laser Light Scattering 4.5 Conclusions: Detection 4.6 References 5. CALIBRATION 5.1 5.2 5.3 5.4 Introduction Calibration with Single-Solute Standards 5.2.1 5.2.2 Single-Solute Calibration for Polymers 5.2.3 Calibration with Multi3olute Standards 5.3.1 5.3.2 Calibration by Direct Search 5.3.3 Calibration by Intrinsic Viscosity Parameter Search The Quantitative Influence of System Conditions on Calibration Curves 5.4.1 Effect of Solute Concentration 5.4.2 5.4.3 5.4.4 5.4.5 Miscellaneous Effects Single-Solute Calibration for "Small" Molecules Single-Solute Universal Calibration for Polymers Methods Using Standards of Known Molecular Weight Distribution Effect of Mobile Phase Composition Eftect 01 Number of Chromatographic Columns Effect of Mobile Phase Flow Rate5.5 Conclusions: Calibration 5.6 References 6. RESOLUTION CORRECTION 6.1 6.2 6.3 6.4 6.5 6.6 6.7 6.8 6.9 6.10 Introduction Geometric Constructions Curve Fitting Accumulated Detector Response Deconvolution Correcting Molecular Weight Averages Calibration Curve Search New Polymer Detectors and Complex Polymers Conclusions: Resolution Correction References 236 237 241 241 242 245 248 249 254 255 256 264 265 Appendix 1 Example of an LC Non-Linear Regression Application: Use of the Nelder-Mead Simplex Search to Fit a Gaussian Shape to an Experimental Chromatogram 267 Appendix 2 Solvent Strength in the Snyder-Glajch-Kirkland Triangular Composition Diagram 286 Nomenclature 288 Subject Index