~ ~ ~ ~ ~ ~ ~ ~ - - ~ ~ r J.0A4cOPY ONLY ~ ~ ~ ~ ~ ~ ~ ~ PROCEEDINGSOF THE FIRST INTERNATIONALCONFERENCE ON CHITIN/CHITOSAN May 1978 Edited by R.A.A. Muzzare111 University of Ancona, Italy E.R. Pariser Sea Grant Program Massachusetts Institute of Technology The hosts for the conference, which was held in Boston, Massachusettson April 11 through 13, 1977, were the MIT Sea Grant Program and the Massachusetts Science and Technology Foundation. MIT Sea Grant Report MITSG78-7 Index No. 78-307-Dmb INTRODUCTION Theobjective of the MITSea Grant Programand the Massachusetts Scienceand Technology Foundation in conveningthe First International Conferenceon Chitin/Chitosanwas to bri ng together those experts and researchers from around the world who are working to expand the uses of this exciting, abundant,renewable natural resource. By providing a forum, we hopedto encouragethe businessand scientific communities to share insights and experiences,to stimulate newideas, and to identify researchthat wouldadvance the applicationof chitin and chitosan in pharmaceuticals,food processing,papermaking, agriculture, adhesive and textile manufacturing, and waste treatment. Weare publishing the proceedings of this conference becausewe believe that continuedinformation sharing is essential if the advances in deve'lopingthis valuable resourceare to continue. Wewish to ex- pressour appreciation to all thosewho participated in andcontributed to the conference, and we sincerely hope that publication of the papers will serve in the future as a comprehensivereference source for them, as well as for those who could not attend. Mr. Irving Sacks Mr. Dean A. Horn Acting Director Director Massachusetts Science and MIT Sea Grant Program Technology Foundation 15 May 1978 Wededicate these proceedings to the National Sea Grant Office, and especially to Dr. Robert Abel and Mr. HaroId Goodwin whose vision and wisdom are responsible for making the study of chitin and chitosan a matter uf international concern. R. A.A. Muzzarelli E.R, Pariser University of Ancona, Massachusetts Institute Italy of Technology ACKNOWLEDGMENTS Wewish to acknowledgethe cooperation and support received from the following organizationswhose contributions madethis conference possible, University of Delaware Sea Grant Program University of WashingtonSea Grant Program Nationa 1 Sea Grant Program, NDAA, DOC Massachusetts Institute of Technology The initiation, planning, organizing and managingof a meetingsuch as this conferencealways requires a taxing and pro- tracted team effort involving manyparticipants whoseefforts it is impossibleto acknowledgeadequately. Thenames of at least two peoplemust, however,be recordedhere in appreciation of the great contributionsthey made: Mr. VincentLoCicero, formerly of the MassachusettsScience and Technology Foundation who was largely in chargeof pre-conferencepreparations and conference organization; the other is Ms. Marie Phaneuf, also of the MassachusettsScience andTechnology Foundation, the organizing genius, whokept all major and minor details, correspondenceand papers in mind and in order and who started the enormousand difficult job of retyping the scientific paperspresented at the conference. RichardDeAmicis should also be mentioned here to acknowledgehis important contri- butionssin initiating the editing work on the papers. We owea very specialvote of thanksto Ms,Margaret M. Sevcenkowho undertook the arduousand complicated task of editing, proofreadingand organizing the text of these proceedings,which we fee'I she did superbly. Last, but by nomeans least, wemust thank the wholeMIT Sea Grant staff for its patient and efficient cooperation over the last year, but especially wewould like to expressour thanksto Ms. JoanneSullivan for her meticulous, tireless and alwayscheerful efforts to ready the manuscript for final printing. To co-host the conference and publish the proceedings of the First International Conference on Chitin/Chitosan, the MIT Sea Grant Program received support from the Office of Sea Grant in the National Oceanic and Atmospheric Administration, U,S. Department of Ccmmierce,through grant number 04-6-158-44081 ~ and from the Massachusetts Institute of Technology. The U,S. Government is authorized to produce and distribute reprints for governmental purposes notwithstanding any copyright notation that may appear hereon. RELATEDREPORTS The following reports contain information related to the project described herein: CHITIN ANDCHITIN DERIVATIVES, MIT/Marine Industry Collegium Opportunity Brief. M!TSG76-5. Cambridge: Massachusetts Institute of Technology, August 1976. 21 pp, $2,5O, Ashford, Nicholas A., Dale Hattis, and Albert E. Murray. INDUSTRIALPROSPECTS FOR CHITIN AND PROTEINFROM SHELLFISHWASTES. MITSG 77-3. Cambridge: Massachusetts Institute of Technology, 1976. 99 pp. $12.50. The Sea Grant Information Center maintains an inventory of all technical publications. We invite orders and inquiries to: Sea Grant Information Center HIT S ea Grant P rogram 77 Mas sachu set t s Avenue Cambridge, Massachusetts 02139 P REFACE ~IIITIN kai'tin!. Zoos, and Chem.Also -ine. [a. F. ch tine, f. Gr. yizDv frock, tunic: see -IN. The etymologicalformation would be chitonin!] The organic substance which forms the elytra and lntegumentsof insects and the carapacesof crustacea. The Oxford English Dictionary, 1961 One of the streets in the old quarter of Nancy, France, bears the nameof Henri Braconnot, the discoverer of chitin. Braconnot, who lived from I/80 to 1856, studied chemistry and botany ln Strasbourgand biology and geology in Paris. Still ln his twenties, he became director of the Botanic Gardens of Nancy. The city honored him, however, apparently not for his scientific contri- butions'~ but for a generous sumof moneyhe left to the town, In the course of his work with mushrooms in 1 811, Braconnot becameintrigued with a cellulosic substancehe had isolated which did not undergochange ln an alkaline solution. Henamed the substance, "fungine." Tenyears later, in 1821,the name"chitlne" wasgiven to a material seemingly identical to fungine, but found by A. Odier while studying insects. Qdier, whopublished the newname in the M6moiresde la Socibtd d'Histoire Naturelle de Paris and in the Dictionnaire Classique d'Historic Naturelle, noted," It is most remarkable tu find the exoskeleton of insects to be identical with the cuticle of plants." ThoughOdier was incorrect in believing the two substances were identical, he is distinguished for not only namingchitin but for being the first personto observethe remarkablesimilarity betweenthe function of cellulose in plants and that of "chitine" in insects. Scientific interest in chitin continued for a time, but eventually muchpublished work fell into disuse and was forgotten until almost 40 years ago whenawareness that this natural polymer hadan impressivenumber of potential applications stimulated new research. The editors of these proceedings believe that this curiosity and subsequentinvestigations into the usesof' chitin contributed to the British war effort by providing a superior adhesive for the woodenfighter planes used by the British during the beginning of World War II. Nowmore than a century and a half after Braconnot madehis discovery, scientists throughoutthe world are fascinated by the potential large-scale, industrial applications for chitin. And they continue to be astonishedby the numberof living organisms in which they are finding chitin, its derivative chitosan, and enzymescapable of interacting with the two substances. Chitin has comeof age.in both basic and applied scienceand technology. At a time when it is accepted, indeed imperative, that the wise utilization of natura'1 resources is a conditio sine gua non f h eeity's se i 1, it legit 1, fe sighted ~i' te e g with the best traditions of international scientific cooperation for the Sea Grant Program of NOAA, U.S. Department of Convaerce, together with listed academic institutions and organizations, to co-sponsor and generously support the first international confer- ence on chitin and chitosan, of which these are the proceedings. Most of the papers in this volume were presented at the conference. Papers by E,R, HAYES, et al., page 103; K. SIMPSON, page 253; O.L. OKE, et al., page 327; lhl. TAKEDA,page 355; B,P. HETTICK, et al,, page 464; M.l . BADE, page 472; S.C. SHRIVASTAVA, et al,, page 492; C.J. BRINE, page 509; K. OKUTANI, page 582; and K.O. PARKER,page 606, however, were received after the conference and are included here because of the contributions they are making to the field. TABLEOF CONTENTS Page Chairman's Address Chitin, an Important Natura'I Polymer Riccardo A. A. Muzzarelli I . SOURCE OF CHITIN Distribution and Quantitative Importance of Chitin in Animals Ch. Je uniaux TheDistribution andQuantitative Importanceof Chitin in Fungi Jose Ruiz-Ilerrera The Detection and Estimation of Chitin in Insect Organs 22 A. Glenn Richards I I, ECONDMICCONSIDERATIONS OF ALTERNATIVESOURCES OF CHITIN 29 Approachesto a PracticalAssessment of Supplyand Demandfor Chitin Products in the United States Albert E. Murray and Dale kattis 3O The Economicsot' Chitin Recoveryand Production 45 Peter M. Perceval Antartic Krill EuphausiaSuperba! as a Sourceof Chitin and Chitosan C. G. Anderson, N. de Pablo and C. R. Rorno 54 A Criti ca'I Evaluation of the Potent i a1 Sourcesof Chitin and Chitosan G. G. A1Ian, J. R. Fox, and N. Kong 64 III. TECHNOOGV OF CHITIN-CHITOSAN PROCESSING 79 The Production of Chitin and Chitosan Edwin Lee Johnsonand Quintin P. Peniston