7 156 7 Carbohydrates
AlginateAlginate belongs to the family of linear (unbranched), nonrepeating copolymers. It consists of variable amounts of βd -mannuronic acid (M) and its C5 -epimer α -lguluronic acid (G) which are linked via β -(1,4) -glycosidic bonds. The glycosidic bonds of mannuronic acid are connected to the following unit by a diequatorial 4 C 1 linkage, while guluronic acids are diaxial 1 C 4 linked. Alginate can be regarded as a true block copolymer composed of homopolymeric M and G regions, called M -and G -blocks, respectively, interspersed with regions of alternating structure [5] (Scheme 7.1 ).The physicochemical properties of alginate have been found to be highly affected by the M/G ratio as well as by the structure of the alternating zones. In terms of specifi c medical applications, alginate materials with a high guluronic acid ratio exhibit a much better compatibility [6] . The fi rst protocol to hydrolyze the glycosidic bonds of alginate has been published by Haug et al. in the 1960s and is based on a pH -dependent acid -catalyzed hydrolysis, which leads to a fragmentation of the polymeric chain. Breaking the glycosidic bonds of both building blocks selectively could be achieved due to different p K a values of mannuronic acid (p K a : 3.38) and guluronic acid (p K a : 3.65) [7] . Therefore, polyguluronic acid can be separated by precipitation in aqueous conditions after protonating the carboxyl groups.Alginate can be extracted from marine brown algae or it can be produced by bacteria. Both species produce alginate as an exopolymeric polysaccharide during their growth phase. Isolated alginates from marine brown algae like Laminaria hyperborea or lessonia , gained by harvesting brown seaweeds from coastal regions, tend to vary in their constitution due to seasonal and environmental changes. Like chitin in shellfi sh, alginates in algae have structure -forming functions. This is due to the intracellular formed gel matrix, which is responsible for mechanical strength, fl exibility, and form. Alginates in bacteria are synthesized only by two genera, Pseudomonas and Azotobacter , and have been extensively studied over the last 40 years. While primarily synthesized in the form of polymannuronic acid, the biosynthesis undergoes chemical modifi cations comprising acetylation and epimerization, which occurs during periplasmic transfer and before fi nal export through the outer membrane. Extracted alginate from Pseudomonas contains only M blocks Scheme 7.1 Chemical structure of alginate with mannuronic acid (M), alternating, and guluronic acid (G) blocks.