The Bile Acids: Chemistry, Physiology, and Metabolism: Volume 4: Methods and Applications

ISBN-13: 9781461282365 / Angielski / Miękka / 2011 / 604 str.

K. D. R. Setchell; David Kritchevsky;Padmanabhan P. Nair

Opis

Over a decade has elapsed since the last volume in this series was published. At that time we considered that we had comprehensively covered all aspects relating to bile acid chemistry and physiology. However, major strides have been made in our understanding of the physiology and pathophysiology of bile acids, due largely to the great advances which have taken place in analytical technology. As a result, the need to document these advances was felt acutely, and therefore this volume is devoted to methodologies in bile acid analysis and their applications. This volume includes twelve chapters written by prominent scientists in the field of bile acid research. The initial chapter discusses techniques of extraction and isolation of bile acids from biological fluids. It is followed by descriptions of physical methods of analysis and discussions of the way these techniques have been applied in the field of bile acid research. Of practical value is the inclusion of a comprehensive list of spectra obtained for refer ences by nuclear magnetic resonance spectroscopy and mass spectrometry . These chapters are followed by reviews of biological methods of immuno assay and bioluminescence. Specific applications of these techniques are then addressed in contributions relating to bile acid analysis of tissue, serum, urine, and feces. With this integrated approach we have attempted to provide a volume which represents a comprehensive review of the analytical field of bile acids, while also serving as a useful reference book for those workers involved in bile acid analysis."

Spis treści

1 Techniques for Extraction and Group Separation of Bile Acids.- 1. Introduction.- 2. Extraction.- 2.1. Solvent Extraction.- 2.2. Solid-Phase Extraction.- 3. Purification and Group Separation.- 3. 1. Adsorption Chromatography.- 3.2. Partition Chromatography.- 3.3. Electrophoresis.- 3.4. IonExchange.- 4. Hydrolysis and Solvolysis.- 4.1. Alkaline Hydrolysis.- 4.2. Cholylglycine Hydrolase.- 4.3. ?-Glucuronidase.- 4.4. Solvolysis.- 4.5. Esterification.- 5. Conclusions.- References.- 2 High-Performance Liquid Chromatography.- 1. Introduction.- 2. Chromatographic Behavior of Bile Acids.- 2.1. Unconjugated, Glycine-, and Taurine-Conjugated Bile Acids.- 2.2. Bile Acid Sulfates and Glucuronides.- 3. Detection Methods.- 3.1. Direct Determination.- 3.2. Coupling with Enzymic Reaction.- 3.3. Derivatization of Carboxyl and Hydroxyl Groups.- 4. Application of HPLC to Biological Specimens.- 4.1. Direct Determination.- 4.2. Derivatization Methods.- 5. Conclusions.- References.- 3 Nuclear Magnetic Resonance.- 1. Introduction: Why Use NMR for Bile Acids?.- 2. Basic Principles of NMR.- 2.1. The NMR Phenomenon.- 2.2. Chemical Shift.- 2.3. Peak Integrals.- 2.4. Multiplicities of Signals: Spin Coupling.- 2.5. 13C-1H Coupling.- 2.6. Preparation of Samples for NMR.- 3. Proton NMR of Bile Acids.- 3.1. Introduction.- 3.2. Methyl Proton Resonances.- 3.3. Solvent Effects.- 3.4. Derivatives of Bile Acids.- 3.5. Spin Coupling: Splitting of Proton Signals.- 4. 13C NMR of Bile Acids.- 5. Recent Advances in NMR Spectroscopy.- 5.1. Superconducting Magnets.- 5.2. Fourier-Transform NMR.- 5.3. Spin Decoupling.- 5.4. Nuclear Overhauser Effect Experiments.- 5.5. Relaxation.- 5.6. Paramagnetic Shift Reagents.- 5.7. Pulse Sequences.- 6. Application of NMR to the Physical Chemistry of Bile Acids.- 7. NMR in the Biosynthesis and Metabolism of Bile Acids.- 8. ConclUding Remarks.- References.- 4 X-Ray Crystallography.- l. Introduction.- 2. X-Ray Diffraction by Single Crystals.- 3. Sample Preparation.- 4. Experimental Measurements.- 5. Structure Determination.- 6. Interpretation of Results.- 7. Pitfalls.- 8. Examples.- References.- 5 Mass Spectrometry of Bile Acids.- 1. Introduction.- 2. Principles and Instrumentation.- 2.1. Ion Separation.- 2.2. Ion Detection.- 2.3. Ion Recording.- 3. Ionization Methods.- 3.1. Electron Impact.- 3.2. Chemical Ionization.- 3.3. Field and Laser Desorption.- 3.4. Fast Atom Bombardment.- 4. Methods of Sample Introduction.- 4. 1. Direct Insertion Probe.- 4.2. Gas Chromatographic Inlet.- 4.3. Liquid Chromatographic Inlet.- 5. Mass Spectrometric Fragmentation of Bile Acids.- 5.1. Monohydroxy Bile Acids.- 5.2. Dihydroxy Bile Acids.- 5.3. Trihydroxy Bile Acids.- 5.4. Tetrahydroxy Bile Acids.- 5.5. Oxo Bile Acids.- 5.6. Unsaturated Bile Acids.- 5.7. Modified Side-Chain Bile Acids.- 5.8. Conjugated Bile Acids.- 6. Quantitative Analysis of Bile Acids.- 7. Bile Acids Labeled with Stable Isotopes.- 8. Application of Mass Spectrometry to the Determination of Bile Acids in Biological Fluids.- 8. 1. Serum.- 8.2. Bile.- 8.3. Feces.- 8.4. Meconium.- 8.5. Amniotic Fluid.- 8.6. Urine.- 8.7. Tissue.- 9. Compendium of Mass Spectra of Bile Acids.- References.- 6 Immunological Methods for Serum Bile Acid Analysis.- 1. Introduction.- 2. Physicochemical State of Bile Acids in Serum.- 3. Immunoassay.- 4. Preparation of Antigenic Bile Acids.- 5. Antibodies.- 5.1. Antibody Characterization: Titer and Affinity.- 5.2. Specificity.- 6. Labeled Bile Acids.- 7. Assay Procedure.- 8. Comparison of Methods.- 9. Comparison between Methods.- 10. Enzyme Immunoassay.- 11. Serum Bile Acids in Physiology and Pathology.- 11.1. Serum Bile Acids as a Mirror of the Enterohepatic Circulation.- 11.2. Determinants of Serum Bile Acid Levels.- 11.3. Serum Bile Acids in Hepatobiliary Disease.- 11.4. Diagnostic Accuracy.- 11.5. Modalities of Serum Bile Acid Detennination.- 11.6. Serum Bile Acids in Bile Acid Malabsorption Syndromes.- 11.7. Serum Bile Acid Levels in Infancy and Childhood.- References.- 7 Bioluminescence Assays Using Immobilized Enzymes in Bile Acid Analysis.- 1. Introduction.- 2. Bioluminescence Assays.- 2.1. Principles.- 2.2. Coimmobilized Enzymes.- 3. Material.- 3. 1. Enzymes.- 3.2. Bile Acids.- 3.3. Samples.- 3.4. Instruments.- 4. Methods.- 4.1. Enzyme Immobilization.- 4.2. Continuous-Flow Systems.- 4.3. Assay Techniques.- 4.4. Standard Curves.- 4.5. Assay Specificity.- 4.6. Stability.- 4.7. Sample Preparation.- 4.8. Recovery and Precision.- 4.9. Calculations.- 4.10. Assay Validations.- 5. Results.- 5.1. Standards.- 5.2. Validation.- 5.3. Some Applications.- 6. Discussion.- 6.1. The Method.- 6.2. Clinical Applications.- 6.3. Experimental Applications.- 7. Summary.- References.- 8 Bile Acids in Extrahepatic Tissues.- 1. Introduction.- 2. Analytical Methods.- 2.1. Chemicals.- 2.2. Extraction Method I.- 2.3. Extraction Method II.- 2.4. Removal of Fatty Acids.- 2.5. TLC Separation of Bile Acids into Groups.- 2.6. TLC Identification of Bile Acids.- 2.7. High-Pressure Liquid Chromatography.- 2.8. Mass Spectrometry.- 2.9. Cholesterol 7?-Hydroxylase and Hydroxymethylglutaryl-CoA Reductase.- 2.10. Lipid Quantitation.- 2.11. Enzymatic Assay of Total Bile Acids.- 2.12. Plasma Lipoprotein Separation.- 2.13. Tissue Collection.- 2.14. Experimental Designs.- 3. Applications.- 3. 1. Identification and Quantitation of Cholanoic Acids.- 3.2. Human Study.- 3.3. Steroid Kinetics in Rats.- 4. Conclusions.- References.- 9 Tissue-Bound Bile Acids.- 1. Introduction.- 2. Methodology.- 2.1. Isolation Procedures.- 2.2. Enzymatic Cleavage of TBL.- 2.3. Isolation of N-?-Lithocholyl Lysine from Tissues by Nonenzymatic Hydrolysis.- References.- 10 Serum Bile Acids.- 1. Introduction.- 2. Serum Bile Acids and the Different Enterohepatic Bile Acid Cycles in Normal Humans.- 2.1. Bile Acid Distribution.- 2.2. Absorption of Bile Acids from the Intestine into the Portal Blood.- 2.3. Bile Acids in the Portal Blood.- 2.4. Hepatic Extraction from the Portal Vein.- 2.5. Hepatic Uptake of Bile Acids from the Systemic Circulation.- 2.6. Compartmental Models and Peripheral Bile Acid Concentrations.- 3. Serum Bile Acid Measurements and the Dynamics of the Normal Enterohepatic Circulations.- 3.1. Radioimmunoassay.- 3.2. Gas-Liquid Chromatography/Mass Spectrometry.- 3.3. High-Pressure Liquid Chromatography.- 3.4. Unconjugated Serum Bile Acid Concentrations.- 3.5. Protein-Bound Serum Bile Acid Concentrations.- 4. Serum Bile Acids and Liver Disease.- 4.1. Total 3a-Hydroxy Bile Acid Concentrations.- 4.2. The Specificity of Serum Bile Acid Measurements for Liver Disease.- 4.3. Elevated Peripheral Bile Acid Concentrations in Liver Cirrhosis.- 4.4. Serum Bile Acid Hydroxylation Patterns in Liver Disease.- 5. Gas Chromatography-Mass Spectrometry and Monohydroxy Bile Acids in Liver Disease.- 6. Serum Bile Acid Composition in Other Circumstances.- 6.1. Serum Bile Acids during Bile Acid Feeding.- 6.2. Serum Bile Acids during Pregnancy.- 7. Conclusion.- References.- 11 Urinary Bile Acids.- 1. Introduction.- 2. Methodology.- 2.1. Liquid-Liquid Extraction.- 2.2. Liquid-Solid Extraction.- 2.3. Separation into Subclasses.- 3. Bile Acids Detected in the Urine.- 3.1. Bile Acid Groups.- 3.2. Bile Acid Pattern in the Urine of Healthy Adults.- 3.3. Bile Acids in the Urine of the Newborn.- 3.4. Urinary Bile Acids in Hepatobiliary Diseases.- 3.5. Other Diseases Associated with Alterations in Urinary Bile Acid Excretion.- 4. Origin of the Atypical Bile Acids in the Urine.- 4.1. Conjugation Reactions.- 4.2. Atypical Hydroxylations.- 4.3. Alterations of the Side Chain.- 4.4. Epimerizations.- 4.5. Unsaturated Bile Acids.- 5. The Renal Clearance of Bile Acids.- 6. Conclusion.- References.- 12 Fecal Bile Acids.- 1. Introduction.- 2. Methods for Determination of Fecal Bile Acids.- 2.1. Early Techniques.- 2.2. Techniques Based on Gas-Liquid Chromatography.- 2.3. Gas-Liquid Chromatography-Mass Spectrometry.- 2.4. Enzymatic Methods.- 2.5. High-Pressure Liquid Chromatography Analysis.- 2.6. Isotopic Methods.- 2.7. General Problems in Fecal Bile Acid Analysis.- 3. Fecal Bile Acid Excretion in Health.- 3.1. Normal Patterns of Fecal Bile Acid Excretion in Adults.- 3.2. Bile Acids in Children and Infants.- 3.3. Meconium.- 3.4. Factors Influencing Bile Acid Excretion.- 4. Fecal Bile Acid Excretion in Disease.- 4.1. Colon Cancer.- 4.2. Adenomatous Polyps.- 4.3. Familial Polyposis.- 4.4. Ulcerative Colitis.- 4.5. Breast Cancer.- 4.6. Crohn’s Disease.- 4.7. Diverticulosis.- 4.8. Diarrhea and Malabsorption.- 4.9. Ileostomy and Ileal Resection.- 4.10. Inborn Errors of Metabolism Involving Bile Acid Metabolism.- 4.11. Hyperlipidemia.- 4.12. Liver Disease.- 4.13. Cholelithiasis.- 4.14. Diabetes.- 5. Effect of Diet and Drugs on Fecal Bile Acid Excretion.- 5.1. Dietary Fiber.- 5.2. Bile Acid Sequestrants.- 5.3. Antibiotics.- 5.4. Dietary Factors Influencing Bile Acid Metabolism.- 5.5. Absorbable Hypolipidemic Drugs.- 5.6. Exogenous Bile Acid Therapy.- 6. Conclusions.- References.