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Kinetics for unidirectional endwise chain depolymerizations. Experiments with amylose in aqueous alkaline solutions

机译:Kinetics for unidirectional endwise chain depolymerizations. Experiments with amylose in aqueous alkaline solutions

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AbstractA kinetic model for the unidirectional endwise chain‐propagated depolymerization of a linear polymer is described in terms of three pseudo‐first‐order rate constants:k1for the unzipping itself;k2for termination through the formation of stable endgroups; andk3for termination through complete degradation of polymer chains. It is shown that the calculated zip length, ν =k1/(k2+k3), will decrease as the initial substrate D.P. is reduced. For the dimer, a maximum value of ν = 1 is expected. During the anaerobic degradation of potato amylose in aqueous alkaline solutions,k1decreases andk2increases in value as the initial amylose concentration is raised. As a result, quantitative depolymerization occurs at low substrate concentrations, while at raised starch levels an alkali‐stable residue is formed. It is proposed that intermolecular association between polymer chains causes these kinetic differences. For amylose, the constantsk1,k2, andk3are approximately related by the ratio 1000:1:1 or 1000:0:1; and for the homologous disaccharide, the ratio is 10:1:10. The relevance of these findings to the kinetics of cellulose decomposition in aqueous alkali is

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