In all cases, the caramelization reactions contributed less to the browning intensity than to the overall UV-absorbance. The UV-absorbance values are more or less representative of intermediate compounds in the nonenzymatic browning reactions (Hodge 1953; Lerici and others 1990), whereas the absorbance values at 420 nm may be related to the content in brown polymers, and the 294/420 nm absorbance ratio is indicative of the polymerization extent. Figure 5 illustrates the effect of pH on
the transformation of intermediates into brown polymers in fructose and fructose-lysine model systems after a 1-h heating period at 100 8C. As regards the caramelization reaction of fructose, a pH increase from 4.0 to 8.0 strongly enhanced the polymerization of the carbonyl compounds generated by the thermal degradation of fructose, whereas at a higher pH value, the intermediates were almost equally transformed into brown polymers. When fructose was heated in the presence of
lysine at a pH value between 4.0 and 8.0, formation of the intermediate olymerization
products decreased, whereas above pH 8.0 the rate of polymerization reactions of the intermediate carbonyl compounds seem not to be dependent on both the pH and the presence of the amino acid. Figure 5 strongly suggests that changes in the mechanism of the nonenzymatic browning reaction occurred around pH 8.0. According to the general scheme of Hodge (1953), dealing with the chemistry
of nonenzymatic browning reactions in model systems, the Amadori compounds are supposed to give rise preferentially to furfurals and related derivatives under acidic conditions, while reductones and highly reactive dicarbonyls are formed essentially under alkaline conditions. As pointed out in the introduction, there are some conflicting data about the reactivity of fructose as compared to glucose as far as browning is concerned.With respect to the intermediate stages of the Maillard reaction, volatile compounds such as furans, pyrans, and pyrroles have been obtained in larger amounts from fructose than from glucose when each sugar was
heated in the presence of â-alanine