Hepatic production of 1,5-anhydrofructose and 1,5-anhydroglucitol in rat by the third glycogenolytic pathway

A unique anhydrohexulose, 1,5-anhydrofructose (1,5AnFru) has been detected in rat livers. Here we describe a microanalytical method for 1,5AnFru using GC/MS and report results on the distribution and production of 1,5AnFru in rats. The highest levels of 1,5AnFru were found in the liver (0.43 mu g/g wet tissue) and appreciable amounts were detected in adrenal gland and spleen (0.12 mu g/g and 0.09 mu g/g, respectively). Other organs contained lower amounts while plasma contained virtually no detectable 1,5AnFru. We also demonstrated that 1,5AnFru is produced in the cytosol fraction of rat liver homogenate when an alpha-1,4-glucan or glycogen was added; 1,5AnFru was readily reduced to 1,5-anhydroglucitol with NADPH or at a reduced efficiency with NADH in the presence of a Mono Q chromatographic fraction obtained from the same cytosol preparation. Based on these results, we propose the existence of a third degradation pathway, in addition to the phosphorolytic and hydrolytic reaction sequences, from glycogen to 1,5-anhydroglucitol via 1,5AnFru in mammals. However, the physiological significance of 1,5AnFru and this putative minor glycogenolytic pathway in mammals remains obscure.