Alkali complexes, with amylose

Polycrystalline and well-oriented specimens of pure amylose have been trapped both in the A- and B-forms of starch, and their diffraction patterns84-85 are suitable for detailed structure analysis. Further, amylose can be regenerated in the presence of solvents or complexed with such molecules as alcohols, fatty acids, and iodine the molecular structures and crystalline arrangements in these materials are classified under V-amylose. When amylose complexes with alkali or such salts as KBr, the resulting structures86 are surprisingly far from those of V-amyloses. 

Another group of crystalline amyloses consists of complexes with ionic substances, for example, alkali or salts such as KBr. 

It should be noted that the different structures of amylose and amylopectin confer distinctive properties to these polysaccharides (Table II). The linear nature of amylose is responsible for its ability to form complexes with fatty acids, low-molecular-weight alcohols, and iodine these complexes are called clathrates or helical inclusion compounds. This property is the basis for the separation of amylose from amylopectin when starch is solubilized with alkali or with dimethylsulfoxide, amylose can be precipitated by adding 1-butanol and amylopectin remains in solution. 

Whereas all of the methods proposed for large-scale fractionation of starch that have been discussed depend directly on the ability of amylose to form itLsoluble complexes with polar organic compounds. Cantor and Wimmer s process is based on a totally different principle. If a molecularly disperse solution of starch contains a sufficient amount of calcium chloride and caustic alkali is added, a rapid and quantitative precipitation of the starch occurs, because of the formation of complexes (of calcium hydroxide with the starch polysaccharides) which are insoluble in an aqueous, saturated solution of calcium hydroxide. The same phenomenon is observed with the hydroxides of barium and strontium. 

It will be noted that this type of complex-formation is entirely different from that in which complexes are formed between amylose and certain polar, organic compounds. In contrast to the precipitates of the latter complexes (which are of a distinct, crystalline appearance), the starch-alkaline-earth hydroxide complexes are amorphous, curdlike flocculates. These complexes di,s.sociate on diluting them with water, and the starch redissolves. According to the patent description, the amylose complexes dissolve much more easily than the amylopectin complexes hence, fractionation must occur if water is added stepwise. Likewise, fractionation will take place if the starch complexes are partially neutralized, by the gradual addition of an acid. For obvious reasons, such acids as carbonic acid and sulfuric acid (which give insoluble calcium salts) are preferred. Furthermore, it is claimed that gradual addition of caustic alkali to a starch solu-... 

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