5-hydroxymethylfurfural and 3-deoxyglucosone

5-Hydroxymethylfurfural (5-HMF) is a harmful substance generated during the processing of black garlic. Our previous research demonstrated that impregnation of black garlic with epigallocatechin gallate (EGCG) could reduce the formation of 5-HMF. However, there is still a lack of relevant research on the mechanism and structural identification of EGCG inhibiting the production of 5-HMF. In this study, an intermediate product of 5-HMF, 3-deoxyglucosone (3-DG), was found to be decreased in black garlic during the aging process, and impregnation with EGCG for 24 h further reduced the formation of 3-DG by approximately 60% in black garlic compared with that in the untreated control. The aging-mimicking reaction system of 3-DG + EGCG was employed to determine whether the reduction of 3-DG was the underlying mechanism of decreased 5-HMF formation in EGCG-treated black garlic. The results showed that EGCG accelerated the decrease of 3-DG and further attenuated 5-HMF formation, which may be caused by an additional reaction with 3-DG, as evidenced by LC-MS/MS analysis. In conclusion, this study provides new insights regarding the role of EGCG in blocking 5-HMF formation.

Topics: Catechin; Deoxyglucose; Dose-Response Relationship, Drug; Furaldehyde; Garlic

This study aims to investigate in depth the mechanism of acrylamide formation in coffee during roasting. For this purpose, a comprehensive kinetic model including the elementary steps for acrylamide formation was proposed. The changes in sucrose, reducing sugars, free amino acids, asparagine, acrylamide, 3-deoxyglucosone, methylglyoxal, glyoxal, and 5-hydroxymethylfurfural were monitored in coffee during roasting at 200, 220 and 240 °C. Dominant pathways of complex reactions leading to acrylamide were unravelled by means of multiresponse kinetic modelling approach. The results of the model indicated that sucrose degrades into glucose and a reactive fructofuranosyl cation. Interestingly, glucose takes part mostly in the formation of intermediates, glyoxal and especially 3-deoxyglucosone rather than acrylamide formation. On the other hand, fructofuranosyl cation contributed mostly to the formation of 5-hydroxymethylfurfural which was found to be the most important intermediate precursor of acrylamide formed in coffee during roasting.

Topics: Acrylamide; Amino Acids; Coffee; Deoxyglucose; Food-Processing Industry; Furaldehyde; Glucose; Glyoxal; Hot Temperature; Kinetics; Pyruvaldehyde; Sucrose

During the conventional production of brown fermented milk (BFM), unhealthy substances (3-deoxyglucosone (3-DG), methylglyoxal (MGO), and 5-hydroxymethylfurfural (HMF)) are generated during the Maillard browning step. Here, an alternative browning process based on the hydrolysis of endogenous lactose was established. Compared with the conventional process, 3-DG and HMF were decreased by 5.91 mg kg-1 and 0.39 mg kg-1 in the brown milk base under the alternative browning process, and thereafter, 3-DG and HMF were decreased by 54.5% and 65.0% in BFM. Investigation into the formation of 3-DG, MGO, and HMF in different chemical models showed that different sugars lead to different Maillard reaction products and browning rates, contributing to the mitigation of 3-DG and HMF. Apart from the mitigation of unhealthy Maillard compounds, hydrolyzing lactose and avoiding the addition of external glucose make the alternative browning process a theoretical and practical basis for improving the quality and safety of BFM.

Topics: Animals; Cattle; Deoxyglucose; Fermentation; Furaldehyde; Glucose; Hot Temperature; Hydrolysis; Lactose; Maillard Reaction; Milk

Ultra-performance liquid chromatography coupled with high-resolution tandem mass spectrometry (UPLC-HRMS/MS) was employed to investigate the inhibitory mechanism of quercetin against the formation of 5-(hydroxymethyl)-2-furaldehyde (HMF) in buckwheat flour bread. The HMF and HMF precursors (3,4-dideoxyglucosone-3-ene (3,4-DGE), 3-deoxyglucosone (3-DG), or fructofuranosyl cation dehydration products (FCDPs)) adducts of quercetin were detected in buckwheat flour bread, with the trapping of these compounds by quercetin to form corresponding adducts with HMF or its precursors in 1:1, 1:2, 1:3, and 1:4 ratios (where "1" refers to quercetin in all cases). The structures of these adducts were elucidated by UPLC-HRMS/MS. Carbohydrate module labeling (CAMOLA) techniques and the labelled quercetin in model reactions were utilized to further confirm the inhibitory mechanism. Effects of baking temperature and time on the HMF inhibition rate were investigated in wheat flour bread, and a maximum inhibition rate of 86.0% was obtained with the baking of wheat flour bread (with the added quercetin concentration of 1.90mg/g) at 160°C for 30min.

Topics: Bread; Chromatography, High Pressure Liquid; Deoxyglucose; Fagopyrum; Flour; Furaldehyde; Quercetin; Tandem Mass Spectrometry

The measurement of α-dicarbonyls and other degradation products of sugars has become important in view of their toxicity. Although there are several methods used for their analysis, most require long reaction times to form UV absorbing or fluorescent derivatives and the nonpolar nature of commonly used derivatives necessitates relatively high concentrations of organic solvents for elution in reverse phase liquid chromatography. The present method describes the use of Girard-T reagent in a simple, one step derivatization of α-dicarbonyls and conjugated aldehydes and analysis using ion-pair reverse phase liquid chromatography. The limit of detection was in the range of 0.06-0.09 μM (4-12 ng/mL) for glyoxal, methylglyoxal, 3-deoxyglucosone and 5-hydroxymethylfurfural with good linear response and reproducibility using UV detection. The hydrazone derivatives were stable for several days in solution. The method was used to study degradation of several sugars and quantification of the target α-dicarbonyls and 5-hydroxymethylfurfural in several soft drinks.

Topics: Betaine; Chromatography, Liquid; Deoxyglucose; Furaldehyde; Glyoxal; High Fructose Corn Syrup; Limit of Detection; Linear Models; Reproducibility of Results

The antiglycative activity of hydroxytyrosol (HT) and olive leaf extract (OLE) was investigated in wheat-flour biscuits. Quercetin (QE) and gallic acid (GA) were used as reference of antiglycative activity of phenolic compounds. HT, OLE, QE and GA were added in the range of 0.25-0.75% (w/w). Samples were compared against a control recipe baked at 180°C/20min. HT biscuit was able to inhibit efficiently the formation of hydroxymethylfurfural (HMF) and 3-deoxyglucosone (3-DG), as well as reduced the formation of overall free fluorescent AGEs and pentosidine. The inhibition of the 3-DG and HMF formation was directly and significantly correlated under controlled baking conditions. However, samples formulated with OLE exerted similar antiglycative capacity against pentosidine and Nε-carboxyethyl-lysine, although the amount of HT in the biscuit was 100-fold lower than the biscuit formulated with HT. Methylglyoxal, 3-DG, and glyoxal were the predominant 1,2-dicarbonyl compounds after baking but only 3-DG was significantly reduced by HT.

Topics: Arginine; Chromatography, Liquid; Deoxyglucose; Flour; Food Handling; Furaldehyde; Gallic Acid; Glycation End Products, Advanced; Lysine; Maillard Reaction; Olea; Phenylethyl Alcohol; Plant Extracts; Plant Leaves; Pyruvaldehyde; Quercetin; Tandem Mass Spectrometry; Triticum

A comprehensive kinetic model indicating the elementary steps of Maillard reaction and caramelization during hazelnut roasting was proposed based on a multi-response kinetic modeling approach. Changes in the concentrations of sucrose, fructose, glucose, amino acids, 3-deoxyglucosone, 1-deoxyglucosone, 3,4-dideoxyglucosone, glyoxal, methylglyoxal, dimethylglyoxal, and 5-hydroxymethylfurfural were examined in hazelnuts during roasting at 150, 160 and 170°C for 15, 30, 60, 90, and 120min. The results suggested that 1,2-enolization was important in the interconversion of glucose and fructose, 5-hydroxymethylfurfural formation mainly proceeded via fructofuranosyl cation dehydration rather than 3-deoxglucosone, glucose contributed more than fructose and fructofuranosyl cation to the early stage of the Maillard reaction. Methylglyoxal and dimethylglyoxal were mainly formed from 1-deoxyglucosone with high reaction rate constants while glyoxal formed through glucose degradation. α-Dicarbonyl compounds could have a role in the formation of melanoidins. The temperature dependence of the reactions was complicated and could not be explained by the Arrhenius equation.

Topics: Amino Acids; Cooking; Corylus; Deoxyglucose; Fructose; Furaldehyde; Glucose; Glyoxal; Kinetics; Maillard Reaction; Pyruvaldehyde; Sucrose

In beer, 3-deoxyglucosone (3-DG) and 3-deoxygalactosone (3-DGal) are important sugar degradation products, but little is known about the relevance of the interconversion reaction between these compounds in different types of beer. In the present study, 3-DG was quantitated at concentrations of 12.9-52.7 mg/L and 3-DGal at concentrations of 6.0-26.4 mg/L in different types of beer (pilsner, wheat, bock, dark, and alcohol-free beers). The concentrations in malt beer tended to be higher. Largely overlapping concentration ranges precluded a classification of beers by their 3-deoxyglycosone contents. 3,4-Dideoxyglucoson-3-ene (3,4-DGE) was identified as an important intermediate and quantitated in beer and malt beer for the first time. The E and Z isomers of the corresponding quinoxaline were synthesized by a new synthetic approach and isolated by semipreparative HPLC. An assay was developed for quantitation of (E)- and (Z)-3,4-DGE by HPLC-MS/MS, and the Z isomer was determined at concentrations of 0.3-1.7 mg/L in beer and 0.5-4.8 mg/L in malt beer samples. The E isomer was shown to be of little importance. Concentrations of 5-hydroxymethylfurfural (HMF) were twice as high as those of (Z)-3,4-DGE in beer samples (0.4-3.7 mg/L) but much higher in malt beer samples (1.6-336 mg/L).

Topics: Beer; Chromatography, High Pressure Liquid; Deoxyglucose; Furaldehyde; Galactose; Stereoisomerism; Tandem Mass Spectrometry; Triticum

1,2-Dicarbonyl compounds, formed from carbohydrates during thermal processing in the course of caramelization and Maillard reactions, are intensively discussed as precursors for advanced glycation endproducts in foods and in vivo. To obtain information about the uptake of individual compounds with commonly consumed foods, a comprehensive analysis of the content of 3-deoxyglucosone (3-DG), 3-deoxygalactosone (3-DGal), and methylglyoxal (MGO) together with 5-hydroxymethylfurfural (HMF) in 173 food items like bakery products, pasta, nonalcoholic and alcoholic beverages, sweet spreads, and condiments was performed. Following suitable cleanup procedures, 1,2-dicarbonyl compounds were quantitated after derivatization with o-phenylenediamine via RP-HPLC with UV detection. 3-DG proved to be the predominant 1,2-dicarbonyl compound with concentrations up to 410 mg/L in fruit juices, 2622 mg/L in balsamic vinegars, and 385 mg/kg in cookies, thus exceeding the corresponding concentrations of HMF. 3-DGal was found to be of relevance in many foods even in the absence of galactose. MGO was only of minor quantitative importance in all foods studied, except for manuka honey. Dietary intake was estimated to range between 20 and 160 mg/day for 3-DG and 5 and 20 mg/day for MGO, respectively.

Topics: Chromatography, High Pressure Liquid; Deoxyglucose; Diet; Food Analysis; Furaldehyde; Galactose; Pyruvaldehyde

Topics: Deoxyglucose; Furaldehyde; Glucose; Thermodynamics

In this study we conducted a survey of the concentrations of the major 1,2-dicarbonyl compounds in 40 commercial honey samples from 12 different floral origins. 3-Deoxyglucosone (3-DG), glyoxal (GO), and methylglyoxal (MGO) were measured, using their corresponding quinoxaline derivatives, by high-performance liquid chromatography (HPLC). The analytical performance of the HPLC method for the analysis of 1,2-dicarbonyl compounds was evaluated in terms of linearity, limits of detection (LODs), limits of quantification (LOQs), and precision. Linearity over 2 orders of magnitude, LODs (0.01-0.04 mg/kg), and LOQs (0.03-0.12 mg/kg) were calculated. Instrumental precision, as measured by the repeatability relative standard deviation% (RSDr%), was found to be between 0.22% and 0.55%. Furthermore, the concentrations of factors GO and MGO with respect to 3-DG were also calculated for rapid quantification in honey. In honey samples, the concentrations of 3-DG ranged from 75.9 to 808.6 mg/kg and were significantly higher (up to 100-fold) than those of 5-hydroxymethylfurfural (HMF). Values for GO and MGO were 0.1-10.9 and 0.2-2.9 mg/kg, respectively. The chemical characteristics that most influenced the levels of 1,2-dicarbonyl compounds in honey were found to be pH and total phenols. This was supported by multivariate analysis used to classify different honey types with respect to their chemical characteristics. In addition, both dicarbonyls and phenols are believed to contribute to the development of the final color of honey.

Topics: Chromatography, High Pressure Liquid; Deoxyglucose; Food Analysis; Furaldehyde; Glyoxal; Honey; Ketones; Limit of Detection; Phenols; Pyruvaldehyde

In this study, the inhibitory effects of antibrowning agents on browning and the formation of intermediates such as 3-deoxyglucosone (3-DG) and hydroxymethylfurfural (HMF) were evaluated with a glucose-glutamic acid model for soybean paste. The initial antibrowning capacity was measured in the following order: pentasodium tripolyphosphate < citric acid and oxalic acid < cysteine and glutathione < sodium sulfite. Our data showed that antibrowning agents, such as pentasodium tripolyphosphate, citric acid, and oxalic acid, were maintained antibrowning capacities during storage at both 4 and 30 °C, respectively. However, both cysteine and glutathione was reduced with storage time, especially in the air. A marked effect of nitrogen treatment was noted for 3 of the antibrowning agents after storage in air at 30 °C in the following order: sodium sulfite < cysteine < glutathione. The formation ratio of 3-DG and HMF was higher after storage at 30 °C than at 4 °C. These compounds were produced most abundantly in the presence of sodium sulfite, and the yields were not related significantly to the degree of browning. Citric acid and oxalic acid were identified as the most effective in inhibitors of browning and intermediates, even during storage in air at 30 °C.

Topics: Citric Acid; Condiments; Deoxyglucose; Ferrous Compounds; Food Handling; Food Preservatives; Furaldehyde; Glucose; Glutamic Acid; Maillard Reaction; Models, Chemical; Osmolar Concentration; Oxalic Acid; Oxygen; Soy Foods; Temperature; Time Factors