CHROMATOGRAPHY AND ISOLATION

OF INSECT HORMONES AND PHEROMONES

CHROMATOGRAPHIC SOCIETY SYMPOSIUM SERIES

CHIRAL SEPARATIONS ·Edited by D. Stevenson and I. D. Wilson

CHROMATOGRAPHY AND ISOLATION OF INSECT HORMONES AND PHEROMONES Edited by A. R. McCaffery and I. D. Wilson

RECENT ADVANCES IN CHIRAL SEPARATIONS Edited by D. Stevenson and I. D. Wilson

RECENT ADVANCES IN THIN-LAYER CHROMATOGRAPHY Edited by F. A. A. Dallas, H. Read, R. J. Ruane, and I. D. Wilson

CHROMATOGRAPHY AND ISOLATION

OF INSECT HORMONES AND PHEROMONES

Edited by

A. R. McCaffery University of Reading

Reading, United Kingdom

and

I. D. Wilson ICI Pharmaceuticals

Macclesfield, Cheshire, United Kingdom

PLENUM PRESS • NEW YORK AND LONDON

Llbrary of Congress Cataloglng-ln-Publleatlon Data

International Symposium on Chromatography and Isolation of Inseet Hormones. Pheromones. and Related Compounds (1st 1989 Readlng. England)

Chromatography and lsolation of lnsect hormones and pheromones Iproeeedlngs of the First InternatIonal SymposIum (Jointly organlzed by the ChromatographIe Soelety and the Royal Entomologleal Soelety of Landon) on Chromatography and IsolatIon of Inseet Hormones. Pheromones. and Related Compounds. held Mareh 21-23. 1989. in Reading. Unlted Kingdoml / edited by A.R. MeCaffery and 1.0. Wilson.

p. em. -- (ChromatographIe Soelety symposium) Ineludes blbliographleal referenees and Indexes.

1. Inseet hormones--Analysis--Congresses. 2. Pheromones­-Analysis--Congresses. 3. Chromatographie analysis--Congresses. I. MeCaffery. A. R. 11. Wilson. Ian D. 111. Chromatographie Soeiety (Great Brltain) IV. Royal Entomologieal Soeiety of Landon. V. Title. VI. Series. QL495.1548 1989 595.7·01927--de20 90-46480

CIP

Proeeedings of the First International Symposium (jointly organized by the Chromatographie Soeiety and the Royal Entomologieal Soeiety of London) on Chromatography

and Isolation of Inseet Hormones, Pheromones, and Related Compounds, held March 21-23, 1989, in Reading, United Kingdom

ISBN 978-1-4684-8062-7 (eBook) DOI 10.1007/978-1-4684-8062-7

© 1990 Plenum Press, New York

Softcover reprint of the hardcover 1 st edition 1990

A Division of Plenum Publishing Corporation 233 Spring Street, New York, N.Y. 10013

All rights reserved

No part of this book may be reprodueed, stored in a retrieval system, or transmitted in any form or by any means, eleetronie, meehanieal, photoeopying, mierofilming,

reeording, or otherwise, without written permission from the Publisher

ISBN 978-1-4684-8064-1

PREFACE

The connection between the study of insects. their development. behaviour and biochemistry. and chromatography is perhaps not immediately obvious. However. this connection exists and it is of fundamental importance to our understanding of many areas of insect physiology. Insects range in size from small to minute and consequently the amounts of hormones or pheromones they produce are equally minute. Ultimately any attempt at understanding the processes which control development, social behaviour or the biochemistry of insects requires some means of isolating the tiny quantities of the hormones and pheromones responsible in sufficient quantity and purity for identification. The ability to devise novel techniques to separate these materials from frequently complex biological mixtures including precursors and metabolites and to devise detection systems for them is vital. Methods for the quantification of these substances at different stages in the life cycle. or in response to environmental change or stress. are then essential. Chromatography. both as a means for isolation and as a method for quantitative analysis. has "been an essential tool in these studies.

This volume represents the outcome of a joint international symposium organized by the Chromatographic and Royal Entomological Societies at the University of Reading between the 21st and 23rd March 1989 aimed specifically at discussing the chromatography and isolation of insect hormones. pheromones and related substances.The papers presented at that meeting. and collected together here. covered many aspects of the subject including the chromatography of juvenile hormones. ecdysteroids. peptides. pheromones and semio­chemicals.

Almost every area of chromatography was discussed. including GLC. HPLC. TLC. SFC. CZE and electrophoresis. with the separations described often of an impressively high standard. Many authors have devised novel combinations of separation and detection or coupled separative techniques to improve resolution. Together with modern immu­nological. molecular and sequencing techniques the science of insect hormone and pheromone isolation has identified many active materials. As shown in this volume. the continued development of sensitive bioassays in combination with chromatographic techniques has been an important factor in this progress. The editors believe that these proceedings represent a body of knowledge and experience which will be of immense value to any researcher in this field for many years to come.

A.R. McCaffery and J.D. Wilson April 1990

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CONTENTS

The Chromatographic Society

The Royal Entomological Society of London

JUVENILE HORMONES

Endogenous Juvenile Hormone III Titres and In Vitro Rates of Hormone Biosynthesis by Corpora Allata During the Reproductive Cycle of Adult Female Periplaneta americana

J.P. Edwards, J. Chambers, J.E. Short, N.R Price, RJ. Weaver, L. Abraham

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xiii

and C.M. Walter 3

Use of Thin-Layer Chromatography, High Performance Liquid Chromatography and Gas Chromatography-Mass Spectrometry to Investigate the Relationship Between Juvenile Hormone Titre and Corpus Allatum Activity in Adult Male Periplaneta americana

RJ. Weaver, J.P.G. Wilkins, AT. Roberts and J.P. Edwards 9

Use of Microderivatization Techniques in Combination with Thin-Layer Chromatography, Liquid Chromatography and Gas Chromatography­Mass Spectrometry for Investigation of Juvenile Hormones and Related Compounds

F.C. Baker, C.C. Reuter, L.W. Tsai, PA Brindle, D.S. Richard, S.S. Tobe and D.A Schooley 19

The Precocene Antijuvenile Hormones (Allatotoxins): A Case History in Insect Toxicology

G.T. Brooks and AR McCaffery 33

The Regulation of the Corpora Allata by the Brain in the Adult Female American Cockroach, Periplaneta americana

1. Ghanem and AR McCaffery 43

ECDYSTEROIDS

Chromatographic Separations of Ecdysone Acyl Esters and Their Application to the Distribution and Identification of Ecdysteroids in Adult House Crickets, Acheta domesticus

P. Whiting and L. Dinan 53

Ecdysteroids in Eggs of Periplaneta americana: Rapid Analysis Using 3~ C 18 Columns and the Binding of Ecdysteroids to Vitellin

RE. Isaac, F. EI-Zoghby, AJ. Slinger and AN. MacGregor 69

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Advances in Ecdysteroid High Performance Liquid Chromatography R. Lafont and J.D. Wilson 79

Examination of Conditions in Supercritical Fluid Chromatography for Analysis of Ecdysteroids

E.D. Morgan, H.-P. Huang and J.D. Wilson 95

Current Status and Recent Advances in the Chromatography and Mass Spectrometry of Ecdysteroids

RP. Evershed, M. Kabbouh, M.C. Prescott, J.L. Maggs and H.H. Rees 103

Thin-Layer Chromatography of Ecdysteroids: Detection and Identification 1.D. Wilson, R. Lafont, C.J. Porter, R G. Kingston, K Longden, 1. Fleming

and P. Wall 117

Overpressure Thin-Layer Chromatography of Ecdysteroids H. Read, J.D. Wilson and R. Lafont 127

Selective Separation of 20,22-Dihydroxyecdysteroids from Insect and Plant Material with Immobilized Phenylboronic Acid

S.J. Murphy, E.D. Morgan and LD. Wilson 131

PEPTIDES

Isolation and Characterization of a Diuretic Peptide, AP-I, from the Corpora Cardiaca of the House Cricket, Acheta domesticus

G.M. Coast, C.H. Wheeler, N.F. Totty, RJ. Philp and G.J. Goldsworthy 139

Manduca Adipokinetic Hormone: Quantification Using High Performance Liquid Chromatography and Radioimmunoassay

AM. Fox and S.E. Reynolds 155

Extraction, Purification and Sequencing of Adipokinetic/Red Pigment­Concentrating Hormone-Family Peptides

G.Gade 165

In Vitro Biosynthesis of Locust Adipokinetic Hormones: Isolation and Identification of the Bioactive Pep tides and Their Prohormones

RC.H.M. Oudejans, F.P. Kooiman, T.KF. &hulz and AM. Th. Beenakkers 183

A Strategy for the Isolation and Structural Characterization of Certain Insect Myotropic Peptides that ModifY the Spontaneous Contractions of the Isolated Cockroach Hindgut

G.M. Holman, RJ. Nachman and M.S. Wright 195

Isolation and Identification of Neuropeptides in Locusta migratoria A De Loof, L. &hoofs, G.M. Holman, T. Hayes, R Nachman and

J. Vanden Broeck 205

Adsorption Chromatography of Small C-Terminal Peptide Amides on Dihydroxyalkyl Bonded Silica High-Performance Liquid Chromatography Columns and Application to Purification of Insect Neuropeptides

T.K Hayes, AA Strey and KW. Beyenbach 213

Isolation and Structural Characterization of Neuroparsins, Polytropic Neurohormones of the African Locust

J. Girardie, J.C. Pernollet, J.C. Huet and A Girardie

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223

Isolation and Identification of a Sulfakinin-like Peptide, with Sequence Homology to Vertebrate Gastrin and Cholecystokinin, from the Brain of Locusta migratoria

L. Schoofs, M. Holman, T. Hayes and A. De Loof 231

Characterization and Sequence Determination of Locust Brain cDNA Clones Selected by Antisera Raised Against Vertebrate Peptide Hormones

J. Vanden Broeck, H. Smet, E. Fias and A. De Loaf 243

A Comparative Immunocytochemical Study on the Presence of Cam-Hr'fH-II- and Lom-AKH-I-like Molecules in the Central Nervous System of Three Stick Insects Species: Carausius morosus, Sipyloidea sipylus and Extatosoma tiara tum

F. Clottens, G. Gade, L. Schoofs, R. Huybrechts and A De Loof 251

PHEROMONES

Insect Trail Pheromones: A Perspective of Progress E.D. Morgan 259

Gas Chromatography Linked to Electroantennography: A Versatile Technique for Identifying Insect Semiochemicals.

A. Cork, P.S. Beevor, AJ.E. Gough and D.R. Hall 271

Techniques for Isolation and Characterization of Volatile Semiochemicals of Phytophagous Insects

M.M. Blight 281

The Use of Coupled Gas Chromatography: Electrophysiological Techniques in the Identification of Insect Pheromones

L.J. Wadhams 289

Gas Chromatography-Mass Spectrometry in Insect Pheromone Identification: Three Extreme Case Histories

J.A. Pickett 299

High Performance Liquid Chromatography-Mass Spectrometry in the Analysis of Semiochemicals

A Mudd 311

Analysis of Gland Secretions of Pentatomoidea (Heteroptera) by Gas Chromatography-Mass Spectrometry Techniques

C.E. Evans, B.W. Staddon and D.E. Games 321

Kairomones of the Great European Spruce Bark Beetle Dendroctonus micans

D.R. Kelly and M. Barghian

Pygidial Glands of Primitive Australian Ants: A New Source of Odorous Chemicals

B.D. Jackson, E.D. Morgan and J.P.J. Billen

Volatiles from Exocrine Glands of some Grassland Ants and Termites from Tropical West Mrica

T.O. Olagbemiro, K.M. Sani and B.W. Staddon

329

335

343

ix

PATTERN RECOGNITION

A Computerized System for Pattern Recognition Designed for Gas Chromatograms

BA. Sommerville, M. A. Green and A. J. Bleasby

Abstracts

Compound Index

Species Index

Subject Index

x

351

357

361

365

369

THE CHROMATOGRAPHIC SOCIE1Y

The Chromatographic Society is the only international organization devoted to the promotion of. and the exchange of information on. all aspects of chromatography and related techniques.

With the introduction of gas chromatography in 1952. the Hydrocarbon Chemistry Panel of the Hydrocarbon Research Group of the Institute of Petroleum. recognizing the potential of this new technique. set up a Committee under Dr. S. F. Birch to organize a Symposium on 'Vapor Phase Chromatography' which was held in London in June 1956. Almost 400 delegates attended this meeting and success exceeded all expectation. It was immediately apparent that there was a need for an organized forum to afford discussion of development and application of the method and. by the end of the year, the Gas Chromatography Discussion Group had been formed under the Chairmanship of Dr. A. T. James with D. H. Desty as Secretary. Membership of this Group was Originally by invitation only but. in deference to popular demand. the Group was opened to all willing to pay the modest subscription of one guinea and in 1957 A.J.P. Martin. Nobel Laureate. was elected inaugural Chairman of the newly-expanded Discussion Group.

In 1958 a second Symposium was organized. this time in conjunction with the Dutch Chemical Society. and since that memorable meeting in Amsterdam the Group. now Society. has maintained close contact with kindred bodies in other countries. particularly France (Groupement pour l'Avancement des Methodes Spectroscopiques et Physico-chimiques d'Analyse) and Germany (Arbeitskreis Chromatographie der Gesellschaft Deutscher Chemiker) as well as interested parties in Eire. Italy. The Netherlands. Scandinavia. Spain and Switzerland. As a result Chromatography Symposia. in association with Instrument Exhibitions. have been held biennially in Amsterdam. Edinburgh. Hamburg. Brighton. Rome. Copenhagen. Dublin. Montreux. Barcelona. Birmingham. Baden-Baden. Cannes. London. Nurnburg. PariS and Vienna.

In 1958 'Gas Chromatography Abstracts' was introduced in journal format under the Editorship of C.E.H. Knapman; first published by Butterworths. then by the Institute of Petroleum. it now appears as 'Gas and Liquid Chromatography Abstracts' produced by Elsevier Applied Science Publishers and is of international status - abstracts. covering all aspects of chromatography. are collected by Members from over 200 sources and collated by the Editor Mr. E. R. Adlard assisted by Dr. P. S. Sewell.

Links with the Institute of Petroleum were severed at the end of 1972 and the Group established a Secretariat at Trent PolytechniC in Nottingham. Professor Ralph Stock playing a prominent part in the establishment of the Group as an independent body. At the same time. in recognition of expanding horizons. the name of the organization was changed to the Chromatography Discussion Group.

In 1978. the 'Father' of Partition Chromatography. Professor A. J. P. Martin was both honoured and commemorated by the institution of the Martin Award which is designed as

xi

testimony of distinguished contribution to the advancement of chromatography. Recipients of the award include:

E.R Adlard Professor U.A Th. Brinkman Professor J.C. Giddings Professor J.F.K. Huber Dr. RE. Kaiser Professor J.H. Knox Professor A Liberti Dr. G. Schomburg Dr. L. Snyder and Dr. GA.P. TUey

Professor E. Bayer Dr. L.S. Ettre Professor G. Guiochon Dr. C.E.R Jones C.E.H. Knapman Dr. E. Kovats Dr. C.S.G. Phillips Dr. RP.W. Scott Professor R. Stock

The Group celebrated its Silver Jubilee in 1982 with the 14th International Symposium held. appropriately. in London. To commemorate that event the Jubilee Medal was struck as means of recognizing Significant contributions by younger workers in the field. Recipients of the Jubilee Medal include: Dr. J. Berridge. Dr. H. Colin. Dr. K. Grob Jr.. Dr. J. Hermannson. Dr. E.D. Morgan. Dr. P.G. Simmonds. Dr. P. Schoenmachers and Dr. R Tijssen.

In 1984 the name was once again changed. this time to The Chromagraphic SOCiety. which title was believed to be more in keeping with the role of a learned SOCiety having an international membership of some 1000 scientists drawn from more than 40 countries. At that time. the Executive Committee instituted Conference and Travel Bursaries in order to assist Members wishing to contribute to. or attend major meetings throughout the world.

The Society is run by an Executive Committee elected by its Members. in addition to the international symposia. seven or eight one-day meetings covering a wide range of subjects are organized annually. One of these meetings. the Spring Symposium. is coupled with the Society's Annual General Meeting when. in addition to electing the SOCiety's Executive Committee. Members have the opportunity to express their views on the Society's activities and offer suggestions for future policy.

Regular training courses in all aspects of chromatography are run in conjunction with the Robens Institute of the University of Surrey and it is hoped that this particular service will eventually include advanced and highly specialized instruction.

Reports of the SOCiety's activities. in addition to other items of interest to its members (including detailed summaries of all papers presented at its meetings). are given in the Chromatographic Society Bulletin which is produced quarterly under the editorship of I.W. Davies.

At the time of writing three grades of membership are offered: Membership with Abstracts. Membership. and Student Membership (includes Abstracts). Members receive the Bulletin free of charge. benefit from concessionary Registration Fees for all Meetings and Training Courses and are. of course. eligible to apply for Travel and/or Conference Bursaries.

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For further information and details of subscription rates please write to:

Mrs. J. Challis Executive Secretary TIlE CHROMATOGRAPHIC SOCIE1Y Trent PolytechniC Burton Street Nottingham NG 1 4BU United Kingdom

TIlE ROYAL ENTOMOLOGICAL SOCIEIY OF LONDON

The objects of the Society are 'the improvement and diffusion of entomological science'. These objects are pursued by holding meetings on all aspects of entomology; publishing the results of entomological research; maintaining a large entomological library; supporting entomological expeditions; and more informally by generating discourse between entomologists, particularly at the Society's Rooms.

The Royal Entomological SocietY of London was founded in 1833 as the Entomological Society of London. It was the successor to a number of short-lived societies dating back as far as 1745. The first meetings were held in the Thatched House Tavern, St. James's Street. Various other places in their tum became the scene of the Society's activities before the freehold of the present headquarters at 41 Queen's Gate was bought in 1920. In 1885 a Royal Charter was granted to the Entomological Society by Queen Victoria, and the privilege of adding the word 'Royal' to the tiUe was granted by King George V in 1933, the Centenary of the SOCiety's foundation. Many eminent scientists of the past, Darwin and Wallace to mention but two, have been Fellows of the SOCiety. Through the years down to the sesquicentennial anniversary (1983) of the SOCiety, most internationally recognized entomologists have been and are, numbered among the Fellowship.

The Society is governed by its Royal Charter and Bye-Laws; it is administered by a Council of 16 persons which includes the President, Honorary Treasurer, Honorary Secretary and Honorary Editorial Officer. All Fellows of three years' standing are eligible for election as Officers of the Society or as Members of Council, such elections being held at the Annual Meeting in June. Standing Committees appointed by Council oversee the Society's finanCial and SCientific affairs. The day-to-day running of the Society's business is carried out by the Registrar and staff at 41 Queen's Gate. London SW7 5HU.

Regular monthly evening meetings are held at the Society's Rooms, and twice a year there are Similar meetings in the Regions. At these meetings a paper is presented by an invited speaker or speakers with a discussion afterwards. Informal discussion takes place during tea before the meetings and afterwards. when refreshments are prOvided. The year's programme is formulated to cover all fields of entomology. One- and two-day Workshops organized by the Special Interest Groups that operate within the Society are held three or four times a year. Symposia take place biennially on specific topics when leading entomologists from all over the world give comprehensive and up-to-date accounts of research in their fields. Joint meetings are organized from time to time with other scientific and learned societies.

The elegant premises at Queen's Gate are open to Fellows and their guests Monday to Friday between 9.30 am and 5.00 pm. The Library may be used for private study. and light refreshments are obtainable. The General Office is open for the sale of publications and enquiries. There are other rooms that may be hired for private meetings.

The Society possesses one of the finest entomological libraries in the world, with a superb collection of eighteenth and nineteenth century works on insects. There are in addition collections of the manuscripts. diaries, drawings and correspondence of entomologists. The Library acts as a 'special source' for the British Library. In 1983 it contained some 9000 monographs and works of reference. 55,000 separates and holdings of over 600 journal titles, of which 270 are taken currently. A loan and photocopying service is

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available to Fellows. The Library is open from 9.30-5.00 pm on all weekdays. and until 7.00 pm on Meeting Days. The Librarian is in the Library on Tuesdays. Wednesdays and Thursdays.

The Society publishes four SCientific journals: Ecological Entomology. Physiological Entomology. Systematic Entomology and Medical and Veterinary Entomology. The Society·s house journal Antenna contains reports on all SOCiety Meetings. Workshops. Symposia and other activities; there are also articles. readers' correspondence. an important Diary Section. and many other items of interest to all entomologists. The Handbooks for the Identification of British Insects is an expanding series of important works. The highly successful Symposia Volumes are published biennially following each Symposium. Details of these and other occasional publications are available from the Registrar's Office.

Fellows are elected to the Society by the Council on the proposal of three Fellows. after consideration by the Fellowship Committee and on the recommendation of the Officers. All interested in entomology are welcome to apply for a Fellowship. However. the activities of the Society are at the graduate level and while academiC qualifications are not a prerequisite. it is possible that only entomologists (whether profeSSional or amateur) whose activities and interests are of that standard will benefit from a Fellowship. At the time of the Society's sesquicentennial anniversary there were some 2100 Fellows. of whom about a quarter were living and working overseas. The privileges of the Fellowship include: the right to attend Ordinary Meetings of the Society and to introduce guests; the use of the Library. including loans (UK only). and facilities for photocopying; the receipt of the quarterly bulletin Antenna free of charge; the right to buy any of the Society's publications at greatly reduced prices; the right to attend. at a greatly reduced fee. those SOCiety activities where a registration fee is charged; the right to propose Candidates; the right to make use of the title 'Fellow of the Royal Entomological Society' and suffix "FRES'; and the right to attend and vote at Annual Meetings. A certificate of Fellowship is issued to Fellows on election to the SOCiety.

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For further information and details of subscription rates please write to:

Mr. G. Bentley Registrar ROYAL ENTOMOWGICAL SOCIEIY OF WNDON 41 Queen's Gate London SW7 5HU United Kingdom