This book provides a first comprehensive summary of acylation methods in a very practical manner. The coverage includes new developments not yet summarized in book form, and reviews spectroscopic methods, in particular FTIR- and NMR spectroscopy including two dimensional methods. A variety of FTIR-, 1H NMR- and 13C NMR spectra are collected on the supplemental CD-ROM. Polysaccharide esters (e.g. cellulose and starch) are among the first polymeric materials applied commercially. The way of producing these technically relevant derivatives, mainly the carboxylic acid esters of C2 to C4 acids, have not been changed significantly during their history of manufacture. The investigation of new acylation methods and strategies of analysis was revived during the last decade by the search for tailored, biocompatible material for specific fields of application, e.g., biotechnology, sensor technique and medicine. Unconventional solvents were developed for completely homogeneous acylation reaction applying state of the art techniques of modern organic chemistry for polysaccharide modification. This book will provide a first comprehensive summary of acylation methods in a very practical manner. Detailed structure analysis is indispensable for the evaluation of structure-property-relationships. Spectroscopic methods in particular FTIR- and NMR spectroscopy including two dimensional methods are of increasing importance. 1 INTRODUCTION AND OBJECTIVES 1(4) 2 STRUCTURE OF POLYSACCHARIDES 5(10) 2.1 Structural Features 5(10) 2.1.1 Cellulose 6(1) 2.1.2 (1 >3)-Glucans 7(1) 2.1.3 Dextran 8(1) 2.1.4 Pullulan 8(1) 2.1.5 Starch 9(1) 2.1.6 Hemicelluloses 9(3) 2.1.7 Guar 12(1) 2.1.8 Inulin 12(1) 2.1.9 Chitin and Chitosan 12(2) 2.1.10 Alginates 14(1) 3 ANALYSIS OF POLYSACCHARIDE STRUCTURES 15(26) 3.1 Optical Spectroscopy 16(2) 3.2 NMR Spectroscopy 18(23) 3.2.1 C NMR Spectroscopy 19(7) 3.2.2 H NMR Spectroscopy 26(5) 3.2.3 Two-dimensional NMR Techniques 31(3) 3.2.4 Chromatography and Mass Spectrometry 34(7) 4 ESTERS OF CARBOXYLIC ACIDS - CONVENTIONAL METHODS 41(12) 4.1 Acylation with Carboxylic Acid Chlorides and Anhydrides 41(12) 4.1.1 Heterogeneous Acylation - Industrial Processes 41(5) 4.1.2 Heterogeneous Conversion in the Presence of a Base 46(7) 5 NEW PATHS FOR THE INTRODUCTION OF ORGANIC ESTER MOIETIES 53(64) 5.1 Media for Homogeneous Reactions 53(22) 5.1.1 Aqueous Media 54(3) 5.1.2 Non-aqueous Solvents 57(5) 5.1.3 Multicomponent Solvents 62(8) 5.1.4 Soluble Polysaccharide Intermediates 70(5) 5.2 In Situ Activation of Carboxylic Acids 75(31) 5.2.1 Sulphonic Acid Chlorides 76(6) 5.2.2 Dialkylcarbodiimide 82(4) 5.2.3 N,N'-Carbonyldiimidazole 86(17) 5.2.4 Iminium Chlorides 103(3) 5.3 Miscellaneous New Ways for Polysaccharide Esterification 106(11) 5.3.1 Transesterification 106(6) 5.3.2 Esterification by Ring Opening Reactions 112(5) 6 SULPHONIC ACID ESTERS 117(12) 6.1 Mesylates 117(3) 6.2 Tosylates 120(8) 6.3 Miscellaneous Sulphonic Acid Esters 128(1) 7 INORGANIC POLYSACCHARIDE ESTERS 129(14) 7.1 Sulphuric Acid Half Esters 129(7) 7.2 Phosphates 136(4) 7.3 Nitrates 140(3) 8 STRUCTURE ANALYSIS OF POLYSACCHARIDE ESTERS 143(26) 8.1 Chemical Characterisation Standard Methods 145(1) 8.2 Optical Spectroscopy 145(4) 8.3 NMR Measurements 149(6) 8.4 Subsequent Functionalisation 155(14) 8.4.1 NMR Spectroscopy on Completely Functionalised Derivatives 155(7) 8.4.2 Chromatographic Techniques 162(7) 9 POLYSACCHARIDE ESTERS WITH DEFINED FUNCTIONALISATION PATTERN 169(12) 9.1 Selective Deacylation 170(2) 9.2 Protective Group Technique 172(8) 9.2.1 Tritylation 173(3) 9.2.2 Bulky Organosilyl Groups 176(4) 9.3 Medium Controlled Selectivity 180(1) 10 SELECTED EXAMPLES OF NEW APPLICATIONS 181(14) 10.1 Materials for Selective Separation 182(4) 10.1.1 Stationary Phases for Chromatography 184(1) 10.1.2 Selective Membranes 184(2) 10.2 Biological Activity 186(1) 10.3 Carrier Materials 187(8) 10.3.1 Prodrugs on the Basis of Polysaccharides 188(2) 10.3.2 Nanoparticles and Hydrogels 190(2) 10.3.3 Plasma Substitute 192(3) 11 OUTLOOK 195(2) 12 EXPERIMENTAL PROTOCOLS 197(20) REFERENCES 217(12) SUBJECT INDEX 229