Ionic liquids (ILs) are composed only of ions. Of special interest to this review are those where at least one ion (the cation) is organic and whose melting points are below or not far above room temperature. ILs are designated as "green" solvents because they have extremely low vapor pressure, are non-inflammable, and thermally and chemically stable. Therefore, many of them can be, in principle, recycled into the process indefinitely. The objective of the present review is to discuss different aspects of the use of ILs in carbohydrate chemistry, in particular, dissolution and functionalization of simple sugars, cyclodextrins, cellulose, starch, and chitin/chitosan. The molecular structure and synthesis of ILs most frequently employed in carbohydrate chemistry are discussed with an emphasis on imidazolium and pyridinium cations with different counterions. The physicochemical properties of ILs that are relevant to the dissolution and functionalization of carbohydrates, in particular their polarities and hydrogen-bonding abilities, are discussed. Dissolution of simple saccharides and biopolymers in ILs is presented with an emphasis on the mechanism of carbohydrate--IL interactions. Finally, the very interesting novel applications of the solutions obtained are addressed. These include, inter alia, spinning of the dissolved biopolymer into fibers, extrusion into slabs and rods, formation of matrixes for a myriad of substrates, including biomacromolecules, formation of nanocomposites, and functionalization to produce important derivatives. The use of ILs in many branches of science is expanding fast; it is hoped that this review will draw the attention of researchers to the "window of opportunities" that these green solvents open into carbohydrate chemistry.

Organic chemistry Z 0200 Applications of Ionic Liquids in Carbohydrate Chemistry: A Window of Opportunities -[177 refs.]. -(EL SEOUD, O. A.; KOSCHELLA, A.; FIDALE, L. C.; DORN, S.; HEINZE, T.; Biomacromol. 8 (2007) 9, 2629-2647; Inst. Quim., Univ. Sao Paulo, 05513 Sao Paulo, Brazil; Eng.) -Lindner 46-241

Summary: Bacterial cellulose (BC), a unique type of cellulose, with high degree of polymerization of 6 500 could be dissolved easily in the ionic liquid 1‐N‐butyl‐3‐methylimidazolium chloride. For the first time, well‐soluble BC acetates and carbanilates of high degree of substitution (up to a complete modification of all hydroxyl groups) were accessible under homogeneous and mild reaction conditions. Characterization of the new BC derivatives by NMR and FTIR spectroscopy shows an unexpected distribution of the acetyl moieties in the order O‐6 > O‐3 > O‐2.13C NMR spectrum (DMSO‐d6) of a cellulose acetate with a DS of 2.25 synthesized in 1‐N‐butyl‐3‐methylimidazolium chloride.image13C NMR spectrum (DMSO‐d6) of a cellulose acetate with a DS of 2.25 synthesized in 1‐N‐butyl‐3‐methylimidazolium chloride.

Some general comments about ionic liquids (ILs) and carbohydrates are given. The main scope of the review is to discuss the present state of the art of chemical modification of cellulose applying IL as reaction media considering own research results. ILs, namely 1‐butyl‐3‐methylimidazolium chloride (BMIMCl), 1‐ethyl‐ 3‐methylimidazolium chloride (EMIMCl), 1‐butyl‐2,3‐dimethylimidazolium chloride (BDMIMCl), 1‐allyl‐2,3‐dimethylimidazolium bromide (ADMIMBr) and 1‐ethyl‐3‐ methylimidazolium acetate (EMIMAc) are solvents for cellulose (even for high molecular bacterial synthesized cellulose) and can easily be applied as reaction media for cellulose modification. We investigated the homogeneous acylation, carbanilation and silylation of the biopolymer cellulose. Under mild conditions and within short reaction time at low temperature (65 °C to 80 °C) and low excess of reagent, various cellulose esters and carbanilates, dendronized cellulose and trimethylsilyl cellulose were obtained. The DS of the cellulose derivatives can be controlled by varying the reaction time, reaction temperature and the IL used as reaction medium.