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In 1891, Villiers isolated for the first time a group of non-reducing oligosaccharides from the enzymatic degradation of starch by an amylase (cyclodextrin glucosyl transferase) produced by different bacilli. Villiers was isolated 3g of a crystalline substance ((C6H10O5)2 3H2O) from the digestion of 1 g of starch by a strain of micro-organisms. The products obtained have physicochemical characteristics similar to those of cellulose, so he dubs “cellulosines.” They are also called dextrins. Schardinger, 20 years later isolated the microbial strain responsible for the formation of these “cellulosines,” he calls Bacillus macerans and describes the mode of purification and preparation of these oligosaccharides. It also highlights the capacity of these dextrins to form specific adducts with di-iodine molecules. The distinction between the α-dextrin and β-dextrin is due to their difference in the crystalline complexes formed with iodine. The complex of α-dextrin is gray-green, while that formed by the β-dextrin is red-brown.
It was in 1932 that Prigsheim and his team demonstrate that these products have the property to form complexes with organic molecules. French, Cramer, and Freudenberg also contributed greatly to the knowledge of cyclodextrins and elucidation of their structure during the year 30-40. Freudenberg and his team demonstrate when these oligosaccharides are composed of a chain of n units to Dglucopyranosidiques, the main fraction containing alpha and beta-cyclodextrin (with units 6 and 7 respectively). Similarly the postulate in the ability of cyclodextrins to form inclusion compounds is set. This same team discovered in 1948 the γ-cyclodextrin (composed to 8 glucose units) and determines its structure completely (Freudenberg, 1953).
In early 1950, teams of French and Cramer studied extensively the enzymatic production of cyclodextrins, their purification, and physicochemical characterizations.
Property of cyclodextrins to form inclusion complexes became the subject of intensive study, in particular by the team Cramer (1957). Thus the first patent on the application of cyclodextrins for the formatting of a compound with biological activity was filed in 1953 (Freudenberg, 1953). From that moment, a recrudescence of the study of cyclodextrins, both in terms of their industrial production, as the exploitation of their properties, their chemical modifications or alternatively, their application areas (Duchêne, 1991).