34570 FM i-xviii.qxd 2/9/07 9:16 AM Page i PHYCOTOXINS Chemistry and Biochemistry 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page iii PHYCOTOXINS Chemistry and Biochemistry Luis M. Botana Editor 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page iv 1 2 3 Dr. Luis M. Botana is professor of Pharmacology, University of Santiago de Compostela, Spain. His group is a 4 world leader in the development of new methods to monitor the presence of phycotoxins, having developed 5 methods to date for saxitoxins, yessotoxin, pectenotoxin, ciguatoxins, brevetoxins, okadaic acid and dinophy- 6 sistoxins. Dr. Botana is the editor of Seafood and Freshwater Toxins: Pharmacology, Physiology and Detection, 7 to date the only comprehensive reference book entirely devoted to marine toxins. 8 ©2007 Blackwell Publishing 9 All rights reserved 10 1 Blackwell Publishing Professional 2 2121 State Avenue, Ames, Iowa 50014, USA 3 4 Orders: 1-800-862-6657 5 Office: 1-515-292-0140 6 Fax: 1-515-292-3348 7 Web site: www.blackwellprofessional.com 8 Blackwell Publishing Ltd 9 9600 Garsington Road, Oxford OX4 2DQ, UK 20 Tel.: +44 (0)1865 776868 1 2 Blackwell Publishing Asia 3 550 Swanston Street, Carlton, Victoria 3053, Australia 4 Tel.: +61 (0)3 8359 1011 5 6 Authorization to photocopy items for internal or personal use, or the internal or personal use of specific clients, 7 is granted by Blackwell Publishing, provided that the base fee is paid directly to the Copyright Clearance Cen- 8 ter, 222 Rosewood Drive, Danvers, MA 01923. For those organizations that have been granted a photocopy 9 license by CCC, a separate system of payments has been arranged. The fee codes for users of the Transactional Reporting Service is ISBN-13: 978-0-8138-2700-1/2007. 30 1 Printed on acid-free paper in the United States of America 2 3 First edition, 2007 4 5 Library of Congress Cataloging-in-Publication Data 6 7 Phycotoxins : Chemistry and biochemistry / edited by Luis Botana.—1st ed. 8 p. cm. 9 Includes bibliographical references. 40 ISBN-13: 978-0-8138-2700-1 (alk. paper) ISBN-10: 0-8138-2700-0 (alk. paper) 1 1. Algal toxins. I. Botana, Luis M. [DNLM: 1. Marine Toxins—chemistry. 2. Marine Toxins— 2 metabolism. QW 630.5.M3 P578 2007] 3 RA1242.A36.P59 2007 4 615.9'45—dc22 2006032585 S5 N6 The last digit is the print number: 987654321 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page v Contents 1 2 3 4 5 6 Preface vii 7 8 Contributors ix 9 10 1. Gambierol 1 1 Makoto Sasaki, Eva Cagide, and M. Carmen Louzao 2 3 2. Brevetoxins: Structure, Toxicology, and Origin 19 4 Ambrose Furey, Keith O’Callaghan, Javier García Fernández, Mary Lehane, Mónica 5 Fernández Amandi, and Kevin J. James 6 7 3. Chemistry of Maitotoxin 47 8 Masayuki Satake 9 20 4. Biochemistry of Maitotoxin 55 1 Laura A. de la Rosa, Emilio Alvarez-Parrilla, and Alejandro Martínez-Martínez 2 3 5. Chemistry of Palytoxins and Ostreocins 75 4 Panagiota Katikou 5 6 6. Biochemistry of Palytoxins and Ostreocins 95 7 Carmen Vale and Isabel R. Ares 8 9 7. Chemistry of Cyanobacterial Neurotoxins — Anatoxin-a: Synthetic Approaches 119 30 Nuria Armesto Arbella, Keith O’Callaghan, Ambrose Furey, and Kevin J. James 1 2 8. Anatoxin-a and Analogues: Discovery, Distribution, and Toxicology 141 3 Kevin J. James, Janet Crowley, Justine Duphard, Mary Lehane, and Ambrose Furey 4 5 9. Pectenotoxins 159 6 Christopher O. Miles 7 8 10. Chemistry, Origins, and Distribution of Yessotoxin and Its Analogues 187 9 Philipp Hess and John A.B. Aasen 40 1 11. Pharmacology of Yessotoxin 203 2 Amparo Alfonso and Carmen Alfonso 3 4 12. Chemistry of Diarrhetic Shellfish Poisoning Toxins 211 5 Paulo Vale 6m 7m v 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page vi vi Contents 1 13. The Molecular and Integrative Basis to Domoic Acid Toxicity 223 2 John S. Ramsdell 3 4 14. Hepatotoxic Cyanobacteria 251 5 Ana Gago-Martinez 6 7 15. Polycavernosides 275 8 Leo A. Paquette and Mari Yotsu-Yamashita 9 10 16. Structural Assignment and Total Synthesis of Azaspiracid-1 297 1 Michael O. Frederick, Kevin P. Cole, Goran Petrovic, Eriketi Loizidou, 2 and K.C. Nicolaou 3 4 17. Biochemistry of Azaspiracid Poisoning Toxins 311 5 Natalia Vilariño 6 7 18. Cyclic Imines:An Insight into this Emerging Group of 8 Bioactive Marine Toxins 319 9 Jordi Molgó, Emmanuelle Girard, and Evelyne Benoit 20 1 Index 337 2 3 4 5 6 7 8 9 30 1 2 3 4 5 6 7 8 9 40 1 2 3 4 S5 N6 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page vii Preface 1 2 3 4 5 6 Marine toxins are important to the scientific community because they pose many challenges. The first 7 one is the obvious food safety issue, that requires a large investment in producing countries to regu- 8 larly monitor the potential presence of these compounds in seafood. A second challenge is the poten- 9 tial these compounds offer as tools for research, since the variety of mechanistic actions is 10 impressive. This book intends to offer a glimpse of this diversity of mechanisms of actions. The third 1 challenge is the chemical structure of the compounds, from the simple domoic acid to the unusual 2 structure of azaspiracid or the large molecule of palytoxin. Another goal to this editorial work is to 3 provide an overall view on the chemical diversity of marine toxins. Not all the known toxins are 4 included in this book, but only those that have been recently discovered or that still provide puzzles 5 on their chemistry or pharmacology. Although to some groups the uncertainties are wide (how many 6 yessotoxin analogs? are they toxic?), to others the mystery goes even to their structure (ovatatoxins?). 7 This book is the silent work of many great scientist who spared some of their very busy time to 8 write their chapters. I express my admiration for their dedication and thank them for their contribu- 9 tions and their hard work. 20 I would like to thank Dr. Leo Nollet and Dr. Y. H. Hui for their editorial help, and the staff at 1 Blackwell, especially Susan Engelken, for their excellent work. 2 3 Luis M. Botana 4 2006 5 6 7 8 9 30 1 2 3 4 5 6 7 8 9 40 1 2 3 4 5 6m 7m vii 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page ix Contributors 1 2 3 4 5 6 John A. B.Aasen (chapter 10) 7 Norwegian School of Veterinary Sciences 8 P.O. Box 8146 9 N-0033, Oslo, Norway 10 Email: [email protected] 1 2 Amparo Alfonso (chapter 11) 3 Departamento de Farmacología 4 Facultad de Veterinaria 5 Universidad de Santiago de Compostela 6 27002 Lugo Spain 7 Ph: 34-982-252-242 8 Email: [email protected] 9 20 Carmen Alfonso (chapter 11) 1 Departamento de Farmacología 2 Facultad de Veterinaria 3 Universidad de Santiago de Compostela 4 27002 Lugo Spain 5 Ph: 34-982-252-242 6 Email: [email protected] 7 8 Isabel R.Ares (chapter 6) 9 Departamento de Farmacología 30 Facultad de Veterinaria 1 Universidad de Santiago de Compostela 2 27002 Lugo Spain 3 Ph: 34-982-252-242 4 Email: [email protected] 5 6 Nuria Armesto Arbella (chapter 7) 7 PROTEOBIO 8 Mass Spectrometry Centre for Proteomics and Biotoxin Research 9 Cork Institute of Technology 40 Bishopstown, Cork, Ireland 1 Ph: 353-21-4326701 2 Fax: 353-21-4345191 3 4 Evelyne Benoit (chapter 18) 5 Laboratoire de Neurobiologie Cellulaire et Moléculaire 6m Unité Propre de Recherche 9040 7m ix 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page x x Contributors 1 Centre National de la Recherche Scientifique 2 Institut Fédératif de Neurobiologie Alfred Fessard 3 1 Avenue de la Terrasse 4 Bâtiments 32–33 5 91198 Gif-sur-Yvette Cedex, France 6 Ph: 33-1-6982-3642 7 Fax: 33-1-6982-4141 8 9 Luis M. Botana (editor) 10 Departamento de Farmacología 1 Facultad de Veterinaria 2 Universidad de Santiago de Compostela 3 27002 Lugo Spain 4 Ph: 34-982-252-242 5 Email: [email protected] 6 Eva Cagide (chapter 1) 7 Departamento de Farmacología 8 Facultad de Veterinaria 9 Universidad de Santiago de Compostela 20 27002 Lugo Spain 1 Ph: 34-982-252-242 2 Email: [email protected] 3 4 Kevin P.Cole (chapter 16) 5 Scripps Institute 6 Department of Chemistry 7 University of California, San Diego 8 10550 North Torrey Pines Road 9 La Jolla, CA 92037, USA 30 Ph: 858-784-2400 1 Fax: 858-784-2469 2 3 Janet Crowley (chapter 8) 4 PROTEOBIO 5 Mass Spectrometry Centre for Proteomics and Biotoxin Research 6 Cork Institute of Technology 7 Bishopstown, Cork, Ireland 8 Ph: 353-21-4326701 9 Fax: 353-21-4345191 40 1 Laura A. de la Rosa (chapter 4) 2 Departmento de Ciencias Básicas 3 Instituto de Ciencias Biomédicas 4 Universidad Autónoma de Ciudad Juárez S5 Cd. Juárez, Chihuahua, Mexico N6 Ph: 52-1613-7679 Email: [email protected] 34570 FM i-xviii.qxd 2/9/07 9:16 AM Page xi Contributors xi Mónica Fernández Amandi (chapter 2) 1 Cork Institute of Technology 2 Department of Chemistry 3 Rossa Avenue 4 Bishopstown, Cork, Ireland 5 Ph: 353-21-4326701 6 Fax: 353-21-4345191 7 8 Michael O.