Activation of the Maillard Reaction Product 5-(Hydroxymethyl)furfural to Strong Mutagens via Allylic Sulfonation and Chlorination

Abstract

5-(Hydroxymethyl)furfural (HMF), one of the major intermediate products in the Maillard reaction, is present in a wide variety of foods. This aldehyde is formed as a decomposition product of glucose and fructose in foodstuffs subject to cooking or heat sterilization. It has been found to possess mutagenic and DNA strand-breaking activity. However, the mechanisms by which HMF exerts its genotoxicity remain unclear. The present study was undertaken to determine if HMF could be metabolically activated via esterification of the allylic hydroxyl group. In support of this concept, the chemically synthesized sulfuric acid ester,5-[(sulfooxy)-methyl]furfural (SMF), exhibited direct mutagenicity at both thymidine kinase and hypoxanthine-guanine phosphoribosyltransferase loci in human lymphoblasts. This reactive ester also induced 8-azaguanine-resistant mutants in Salmonella typhimurium TM677 in a dose-dependent manner. The intrinsic mutagenicity of SMF was enhanced by addition of extra chloride ion to the assay medium. The model allylic derivative, 5-(chloromethyl)furfural, was also mutagenic and cytotoxic in bacteria, but much more active than the sulfuric acid ester in this regard. In contrast to (sulfooxy)methyl and chloromethyl derivatives of HMF,2-[(sulfooxy)-methyl]- and 2-(chloromethyl)furans which lack the aldehyde functionality did not exhibit significant mutagenicity. Rodent hepatic cytosols contained sulfotransferase activity responsible for the formation of the reactive allylic sulfuric acid ester metabolite from HMF.

The FAST method, a rapid approach of the nutritional quality of heat-treated foods

“…In breakfast cereals, free HMF was chosen as a marker of the Maillard reaction because of the particularly rapid formation of this mutagenic compound [23] due to intense heating and low water content, as compared to dairy products where only traces of HMF are detected [24]. The high HMF content is also in agreement with the data previously reported for extrudated baby cereals (8 to 40 lmol/100 g) [25] or breakfast cereals (8 to 128 lmol/100 g).…”

High temperature-short time glycation to improve heat stability of whey protein and reduce color formation

“…The brown pigments are needed in processes such as baking and coffee roasting as they are associated with sensory characteristics of these products, but are undesirable in most dairy products (Martins & Van Boekel, 2005). In addition to impacting color and flavor, some Maillard reaction products have negative effects on health, e.g., 5-hydroxymethyl-2-furfural (HMF) that has been investigated extensively for its potential mutagenicity, toxicity, carcinogenicity (Capuano & Fogliano, 2011;Janzowski, Glaab, Samimi, Schlatter, & Eisenbrand, 2000;Surh & Tannenbaum, 1994), and adverse effects on human blood cells (Rufian-Henares & de la Cueva, 2008). Therefore, minimizing the formation of HMF and color is needed to produce functional glycated whey proteins.…”

Effect of digestive process on Maillard reaction indexes and antioxidant properties of breakfast cereals

“…Furosine has been considered a useful indicator of the degree of damage during the initial steps of the MR in cereal products such as pasta (Resmini, Pagani, & Pellegrino, 1991), commercial baby cereals (Guerra-Hernández, Corzo, & García-Villanova, 1999), bread (Ramírez-Jiménez, and breakfast cereals (Delgado-Andrade, . Although less valuable as index of thermal damage in cereal-derived products but getting important due to the possible mutagenic activity of its in vivo metabolites (Surh & Tannenbaum, 1994), HMF has also been detected in these foodstuffs (García-Villanova, Guerra-Hernández, Martínez-Gómez, & Montilla, 1993;Guerra-Hernández, García-Villanova, & Montilla-Gomez, 1992;Resmini, Pellegrino, Pagani, & De Noni, 1993;; Rufián-Henares, Delgado-Andrade, & Morales, 2006a).…”