Handbuch der experimentellen Pharmakologie Handbook of Experimental Pharmacology O.Eichler Heidelberg Heffter-Heubner New Series Herausgegeben von / Editorial Board A.Farah H. Herken A. D. Welch Rensselaer, NY Berlin New Brunswick, N J Beirat/ Advisory Board G. Acheson· E. J. Ariens . Z. M. Bacq . F. v. Briicke . P. Calabresi . S. Ebashi E. G. Erdos . V. Erspamer . U. S. von Euler . W. Feldberg . R. Furchgott A. Goldstein· G. B. Koelle' O. Krayer . H. Raskova . M. Rocha e Silva F. Sakai· P. Waser . W. Wilbrandt Vol.XX/2
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Handbuch der experimentellen Pharmakologie
Handbook of Experimental Pharmacology
O.Eichler Heidelberg
Heffter-Heubner New Series
Herausgegeben von / Editorial Board
A.Farah H. Herken A. D. Welch Rensselaer, NY Berlin New Brunswick, N J
Beirat/ Advisory Board
G. Acheson· E. J. Ariens . Z. M. Bacq . F. v. Briicke . P. Calabresi . S. Ebashi
E. G. Erdos . V. Erspamer . U. S. von Euler . W. Feldberg . R. Furchgott
A. Goldstein· G. B. Koelle' O. Krayer . H. Raskova . M. Rocha e Silva
F. Sakai· P. Waser . W. Wilbrandt
Vol.XX/2
Pharmacology of Fluorides
Part 2
Contributors
P. Borrevang . F. S. Caruso' P. S. Chen jr .. V. Di Stefano
This volume is the completion of work initially planned several years ago as a compilation of selected aspects of the biological effects of fluorides. The first portion appeared in Volume XXII (1966) of this Handbuch, under the title "Pharmacology of Fluorides, Part 1."
Inasmuch as the present volume is an integral part of the original project, justification for offering it to the scientific community remains the same as that originally set forth. This may be recapitulated as follows. The tremendous increase in the annual production of fluorides over the amounts produced thirty years ago, together with the increased diversity of their uses has correspondingly increased the hazard associated with these materials. That is to say, the possibilities of encountering their characteristic toxic effects under the conditions of their use has increased because the variety, amounts and ways of usage have increased. Their inherent toxicity, of course has not changed, but the increased hazard has led to a vast increase in the amount and scope of research reported. It is the purpose of these volumes to review selected aspects of this literature.
Rochester, N.Y., February 1970 FRANK A. SMITH
Acknowledgements
Even the casual reader of this volume will soon realize that contributing authors, as well as those contributing to its predecessor, Volume XX/I, have made good use of tables of data, figures and pertinent quotations from previously published work. The use of this material has added much to the effectiveness with which the present writers have been able to develope their reviews. In each instance the source of the material used has been acknowledged by indicating the author and citing the appropriate reference in the bibliography. Before falling back on that somewhat impersonal procedure however, the editor takes this opportunity to extend his warm thanks to each of those authors of previously published work, to journal editors, to professional societies, and to publishers who so kindly permitted us to reproduce copyrighted matter in Volumes XXII and/or XX/2 of this Handbuch. The list of journals, publishers and professional societies includes Academic Press, Inc., Acta Chemica Scandinavica, Acta Obstetricia et Gynecologica Scandinavica, Acta Pharmacologica et Toxicologica, Air Pollution Control Association, American Chemical Society, American Association for the Advancement of Science, American Dental Association, American Journal of Botany, American Journal of Physiology, American Journal of Public Health, American Journal of Veterinary Research, American Medical Association, American Physiological Society, American Society of Animal Science, American Society of Plant Physiologists, American Veterinary Medical Association, American Veterinary Publications, Inc., Analytical Chemistry, Anesthesia, Anesthesia and Analgesia, Anesthesiology, Annals of Human Genetics, Annals of the New York Academy of Sciences, Archives of Biochemistry and Biophysics, Archives of Oral Biology, Berliner und Miinchener Tierarztliche Wochenschrift, Biochemische Zeitschrift, Biochimical et Biophysica Acta, Biochemical Journal, Biochemical Pharmacology, Boyce Thompson Institute for Plant Research, British Dental Association, British Dental Journal, British Journal of Anesthesia, British Journal of Experimental Pathology, Bulletin of the Research Council of Israel, Burgess Publishing Co., Cambridge University Press, Cancer Research, Charles C. Thomas, Publisher, Columbia University Press, Comptes rendus de l'academie des sciences, Contributions of the Boyce Thompson Institute for Plant Research, F.A. Davis Co., Deutsche Tierarztliche Wochenschrift, Elsevier Publishing Co., Endeavour, Endocrinology, Entomological Society of America, European Journal of Pharmacology, The Gerrard Press, Illinois State Geological Survey (Section of Fluorine Chemistry), Industrial and Engineering Chemistry, International Anesthetic Research Society, International Journal of Air and Water Pollution, Interscience Publishers, Inc., John Sherratt and Son, Johns Hopkins Press, Journal of Agricultural and Food Chemistry, Journal of the Air Pollution Control Association, Journal of the American Dental Association, Journal of the American Medical Association, Journal of Animal Science, Journal of Biochemistry (Tokyo), Journal of Comparative Pathology and Therapeutics, Journal of Dairy Science, Journal of Dental Research, Journal of Economic Entomology, Journal of Nutrition, Journal of Pathology and Bacteriology, Journal of Pharmacology and Experimental Therapeutics, Journal of Pharmaceutical Sciences, Journal of Physiology, H.K. Lewis, and Co., Ltd., J.B. Lippincott Co., Metabolism, Clinical and Experimental, Michigan State Medical Society, Nature, New York Academy of Sciences, Paul Parey-Verlag, Pergamon Press, Ltd., Plant Physiology, Proceedings of the American Society for Horticultural Science, Proceedings of the Royal Society (London), Proceedings of the Society for Experimental Biology and Medicine, Public Health Reports, The Royal Society, The Royal Veterinary College, M. and H. Schaper-Verlag, Science, Society of Toxicology, Springer-Verlag, Toxicology and Applied Pharmacology, University of Chicago Press, U.S. Department of Health, Education and Welfare, Williams and Wilkins Company, Wistar Institute of Anatomy and Biology, World Health Organization.
Contents
Chapter 1: Methods of Analysis for Fluorine. A.M.G. MAODONALD
I. Introduction . . . . . . . .
IT. Methods of Sample Preparation A. Organic Compounds
1. The Oxygen-Flask Method .. . . . Procedure for Oxygen-Flask Combustion
2. Fusion with Alkali Metals. . . . . • . Procedure for Alkali Metal Fusion . . . . . . .
3. Reduction with Alkali Metal in Organic Solvents . 4. Wickbold Oxyhydrogen Flame Method
B. Inorganic Samples . . . . . . C. Agricultural and Food Samples D. Miscellaneous Samples
lIT. Methods of Separation . . . . . . A. Separation of Fluorosilicic Acid by Distillation _ B. Separation by Pyrohydrolysis C. Separation by Diffusion. . . . . . . . . . . D. Separation by Ion-exchange . . . . . . . . . E. Chromatographic Separation on Paper and Thin Layers . F. Other Methods of Separation .....
IV. The Detection of Fluoride . . . _ . . . . Procedure for the 8-Hydroxyquinoline Test .
V. The Determination of Fluoride . . . . . A. Gravimetric Methods •.......•....
1. Precipitation as Lead Chlorofluoride . . . . . a) Recommended Lead Chlorofluoride Procedure
2. Precipitation as Calcium Fluoride B. Titrimetric Methods . . . . . .
1. Titration with Thorium Solution a) Interferences . . . . . . . b) Direct Titration Procedure . c) Back-Titration Procedure. . .
2. Titration with Aluminum Solution . . . 3. Acid-Base Titration of Hydrofluoric Acid 4. Titration with Rare Earth Solutions . . 5. Other Titrimetric Methods. . . . . . .
a) Titration with Calcium Solutions. . . . . . . . b) Titrations based on Lead Halofluoride Formation c) Titration with lron(IIT) Solutions .. d) Titrations based on Fluorosilicic Acid.
3. The Bleaching of Thorium-Dye Complexes. . 25 4. The Bleaching of Aluminum-Dye Complexes. 26 5. Other Colorimetric Methods . 26
a) Titanium(IV) Complexes . 26 b) Iron(III) Complexes . . . 27 c) Chloranilic Acid Methods . 27 d) Molybdenum Blue Methods 27
D. Polarographic Methods . . . 28 E. Direct Electrometric Methods 28 F. Radiometric Methods. . . . 31 G. Catalytic Methods . . . . . 31 H. Determination of Elemental Fluorine 32
VI. The Determination of Common Elements in Organic Fluorine Compounds. 32 A. Carbon, Hydrogen and Nitrogen . . . . 32 B. Other Halogens, Sulfur and Phosphorus . 33
References • . . . . . . . . . . . . . . . . . 34
Chapter 2: Effect of Inorganic Fluoride on Enzymes. A. WISEMAN. With 34 Figures 48
IV. Enzymes Inhibited by Fluoride; No Requirement for Metal Ions Demonstrated 83 A. Liver Esterase . . . . . . 83 B. 5'-Adenylic Acid Deaminase 88 C. Phosphoglycerate Mutase . 88 D. Hydrazidase. . • . . . . 89
V. Enzymes, Inhibited by Fluoride, Containing Trivalent Metal Ions 90 A. Catalase. . . . . 91 B. Peroxidase. . . . 91
VI. Concluding Comments 91
References . . . . . . . . 93
Chapter 3: Changes in Cen Function Due to Inorganio Fluoride. J. MATTHEws. With 7 Figures . . • . . . . . . . . . 98
I. Introduction . . . . . . . . . . . . . 98
IT. Effect of Fluoride on Metabolic Pathways 99 A. Outline of Intermediary Metabolism. . 99 B. Glycolysis . . . . . . . . . . . . . 101 C. Pyruvate Metabolism and Oxidation in the Tricarboxylic Acid Cycle 104 D. Oxidative Phosphorylation 109 E. Respiration . . . . . . . . . . . . 112 F. Protein Synthesis ......... 113 G. The Response of Tissues to Hormones 118 H. Fat Metabolism in Adipose Tissue . . 118 I. Lipa.ses . . . . . . . . . . . . . . 121
ITl. Effects of Fluoride on Physical Activity of Cells . 122 A. Movement. . . • . . . . . . . 122
IT. Effect of Sodium Fluoride on Blood Pressure and the Heart. 145 A. Hypotensive Activity of Fluoride. . . . . . . . . . . 145 B. Pressor Effect of Fluoride . . . . . . . . . . . . . . 148 C. Stimulatory Effect of Sodium Fluoride on Isolated Heart Preparations 155
ITl. Effect of Sodium Fluoride on the Gut . . 157 A. Effect of Fluoride on the Gut, in Vivo 157 B. Effect of Fluoride on Dog Gut, in Vitro 158
IV. Effect of Sodium Fluoride on Respiration. 158
V. Summary and Conclusions 162
References. . . . . . . . . . 163
Chapter Ii: Fluoroamino Acids and Microorganisms. R. E. MARQUIS 166
IT. Fluoroamino Acids and Cellular Microorganisms . 167 A. General Toxicity and Effects on Growing Cells 167 B. Incorporation of Fluoroamino Acids into Proteins 172 C. Effects of Fluoroamino Acids on Specific Cell Functions 177
E. Pyrazol Ring Attached to Ring A. . . . . . . . . . . . 205
F. Other Groups in 6a-Fluoro Compounds without 9a-Fluoro Substitution 205 1. 6a-Fluoro, 2-Methyl, 16a-Hydroxy, Acetonide, .1 1 • • 205 2. 6a-Fluoro, 16a-Hydroxy, and 6a-Fluoro, 16a-Methyl 206 3. 6a-Fluoro, 16a-Hydroxy, .1 8 and Acetonide . . 206 4. 6a-Fluoro, 3P-Acetoxy, 16a-Hydroxy Acetonide 206
G. Analytical Problems in Studying Fluorosteroids 206 1. General Aspects . . . . . . . . . . . . 206 2. Extraction. . . . . . . . . . . . . . . 207 3. Fluorosteroid Color Reaction . . . . . . 207 4. Determination in Urine as 17-Ketosteroids 207 5. Paper and Column Chromatography . . . . . 207 6. Preparation of Tritium-Labeled Triamcinolone . 208 7. Isomerization 208
H. Metabolism . . . 208 1. Absorption . . 208
a) Intestinal. . 208 b) Percutaneous 209 c) Intra-Articular 210
2. In Vitro Studies . . . . . . . 210 a) Liver Slices or Homogenates. . 210 b) Metabolism by Micro-Organisms .. .. . 212 c) Adrenal Metabolism of 9a-Fluoroandrostenedione 212
4. Effects in Man. . . . . . . . . .• 220 a) Extrapolation from Animal Biol1ssays to Man 220 b) Use of Corticosteroids . . . . . . . 222 c) Adrenal Suppression . . . . . . . . . . . 222 d) Side Effects of Therapeutic Doses . . . . . 223 e) Topical Effectiveness of Fluorosteroids . . . 223
III. Fluoro-Steroids with Respect to Gestagenic, Anti-Androgenic, Anti-Estrogenic, Anti-Ovulatory, and Anti-Gonadotrophic Effects. . . 224 A. The 9a-Fluoro-Substitution in . . . . . . • . . 224
B. Fluorination at other Positions. . . . . . . . . . . . . . . . . . .. 225 1. In Progesterone, and Its 9a-Halogenated and ll-Oxygenated Derivatives 225
IV. Fluoro-Steroids with Respect to Androgenic, Anabolic, Anti-Androgenic, Anti-Tumor and Anti-Gonadotropic Effect. . . . 230 A. The 9a-Fluoro Substitution in . . . . . . 230
POUL BORREVANG, Ph.D., Steroid Department, Novo Terapeutisk Laboratorium A/S, Copenhagen/Denmark
FRANK S. CARUSO, Ph.D., Bristol Laboratories, Syracuse, N.Y./USA
PmLIP S. CHEN JR., Ph.D., National Institutes of Health, Public Health Service, U.S. Department of Health, Education and Welfare, Bethesda, Md.20014/USA
VICTOR DISTEFANO, Ph. D., University of Rochester, School of Medicine and Dentistry, Department of Pharmacology and Toxicology, Rochester, N. Y. 14620jUSA
A.M.G. MACDONALD, Ph.D., University of Birmingham, Department of Chemistry, Birmingham 15/England
ROBERT E. MARQUIS, Ph.D., University of Rochester School of Medicine and Dentistry, Department of Microbiology, Rochester, N.Y. 14620/USA
J. MATTHEWS, Ph.D., CIBA Laboratories, Ltd., Horsham, Sussex/England
E.A. MAYNARD, University of Rochester, School of Medicine and Dentistry, Department of Radiation Biology and Biophysics, Rochester, N. Y. 14620/USA, Deceased
FRANK A. SMITH, Ph.D., University of Rochester School of Medicine and Dentistry, Department of Radiation Biology and Biophysics, Rochester, N.Y. 14620/USA
ALLAN WISEMAN, Ph.D., University of London, Biochemistry Unit, London SW ll/England