Esterification of Polysaccharides
Springer Laboratory Springer Laboratory Manuals in Polymer SciencePasch, Trathnigg: HPLC of PolymersISBN: 3-540-61689-6 (hardcover)ISBN: 3-540-65551-4 (softcover)Mori, Barth: Size Exclusion ChromatographyISBN: 3-540-65635-9Pasch, Schrepp: MALDI-TOF Mass Spectrometry of Synthetic PolymersISBN: 3-540-44259-6Kulicke, Clasen: Viscosimetry of Polymers and PolyelectrolytesISBN: 3-540-40760-XHatada, Kitayama: NMR Spectroscopy of PolymersISBN: 3-540-40220-9Brummer, R.: Rheology Essentials of Cosmetics and Food EmulsionsISBN: 3-540-25553-2Mächtle, W., Börger, L.: Analytical Ultracentrifugation of Polymersand NanoparticlesISBN: 3-540-23432-2Heinze, T., Liebert, T., Koschella, A.: Esterification of PolysaccharidesISBN: 3-540-32103-9 Thomas Heinze · Tim Liebert · Andreas KoschellaEsterificationof PolysaccharidesWith 131 Figures, 105 Tables, and CD-ROM123 Thomas HeinzeTim LiebertAndreas KoschellaFriedrich-Schiller-Universit¨at JenaHumboldtstraße1007743 JenaGermanye-mail: thomas.heinze@uni-jena.detim.liebert@uni-jena.deandreas.koschella@uni-jena.deLibrary of Congress Control Number: 2006922413DOI 10.1007/b98412ISBN-10 3-540-32103-9 Springer Berlin Heidelberg New YorkISBN-13 978-3-540-32103-3 Springer Berlin Heidelberg New Yorke-ISBN 3-540-32112-8This workis subjectto copyright. All rights are reserved, whether the whole or part of the material is concerned,specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproductionon microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereofis permitted only under the provisions of the German Copyright Law of September 9, 1965, in its currentversion, and permissions for use must always be obtained from Springer. Violations are liable for prosecutionunder the German Copyright Law.The publisher and the authors accept no legal responsibility for any damage caused by improper use of theinstructions and programs contained in this book and the CD-ROM. Although the software has been testedwith extreme care, errors in the software cannot be excluded.Springer is a part of Springer Science+Business Mediaspringer.com© Springer-Verlag Berlin Heidelberg 2006PrintedinGermanyThe use of general descriptive names, registered names, trademarks, etc. in this publication does not imply,even in the absence of a specific statement, that such names are exempt from the relevant protective laws andregulations and therefore free for general use.Cover design: design&production, Heidelberg, GermanyTypesetting and production: LE-TEX Jelonek, Schmidt & Vöckler GbR, Leipzig, Germany2/3141 YL 5 4 3 2 1 0 - Printed on acid-free paper Springer Laboratory Manuals in Polymer ScienceEditorsProf. Howard G. BarthDuPont CompanyP.O. box 80228Wilmington, DE 19880-0228USAe-mail: Howard.G.Barth@usa.dupont.comPriv.-Doz. Dr. Harald PaschDeutsches Kunststoff-InstitutAbt. AnalytikSchloßgartenstr. 664289 DarmstadtGermanye-mail: hpasch@dki.tu-darmstadt.deEditorial BoardPD Dr. Ingo AligDeutsches Kunststoff-InstitutAbt. PhysikSchloßgartenstr. 664289 DarmstadtGermanyemail: ialig@dki.tu-darmstadt.deProf. Josef JancaUniversité de La RochellePole Sciences et TechnologieAvenue Michel Crépeau17042 La Rochelle Cedex 01Franceemail: jjanca@univ-lr.frProf. W.-M. KulickeInst. f. Technische u. Makromol. ChemieUniversität HamburgBundesstr. 4520146 HamburgGermanyemail: kulicke@chemie.uni-hamburg.deProf.H.W.SieslerPhysikalische ChemieUniversität EssenSchützenbahn 7045117 EssenGermanyemail: hw.siesler@uni-essen.de PrefaceThe recent world attention towards renewable and sustainable resources has re-sulted in many unique and groundbreaking research activities. Polysaccharides,possessing various options for application and use, are by far the most impor-tant renewable resources. From the chemist’s point of view, the unique structureof polysaccharides combined with many promising properties like hydrophilicity,biocompatibility, biodegradability (at least in the original state), stereoregularity,multichirality, and polyfunctionality, i.e. reactive functional groups (mainly OH−,NH−, and COOH− moieties) that can be modified by various chemical reactions,provide an additional and important argument for their study as a valuable andrenewable resource for the future.Chemical modification of polysaccharides has already proved to be one of themost important paths to develop new products and materials. The objective of thisbook is to describe esterification of polysaccharides by considering typical syn-thesis routes, efficient structure characterisation, unconventional polysaccharideesters, and structure-property relationships. Comments about new applicationareas are also included.The content of this book originated mainly from the authors’ polysaccharideresearch experience carried out at the Bergische University of Wuppertal, Ger-many and the Friedrich Schiller University of Jena, Germany. The interaction oftheauthorswithProf.D.Klemmwasagreatstimulustoremainactiveinthisfascinating field. In addition, there is increasing interest from industry in the fieldof polysaccharides that is well documented by the establishment of the Centerof Excellence for Polysaccharide Research Jena-Rudolstadt. The aim of the centreis to foster interdisciplinary fundamental research on polysaccharides and theirapplication through active graduate student projects in the fields of carbohydratechemistry, bioorganic chemistry, and structure analysis.The authors would like to stress that the knowledge discussed in this book doesnot represent an endpoint. On the contrary, the information about polysaccharideesters provided here will hopefully encourage scientists in academia and industryto continue the search for and development of new procedures, products, andapplications. The authors strongly hope that the polysaccharide ester informationhighlighted in this book will be helpful both for experts and newcomers to thefield.During the preparation of the book, the members of the Heinze laboratorywere very helpful. We thank Dr. Wolfgang Günther for the acquisition of NMR VIII Prefacespectra, Dr. Matilde Vieira Nagel for preparing many tables and proofreading thetext as well as Stephanie Hornig, Claudia Hänsch, Constance Ißbrücker, and SarahKöhler for technical assistance. Special thanks go to Prof. Werner-Michael Kulicke,University of Hamburg, who encouraged us to contribute a synthetic topic to theSpringer Laboratory series. Dr. Stan Fowler (ES English for Scientists) is gratefullyacknowledged for proofreading the manuscript.The authors would like to express gratitude to Springer for agreeing to publishthis book in the Springer Laboratory series. We thank Dr. Marion Hertel of Springerfor her conscientious effort.Jena, February 2006 Thomas HeinzeTim LiebertAndreas Koschella List of Symbols and Abbreviations[C4mim]Br 1-N-Butyl-3-methylimidazolium bromide[C4mim]Cl 1-N-Butyl-3-methylimidazolium chloride[C4mim]SCN 1-N-Butyl-3-methylimidazolium thiocyanateAc AcetylAFM Atomic force microscopeAGU Anhydroglucose unitsAMIMCl 1-N-Allyl-3-methylimidazolium chlorideAPS Amino propyl silicaArafα-l-ArabinofuranosylArap ArabinopyranosylAX ArabinoxylansAXU Anhydroxylose unitBu ButylCadoxen Cadmiumethylenediamine hydroxideCDI N, N-CarbonyldiimidazoleCI-MS Chemical ionisation mass spectroscopyCOSY Correlated spectroscopyCTFA Cellulose trifluoroacetateCuen Cupriethylenediamine hydroxideDB Degree of branchingDCC N, N-DicyclohexylcarbodiimideDDA Degree of deacetylationDEPT Distortionless enhancement by polarisation transferDMAc N, N-DimethylacetamideDMAP 4-N, N-DimethylaminopyridineDMF N, N-DimethylformamideDMI 1,3-Dimethyl-2-imidazolidinoneDMSO Dimethyl sulphoxideDP Degree of polymerisationDS Degree of substitutionDQF Double quantum filterEI-MS Electron impact ionisation mass spectroscopyFAB-MS Fast atom bombardment mass spectroscopyFACl Fatty acid chlorideFTIR Fourier transform infrared spectroscopy X List of Symbols and AbbreviationsGAα-d-Glucopyranosyl uronic acidGalNAc N-Acetyl-d-galactosamineGalp GalactopyranoseGalpN GalactopyranosylamineGalpNAc N-AcetylgalactopyranosylamineGLC Gas liquid chromatographyGLC-MS Gas liquid chromatography-mass spectroscopyGlcN d-GlucosamineGlcNAc N-Acetyl-d-glucosamineGlcA Glucuronic acidGlcp GlucopyranoseGPC Gel permeation chromatographyGX 4-O-Methyl-glucuronoxylanHMBC Heteronuclear multiple bond correlationHMPA Hexamethylphosphor triamideHMQC Heteronuclear multiple quantum coherenceHPLC High-performance liquid chromatographyHSQC Heteronuclear single quantum correlationIcCrystallinity indexINAPT Selective version of insensitive nuclei enhanced by polarisa-tion transferMaldi-TOF Matrix assisted laser desorption ionisation time of flightManp MannopyranoseMeGA 4-O-Methyl-α-d-glucopyranosyl uronic acidMEK MethylethylketoneMesCl Methanesulphonic acid chlorideMethyl triflate Trifluoromethanesulphonic acid methylesterMwMass average molecular massn.d. Not determinedNa dimsyl Sodium methylsulphinylNBS N-BromosuccinimideNIR Near-infraredNitren Ni(tren)(OH)2[tren=tris(2-aminoethyl)amine]NMMO N-Methylmorpholine-N-oxideNMP N-Methyl-2-pyrrolidoneNMR Nuclear magnetic resonanceNOE Nuclear Overhauser effectNOESY Nuclear Overhauser effect spectroscopyPAHBA p-Hydroxybenzoic acid hydrazidePP 4-PyrrolidinopyridinePy PyridineRI Refractive indexRT Room temperatureRU Repeating unitSNNucleophilic substitution [...]... content of the polysaccharide can be increased by epimerization of the C-5 centre of α -l-guluronic acid to give β -d-mannuronic acid. In view of the fact that the structural features of the polysaccharides discussed above may change dueto, for example,seasonal conditions,comprehensive analysis of the specific biopolymer is recommended as discussed in the next chapter. Fig. 2.11. Chemical structure of alginate ... Chemical shifts of the 13 C NMR signals of chitin in CD 3 COOD and mixture of CD 3 COOD/TFA Solvent Chemical shift (ppm) C-1 C-2 C-3 C-4 C-5 C-6 TFA/CD 3 COOD 98.2 56.2 70.7 77.9 75.3 60.8 CD 3 COOD 100.5 58.7 73.0 79.4 77.7 62.9 In addition to the detection of substructures, the general assignment of 13 C NMR spectra discussed is also useful for the elucidation of structural features of unknown polysaccharides. ... on the chemical shifts of the signals. Measurements in D 2 O commonly lead to a downfield shift (higher ppm values) in the range of 1–2 ppm. In Table 3.4, an overview of relevant chemical shifts and corresponding carbon atoms for 13 C NMR signals of polysaccharides is given. Table 3.4. General overview of chemical shifts and the corresponding carbon atoms for 13 C NMR signals of polysaccharides C atom... classical concepts of esterification, such as conversions of cellulose to carboxylic acid esters of C 2 to C 4 acids including mixed derivatives of phthalic acid and cellulose nitrate, which are produced in large quantities. These commercial paths of polysaccharide esterification are carried out exclusively under heterogeneous conditions, at least at the beginning of the conversion. The majority of cellulose... the spectragiveinsightsintothelinkageofacetylated(A) and deacetylated (D)RU, and may be used for sequence analysis (Fig. 3.10). An interesting approach for the analysis of complex polysaccharide structures or mixtures of polysaccharides is the complete degradation (acid hydrolysis) and determination of the type of sugar and the concentration using the α -and β - anomeric protons (H-1) as “probes”. A list of chemical shifts... laboratory-scale synthesisofthepolymerbyAcetobacter xylinum and Acanthamoeba castellani [28], which circumvents problems associated with the extraction of cellulose. 2.1.2 β -(1→3)-Glucans There are a number of structural variations within the class of polysaccharides classified as β -(1→3)-glucans. The group of β -(1→3, 1→6) linked glucans has been shown to stimulate and enhance the human immune system. Althoughpolysaccharidesofthecurdlantypearepresentinavarietyofliv- ing... methods of modification and analysis described are mainly focused on glucans because they represent a large part of naturally occurring polysaccharides. Moreover, glucans are structurally most uniform. In contrast, polysaccharides consisting of various monosaccha- rides and substructures, e.g., galactomannans, or algal polysaccharides exhibit a broad diversity in properties caused by a large number of irreproducible... 63 Solid state 13 C NMR spectroscopy of chitin shows an upfield shift of the C-2 signal to about 58 ppm, compared to cellulose. The technique can be used to calculate the degree of N-acetylation from the signal ratio of the methyl moieties of the acetyl function at about 21 ppm versus the carbons of the AGU in the range 58–103 ppm [47]. For solution 13 C NMR investigation of cellulose and chitin, specific... treatment of the biopolymers is enzymatic digestion com- bined with chromatographic investigation of the resulting mixtures of oligosaccha- rides. Thus, the enzymatic digestion of pullulan followed by HPLC analysis of the resulting digest can be applied to determine the presence of maltooligosaccharides with more than ten glucose units [57]. For dextran, it is used for the determination of the branching... as they provide easy access to a variety of bio-based materials with valuable properties. In particular, state -of- the-art esterification can yield a broad spectrumofpolysaccharidederivatives,asdiscussedintheframeofthisbookfrom a practical point of view but are currently only used under lab-scale conditions. In contrast, simple esterification of the most abundant polysaccharides cellulose and starch are . fieldof polysaccharides that is well documented by the establishment of the Centerof Excellence for Polysaccharide Research Jena-Rudolstadt. The aim of the. modification of polysaccharides has already proved to be one of themost important paths to develop new products and materials. The objective of thisbook