Alkaloids

It is refreshing to find a book treating alkaloid analysis with all the latest techniques such as inverse-detected two dimensional NMR, GC/MS, and HPLC associated techniques. There have been many developments in the field of alkaloid analysis since the 1950s, not the least of which are the various powerful spectroscopic methods, which dominate this volume. Included also are the various aspects of tobacco alkaloids and analysis in various situations. The complexities of sampling and analysis in tobacco smoke is explained. Analysis of alkaloids produced by tobacco root cell cultures is included, while genetic and chemical analysis is described for Papaver, a plant of considerable medicinal significance.

Contenu

Isolation, Identification, and Structure Elucidation of Alkaloids A General Overview.- 1 Introduction.- 2 Isolation.- 2.1 Extraction.- 2.2 Chromatography.- 2.3 Artifacts.- 2.4 Selective Detection.- 3 Identification and Structure Elucidation.- 3.1 Spectroscopic Method.- 3.1.1 UV (Ultaviolet).- 3.1.2 IR (Infrared).- 3.1.3 ORD and CD (Optical Rotation Dispersion and Circular Dichromism).- 3.1.4 X-Ray Crystallography.- 3.1.5 MS (Mass Spectrometry).- 3.1.6 NMR (Nuclear Magnetic Resonance).- 3.1.7 1H-NMR.- 3.1.8 13C-NMR.- 3.1.9 2D-NMR.- 4 Strategy.- 5 Future Prospects.- References.- Inverse-Detected 2D-NMR Applications in Alkaloid Chemistry.- 1 Introduction.- 2 Historical Background.- 3 Suppression of Unwanted Magnetization Arising from 1H-12C Species.- 4 Inverse-Detected One-Bond Heteronuclear Shift Correlation Experiments.- 4.1 HMQC.- 4.2 DEPT-HMQC.- 4.3 HSQC.- 4.4 HMQC Using Spin-Locking Fields.- 4.5 Comparison of the Available Inverse-Detected One-Bond Heteronuclear Correlation Experiments.- 5 Long-Range Heteronuclear Chemical Shift Correlation - HMBC.- 6 HMQC-TOCSY and Other Hyphenated Inverse-Detected 2D Experiments.- 6.1 Interpretation of HMQC-TOCSY Spectra.- 6.2 Modifications of the HMQC-TOCSY Experiment - Inverted Direct Responses.- 6.3 DEPT-HMQC-TOCSY.- 6.4 Suppression of Direct Responses in HMQC-TOCSY Spectra.- 7 Other Inverse-Detected NMR Experiments -Selective and F1 Region-Selected Experiments.- 7.1 Selective One-Dimensional Analogs of HMBC - SIMBA.- 7.2 One-Dimensional HMQC-TOCSY.- 7.3 F1 Region-Selected HMBC.- 7.4 HMQC-NOESY and HMQC-ROESY.- 8 Sample Requirements.- 9 Applications of Inverse-Detected NMR Techniques to Alkaloid Chemistry. Structural Problems.- 9.1 Terrestrial Alkaloids.- 9.1.1 Carbazole Alkaloids.- 9.1.2 Indolizidine Alkaloids.- 9.1.3 Diterpene Alkaloids.- 9.1.4 Indole-Derived Alkaloids.- 9.1.5 Pyrrole, Imidazole, Pyrrolizidine, Pyridine, and Related Alkaloids.- 9.2 Marine Alkaloids.- 9.2.1 Quinoline Alkaloids.- 9.2.2 Acridine Alkaloids.- 9.2.3 Tetrahydroisoquinoline Alkaloids.- 9.2.4 Pyrrole and Imidazole-Derived Alkaloids.- 9.2.5 Pyridine-Containing Alkaloids.- 9.2.6 Indole Alkaloids.- 9.2.7 Carbazole Alkaloids.- 9.2.8 Oxazole/Thiazole Containing Alkaloids.- 9.2.9 Bromotyrosine/Bromodopamine-Derived Alkaloids.- 9.2.10 Guanidine-Derived Alkaloids.- 10 Conclusion.- References.- Electrochemical Detection of Alkaloids in HPLC.- 1 Introduction.- 2 Principles of HPLC with Electrochemical Detection.- 2.1 Basic Principles of Electrochemical Detection.- 2.2 Electroactive Functional Groups in Alkaloids.- 2.3 Mobile Phase.- 2.3.1 Conductivity.- 2.3.2 Background Current and Noise.- 2.3.3 pH.- 2.4 Electrode Materials and Flow Cells.- 2.5 Selection of Applied Potential.- 3 Methods of Detection in Plants.- 3.1 Psilocin and Psilocybin in Fungi.- 3.2 Hordenine in Germinating Barley.- 3.3 Catharanthus Alkaloids in Cell Culture.- 3.4 Atropine in Belladonna Preparations.- 3.5 Castanospermine in Leaves.- 4 Possible Methods for Detecting Other Alkaloids.- 4.1 Opium Alkaloids.- 4.2 Physostigmine.- 4.3 Coca Alkaloids.- 4.4 Sparteine.- 5 Conclusions and Future Directions.- References.- Gas Chromatography in the Analysis of Alkaloids.- 1 Introduction.- 2 Pyrrolizidine Alkaloids.- 3 Quinolizidine Alkaloids.- 4 Tropane Alkaloids.- 5 Quinoline Alkaloids.- 6 Morphinan Alkaloids.- 7 Terpenoid Indole Alkaloids.- 8 Ergot Indole Alkaloids.- 9 Steroidal Alkaloids.- 10 Diterpenoid Alkaloids.- 11 Other Alkaloids.- 12 Conclusion.- References.- Alkaloid Analysis in Flue-Cured Tobacco.- 1 Introduction.- 2 Factors Affecting Alkaloid Concentration.- 3 Methods of Analysis of Tobacco Alkaloids.- 3.1 Steam Distillation.- 3.2 Autoanalyzer.- 3.3 Chromatographic Analysis of Tobacco Alkaloids.- 3.3.1 Paper Chromatography.- 3.3.2 Paper Chromatography - Ultraviolet Spectrophotometer.- 3.3.3 Thin-Layer Chromatography.- 3.3.4 Gas Chromatography.- 3.3.5 High Performance Liquid Chromatography.- 3.4 Cundiff-Markunas Extraction Method.- 3.5 Alternative Methods.- 4 Summary.- References.- Assessment of Burley and Dark Tobacco Alkaloids During Storage, Aging, and Fermentation.- 1 Importance of Pyridine Alkaloids to Tobacco Quality and Usability.- 2 Importance of Storage, Aging, and Fermentation.- 3 Chemical Analyses.- 3.1 Total Tobacco Alkaloids.- 3.2 Individual Tobacco Alkaloids.- 3.3 Nitrite.- 3.4 Calcium.- 3.5 Moisture.- References.- Detection of Alkaloids in Environmental Tobacco Smoke.- 1 Introduction.- 1.1 Tobacco and Tobacco Smoke.- 1.2 Tobacco-Related Alkaloids.- 1.3 Pyrolysates of Tobacco Alkaloids.- 1.4 Tobacco-Related Alkaloids as Tracers of ETS in Indoor Air.- 2 Overview of Sampling and Analysis Methods.- 3 Time-Integrated Sampling/Gas Chromatographic Analysis.- 3.1 Active Sampling and XAD-4 Sorbent Collection.- 3.1.1 Principle.- 3.1.2 Apparatus.- 3.1.3 Reagents.- 3.1.4 Preparation of Standard Solutions.- 3.1.5 Collection and Preparation of Samples.- 3.1.6 Alkaloids Determination.- 3.1.7 Desorption Efficiency Determination.- 3.1.8 Calculations.- 3.2 Active Sampling and Bisulfate-Treated Filter Collection.- 3.2.1 Principle.- 3.2.2 Apparatus.- 3.2.3 Reagents.- 3.2.4 Preparation of Standard Solutions.- 3.2.5 Collection and Preparation of Samples.- 3.2.6 Alkaloids Determination.- 3.2.7 Desorption Efficiency Determination.- 3.2.8 Calculations.- 3.3 Passive Sampling and Bisulfate-Treated Filter Collection.- 3.3.1 Principle.- 3.3.2 Apparatus.- 3.3.3 Reagents.- 3.3.4 Preparation of Standard Solutions.- 3.3.5 Collection and Prekparation of Samples.- 3.3.6 Alkaloids Determination.- 3.3.7 Desorption Efficiency Determination.- 3.3.8 Calculations.- 4 Real-Time Sampling/Mass Spectrometric Analysis.- 4.1 Atmospheric Pressure Chemical Ionization Mass Spectrometry.- 4.2 Real-Time Quantitative Analysis.- 4.2.1 Calibration.- 4.2.2 Alkaloids Determination.- 4.2.3 Internal Standard.- 5 Summary.- References.- Methods for Production of Alkaloids in Root Cultures and Analysis of Products.- 1 Introduction.- 2 Induction of Transformed Roots.- 2.1 Choice of Bacterial Strains.- 2.2 Culture of Bacteria.- 2.3 Transformation of Plant Tissues.- 2.4 Culture of Root Tissues and Decontamination.- 2.5 Growth and Maintenance of Root Cultures.- 2.6 A Protocol for Cryopreservation of Transformed Roots of Nicotiana rustica.- 3 Proof of Transformation.- 3.1 DNA Extraction from Transformed Roots.- 3.1.1 "Pure DNA" Isolation Procedure.- 3.1.2 DNA "Miniprep" Method.- 3.2 Detection of T-DNA.- 3.2.1 Sources of Probes.- 3.2.2 Recovery of DNA from Agarose Gels.- 3.3 Southern Blotting to Detect T-DNA in Tissues of Plant Material.- 3.4 DNA Labeling and Hybridization.- 3.4.1 Labeling Buffer.- 3.4.2 DNA Labeling.- 3.5 DNA Hybridization.- 3.6 Detection of T-DNA by Polymerase Chain Reaction (PCR).- 4 Alkaloid Extraction and Quantification.- References.- Genetic and Chemical Analysis for Alkaloids in Papaver.- 1 Introduction.- 2 Genetics of Major Opium Alkaloids and Importance of Chemical Analysis.- 2.1 Genetics of Alkaloids of Sections Papaver and Oxytona.- 2.2 Importance of Chemical Analysis.- 3 Chemical Analysis of Major Opium Alkaloids.- 3.1 Isolation of Alkaloids from Opium.- 3.2 Quantitation of Alkaloids.- 3.2.1 Gravimetric/Volumetric Methods.- 3.2.2 Colorimetric Methods.- 3.2.3 Spectrofluorimetric…