Fructose-induced fluorescence generation of reductively methylated glycated bovine serum albumin: Evidence for nonenzymatic glycation of Amadori adducts

In vitro glycation of bovine serum albumin by fructose (fructation) induces fluorescence generation about 10-times faster than glucose (G. Suárez et al. (1989) J. Biol. Chem. 264, 3674-3679). In order to gain further insight into possible mechanisms that would explain this difference, the protein was glycated with either glucose or fructose and then reincubated in the absence of sugars. In contrast to the previous findings, albumin that had been glycated with glucose generated fluorescence at a higher rate during the sugar-free incubation. However, when partially glycated BSA was reincubated with sugars under conditions where de novo glycation was prevented by reductive methylation of amino groups fructose induced fluorescence to a much larger extent than glucose. These results are consistent with the notion of covalent addition of sugars to Amadori groups, the earliest stable products of the Maillard reaction. A chemical pathway is proposed where pyrrolic structures result from the double sugar adducts by aldol condensation and dehydration. These structures might be precursors of fluorophores.