Gas Phase Chromatography of Steroids

1 Gas Phase Analytical Methods for the Study of Steroid Hormones and their Metabolites.- I. Historical.- II. Analytical Methods.- 1. Single Component Analyses.- a) By High-sensitivity Non-selective Detection.- b) By High-sensitivity Selective Detection.- 2. Group Analyses.- 3. Multicomponent Analyses.- III. Instrumental Components.- 1. The Column and its Packing.- a) Column Types.- b) Supports.- c) Liquid Phases.- d) Preparation of Column Parkings.- 2. Detection Systems.- a) Hydrogen Flame Ionization.- b) Electron Capture.- c) Other Systems.- 3. Sample Introduction.- a) Samples in Solution.- b) Solid Injection.- IV. Derivatives.- 1. Reactions of Hydroxyl Groups.- 2. Reactions of Keto Groups.- 3. Reactions of Acids.- 4. Steroid Hormone Derivatives.- V. Separation Methods.- 1. With Non-selective Phases.- 2. With Selective Phases.- 3. Column Efficiency.- VI. GLC Characterization of Steroids.- 1. Relative Retention Time.- 2. Methylene Unit (MU) Values.- 3. Steroid Number (SN) Values.- VII. Problems of Quantification.- 1. Precision of GLC Systems (Flame Detection).- 2. Accuracy of GLC Systems (Flame Detection).- 3. Radioassay of GLC Effluent.- VIII. Analytical Applications with High-sensitivity Selective Detection.- IX. Structural Analysis by Gas Chromatography-Mass Spectrometry.- 1. The Gas Chromatograph-Mass Spectrometer as a Combined Instrument.- 2. Structural Analytical Methods.- X. Steroid Conjugates.- 1. ?-D-Glucosiduronic Acids.- 2. Sulfates.- References.- 2 Gas Phase Chromatographic Methods for Estrogens in Biological Fluids.- I. Introduction.- II. General Considerations.- 1. Hydrolysis.- 2. Extraction.- 3. Purification.- a) Solvent Partition.- b) Column Chromatography.- c) Thin-layer Chromatography.- d) Paper Chromatography.- e) Gel Chromatography.- III. Use of Estrogen Derivatives.- 1. Girard Separation.- 2. Methyl Ethers.- 3. Acetates.- 4. Trimethylsilyl Ethers (TMSi Ethers).- 5. O-Methoximes.- 6. Acetonides.- 7. Derivatives of Estrogens for Electron Capture Detection.- a) Chloroacetates.- b) Heptafluorobutyrates.- c) Monochloroalkylsilyl Ethers.- d) Pentafluorophenylhydrazones.- IV. Quantification and Identification of Gas Chromatographic Peaks of Estrogens.- V. Methods for the Estimation of Estrogens in Biological Extracts.- 1. Methods for Estriol in Urine of Pregnant Women.- 2. Methods for the Estimation of Estrone, Estradiol-17? and Estriol in Pregnancy Urine.- 3. Methods for the Estimation of Estrone, Estradiol and Estriol in Nonpregnancy Urine.- 4. Methods for the Estimation of Estrone, Estradiol, Estriol and other Estrogens in Pregnancy Urine.- 5. Methods for the Estimation of Estrogens in Blood.- 6. Methods for the Estimation of Estrogens in Bile.- 7. Method for the Estimation of Estrogens in Tissue Extracts.- VI. Conclusion.- References.- 3 Gas Phase Chromatography of Progesterone and Related Steroids.- I. Introduction.- 1. "Metabolism"1 Gas Phase Analytical Methods for the Study of Steroid Hormones and their Metabolites.- I. Historical.- II. Analytical Methods.- 1. Single Component Analyses.- a) By High-sensitivity Non-selective Detection.- b) By High-sensitivity Selective Detection.- 2. Group Analyses.- 3. Multicomponent Analyses.- III. Instrumental Components.- 1. The Column and its Packing.- a) Column Types.- b) Supports.- c) Liquid Phases.- d) Preparation of Column Parkings.- 2. Detection Systems.- a) Hydrogen Flame Ionization.- b) Electron Capture.- c) Other Systems.- 3. Sample Introduction.- a) Samples in Solution.- b) Solid Injection.- IV. Derivatives.- 1. Reactions of Hydroxyl Groups.- 2. Reactions of Keto Groups.- 3. Reactions of Acids.- 4. Steroid Hormone Derivatives.- V. Separation Methods.- 1. With Non-selective Phases.- 2. With Selective Phases.- 3. Column Efficiency.- VI. GLC Characterization of Steroids.- 1. Relative Retention Time.- 2. Methylene Unit (MU) Values.- 3. Steroid Number (SN) Values.- VII. Problems of Quantification.- 1. Precision of GLC Systems (Flame Detection).- 2. Accuracy of GLC Systems (Flame Detection).- 3. Radioassay of GLC Effluent.- VIII. Analytical Applications with High-sensitivity Selective Detection.- IX. Structural Analysis by Gas Chromatography-Mass Spectrometry.- 1. The Gas Chromatograph-Mass Spectrometer as a Combined Instrument.- 2. Structural Analytical Methods.- X. Steroid Conjugates.- 1. ?-D-Glucosiduronic Acids.- 2. Sulfates.- References.- 2 Gas Phase Chromatographic Methods for Estrogens in Biological Fluids.- I. Introduction.- II. General Considerations.- 1. Hydrolysis.- 2. Extraction.- 3. Purification.- a) Solvent Partition.- b) Column Chromatography.- c) Thin-layer Chromatography.- d) Paper Chromatography.- e) Gel Chromatography.- III. Use of Estrogen Derivatives.- 1. Girard Separation.- 2. Methyl Ethers.- 3. Acetates.- 4. Trimethylsilyl Ethers (TMSi Ethers).- 5. O-Methoximes.- 6. Acetonides.- 7. Derivatives of Estrogens for Electron Capture Detection.- a) Chloroacetates.- b) Heptafluorobutyrates.- c) Monochloroalkylsilyl Ethers.- d) Pentafluorophenylhydrazones.- IV. Quantification and Identification of Gas Chromatographic Peaks of Estrogens.- V. Methods for the Estimation of Estrogens in Biological Extracts.- 1. Methods for Estriol in Urine of Pregnant Women.- 2. Methods for the Estimation of Estrone, Estradiol-17? and Estriol in Pregnancy Urine.- 3. Methods for the Estimation of Estrone, Estradiol and Estriol in Nonpregnancy Urine.- 4. Methods for the Estimation of Estrone, Estradiol, Estriol and other Estrogens in Pregnancy Urine.- 5. Methods for the Estimation of Estrogens in Blood.- 6. Methods for the Estimation of Estrogens in Bile.- 7. Method for the Estimation of Estrogens in Tissue Extracts.- VI. Conclusion.- References.- 3 Gas Phase Chromatography of Progesterone and Related Steroids.- I. Introduction.- 1. "Metabolism" of Progesterone.- 2. Qualitative Considerations.- 3. Quantitative Considerations.- II. Progesterone and Reduced Metabolites: Progesterone, 20?- and 20?-Hydroxypregn-4-en-3-one, 3? and 3?-Hydroxypregn-4-en-3-one, and Pregn-4-ene-3,20-Diols.- 1. Qualitative Observations.- 2. Excretion in Urine.- 3. Quantitative Estimation in Blood and Tissue.- 4. Sensitivity of Detection.- 5. Methods for Estimation in Human Peripheral Blood.- 6. Measurement of Progestins in Laboratory Animals.- 7. Conclusion.- III. Pregnanolones.- IV. Pregnanediols.- 1. Gas Chromatographic Separation of Isomeric Pregnanediols.- 2. Quantitative Estimation of Pregnanediol in Human Urine.- 3. Sensitivity of Detection.- 4. Specificity.- 5. Routine Estimations of Free Pregnanediol.- 6. Routine Estimations of Pregnanediol Diacetate.- 7. Routine Estimations of Pregnanediol Trimethylsilyl Ether.- 8. Accuracy and Precision.- 9. Conclusion.- V. 17?-Hydrogyprogesterone and Reduced Metabolites.- VI. Pregnanetriol in Human Urine.- VII. 6-Oxygenated Progesterone and Reduced Metabolites.- VIII. 11-Oxygenated Progesterone and Reduced Metabolites.- IX. 16-Oxygenated Progesterone and Reduced Metabolites.- X. 17?-Pregnanes.- XI. Other Pregnanes.- References.- 4 Gas Phase Chromatography of Androgens in Biological Samples.- I. Introduction.- II. Androgens in Blood Plasma.- 1. Testosterone in Plasma.- Conclusion.- 2. ?4-Androstenedione in Plasma.- Conclusion.- 3. 17-Ketosteroids (17-KS) in Plasma.- Conclusion.- III. Androgens in Urine.- 1. Testosterone in Urine.- Conclusion.- 2. 17-Ketosteroids in Urine.- Conclusion.- References.- 5 Gas Phase Chromatography of Corticosteroids in Biological Samples.- I. Introduction.- II. Cortisol, Prednisolone and Some of Their Metabolites.- 1. Thermal Decomposition Products.- 2. Oxidation Products.- a) Extraction.- b) Thin-layer Chromatography.- c) Bismuthate Oxidation.- d) Trimethylsilyl (TMSi) Ether Formation.- e) Gas Phase Chromatography.- f) Reproducibility.- g) Accuracy.- h) Recovery.- 3. Group Assay.- 4. Derivatives.- a) Bismethylenedioxy Derivatives.- b) 17?-Carbomethoxy Derivatives.- c) Acetates.- d) Heptafluorobutyrate Derivatives.- e) O-Methyloxime or Methoxime (MO) Derivatives.- f) Trimethylsilyl Ether Derivatives.- g) O-Methyloxime-trimethylsilyl Ether Derivatives.- h) Acetonides.- III. Corticosterone and its Metabolites.- 1. Oxidation Products.- 2. Derivatives.- a) 17?-Carbomethoxy Derivatives.- b) Acetates.- c) Trimethylsilyl Ether Derivatives.- d) O-Methyloxime-trimethylsilyl Ether Derivatives.- e) Acetonides.- IV. Aldosterone.- 1. Oxidation Products.- 2. Derivatives.- a) Acetates.- b) Trimethylsilyl Ether Derivatives.- V. Conclusion.- References.- Trivial and Systematic Names of Steroids.- Author Index.- Compound Index.- Steroid Technique Index.- Steroid Assay Index.