Pharmacology of Fluorides: Part 2 PDF
Preview Pharmacology of Fluorides: Part 2
Handbuch der experimentellen Pharmakologie Handbook of Experimental Pharmacology Heffter-Heubner New Series Herausgegeben von / Editorial Board O.Eichler A.Farah H. Herken A. D. Welch J Heidelberg Rensselaer, NY Berlin New Brunswick, N 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 J. A. M. G. Macdonald' R. E. Marquis' Matthews E. A. Maynard' F. A. Smith, A. Wiseman Editor Frank A. Smith With 59 Figures Springer-Verlag Berlin· Heidelberg' New York 1970 ISBN-13: 978-3-642-99975-8 e-ISBN-13: 978-3-642-99973-4 DOl: 10.1007/978-3-642-99973-4 This work is subject to copyright. All rights are reserved, whether the whole or part of the material Is concerned specifically those of translation, reprinting, re·use of illustrations, broadcasting, reproduction by photocopying machine or similar means, and storage in data banks. Under § 54 of the German Copyright Law where copies are made for other than private use, a fee is payabie to the publisher, the amount of the fee to be determined by agreement with the publisher. © by Springer·Verlag Berlin· Heidelberg 1970. Library of Congress Catalog Card Number AGR 25·699. Softcover reprint of the hardcover 1st edition 1970 The use of general descriptive names, trade names, trade marks, ete. in this publication, even if the former are not especially identified, is not to be taken as a sign that such names, as understood by the Trade Marks and Mer chandise Marks Act, may accordingly be used freely by anyone. Title No. 5731 Preface 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 Scandi navica, 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, Ameri can Journal of Physiology, American Journal of Public Health, American Journal of Veteri nary 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, Anest hesia, 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 Compa rative Pathology and Therapeutics, Journal of Dairy Science, Journal of Dental Research, Journal of Economic Entomology, Journal of Nutrition, Journal of Pathology and Bacterio logy, 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 1 I. Introduction . . . . . . . . 1 IT. Methods of Sample Preparation 1 A. Organic Compounds 1 1. The Oxygen-Flask Method .. . . . 2 Procedure for Oxygen-Flask Combustion 3 2. Fusion with Alkali Metals. . . . . • . 4 Procedure for Alkali Metal Fusion . . . . . . . 4 3. Reduction with Alkali Metal in Organic Solvents . 4 4. Wickbold Oxyhydrogen Flame Method 5 B. Inorganic Samples . . . . . . 5 C. Agricultural and Food Samples 6 D. Miscellaneous Samples 6 lIT. Methods of Separation . . . . . . 7 A. Separation of Fluorosilicic Acid by Distillation _ 7 B. Separation by Pyrohydrolysis 8 C. Separation by Diffusion. . . . . . . . . . . 10 D. Separation by Ion-exchange . . . . . . . . . 11 E. Chromatographic Separation on Paper and Thin Layers . 12 F. Other Methods of Separation ..... 12 IV. The Detection of Fluoride . . . _ . . . . 13 Procedure for the 8-Hydroxyquinoline Test . 13 V. The Determination of Fluoride . . . . . 14 A. Gravimetric Methods •.......•.... 15 1. Precipitation as Lead Chlorofluoride . . . . . 15 a) Recommended Lead Chlorofluoride Procedure 16 a) Reagents. . . . . . _ . . 16 p) Procedure . . . . . . . . 16 2. Precipitation as Calcium Fluoride 16 B. Titrimetric Methods . . . . . . 16 1. Titration with Thorium Solution 16 a) Interferences . . . . . . . 18 b) Direct Titration Procedure . 18 c) Back-Titration Procedure. . . 18 2. Titration with Aluminum Solution . . . 18 3. Acid-Base Titration of Hydrofluoric Acid 19 4. Titration with Rare Earth Solutions . . 20 5. Other Titrimetric Methods. . . . . . . 20 a) Titration with Calcium Solutions. . . . . . . . 20 b) Titrations based on Lead Halofluoride Formation 21 c) Titration with lron(IIT) Solutions .. 21 d) Titrations based on Fluorosilicic Acid. 21 C. Colorimetric Methods . . . . • • _ . . . 21 1. The Alizarin Fluorine Blue Methods . . . . . . . . . . . . 21 a) Recommended Lanthanum-Alizarin Fluorine Blue Procedure 23 a) Reagents .........•............ 23 ft) Calibration Graph . • . • • • • • • • • • • . . • . • 24 vm Contents 2. The Bleaching of Zirconium-Dye Complexes • . . . • . • . • 24 a) Recommended Zirconium-Eriochrome Cyanine R Procedure. 24 a) Reagents. . . _ . . . • • • . . . • 24 P) Calibration Graph . . • . . . . . • . 24 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 I. General Introduction. . . . . . . . . . . . . . . . . . . . . . . . . 48 II. Enzymes, Inhibited by Fluoride, Requiring Metal Ions, and Whose Inhibition is Enhanced by Phosphate 51 A. Enolase . . . . . . . • . . . • . . 51 B. Phosphoglucomutase . . . . . . . . 56 C. Lecithinase (from Olo8tridium welekii) . 58 D. Succinic Dehydrogenase. . . . . . . 59 III. Enzymes, Inhibited by Fluoride, Requiring Divalent Metal Ions . 66 A. Phosphatases. . . . . . 66 1. Acid Phosphatases . . 66 2. Alkaline Phosphatases 69 B. Pyrophosphatases. . . . 76 1. Acid Pyrophosphatases . 76 2. Alkaline Pyrophosphatases 76 C. Kinases . . . . 78 D. General . . . . • . • • . . 78 1. Cholinesterase . . . . . . 78 2. Glutamine Synthetase . . 80 3. Alcohol Dehydrogenase (Liver) . 81 4. a-Amylase (Ca++-activated) . . . . . . . . . . . . . • . . . . . . . 82 5. Comments on Non-Inhibition by Fluoride of some Enzymes Activated by Divalent Metals . . . . . . . . . . . . . . . . . . . . . . . .. 83 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 1. Motility. . . . . . . . . . . 122 2. Phagocytosis . . . . . . . . 124 3. Contractility ........ 126 B. Transport Across Cell Membranes. 131 1. Intestinal Epithelium. . . . . 131 2. Non-Polar Cells . . . . . . . 135 IV. Effects of Fluoride on the Growth and Development of Cells in Tissue Culture. 136 V. Concluding Remarks. 138 References . . . . . . . . 141 Chapter 4: Pharmacology of Sodium Fluoride. F. S. CARUSO, E. A. MAYNARD, V. DISTEFANO. With 10 Figures. 144 I. Introduction . . . . . . . . . . . . . . . . . . . • . 144 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 I. Introduction . . . . . . . . . . . • . . . . 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 1. Cell Division .............. 177 2. Motility . . . . • . . . . . . . . . . . . 178 3. Capsule Formation . . . . . . . . . . . . 179 4. Regulation of Enzyme Synthesis and Activity 179 x Contents 5. Transport Systems. . . . 182 6. Bacterial Sporogenesis .• 182 7. Respiration and Photosynthesis. 183 8. Ribosome Synthesis . • . . . . 183 9. Antibiotic Production . . . . . . . . 184 10. Maintenance of Diploid State in Fungi . 184 11. Virus and Bacteriocin Production ... 184 D. Catabolism of Fluoroamino Acids by Bacteria 185 E. Bacterial Adaptation to Fluoroamino Acids . 186 1. Physiologic Adaptation. . . . . . . . . 186 2. Amino Acid-Secreting Mutants . . . . . 186 3. Mutants with Altered Transport Systems. . . . . . 187 4. Mutants with Altered Amino Acyl-tRNA Synthetases 187 5. Mutants with Altered Ribosomes 187 References . . . . . . . . . . . . . . . . . . . . . . . . . 188 Chapter 6: Fluorine-Containing Steroids. PHILIP S. CHEN JR., and POUL BORREVANG 193 I. Introduction . . . . . • . . . . . . . . . . . . . . . . . . . . . . . . 193 n. Fluoro Steroids with Respect to Glucogenic, Anti-In1l.ammatory and Mineralocorti- coid Effect . . . . . . . . . . 194 A. The 9a-Fluoro-Substitution in 194 1. Cortisol. . . . . . . . . 194 2 . .J1-Cortisol (Prednisolone) . 194 3 . .Js-Cortisol. . . . . . . . 195 4. Other Pregnane Derivatives 195 B. Fluorination at other Positions and in Combination with 9a-Fluoro 195 1. In Cortisone, Cortisol, Prednisone or Prednisolone 195 a) 2a-Fluoro. . . . . . . . . . . . . . . . . . . . . . . 195 b) 4-Fluoro . . . . . . . . • . . . • . . . . . . . . . . 195 c) 6a-Fluoro and 6a,9a-Difluoro . . . . . . . . . . . . . . 195 d) 15P-Fluoro and 9a,15p-Difluoro . . . . . . . . . . . . . . .. 196 e) 16a-Fluoro, 9a,16a-Difluoro, 6a,16a-Difluoro and 6a,9a,16a-Trifluoro 196 f) 16p-fluoro and 9a,16p-Difluoro . 196 2. In other Pregnane Derivatives . 196 a) 11p-Fluoro . . . . . . . 196 b) 12a-Fluoro . . . . . . . 196 c) 17a-Fluoro ... _ . . . 197 d) 21-Fluoro. . . . . . . . 197 e) Fluorine in 16a,17a-Ketal . 197 C. Other Groups in . . . . . . . . . . . . . . 197 1. 9a-Fluorocortisol and 9a-Fluoroprednisolone . 197 a) I-Hydroxy . . . . • 197 b) 2a-Methyl . . . . . 197 c) 4-Methyl and 4-Ethyl 198 d) 6a- and 6p-Chloro . 198 e) 6a-Fluoromethyl 198 f) 6a-Methoxy . 198 g) 6a-Methyl . . 198 h) 7a-Acetylthio . 198 i) 16P-Acetoxy . 198 j) 16a-Chloro . . 199 k) 16a-Ethyl . . . . 199 1) 16a-Fluoromethyl. 199 m) 16a-Hydroxy . . . 199 n) 16a,17a-Ketal 200 0) 16a-Methoxy . . . . 200 p) 16a- and 16p-Methyl. . . . . 200 q) 16-Methylene or .J15-16-Methyl 200 r) 16a, 17 a-Orthoesters (Cyclic). . 200 s) 21-Methyl . • . . . • . . . 201
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