3-Deoxygalactosone, a “New” 1,2-Dicarbonyl Compound in Milk Products

Abstract

1,2-Dicarbonyl compounds are formed in food during Maillard and caramelization reactions. 3-Deoxy-D-threo-hexos-2-ulose (3-deoxygalactosone, 3-DGal) and galactosone, two 1,2-dicarbonyl compounds originating from the degradation of galactose, were synthesized and converted to the respective quinoxalines, which were characterized by NMR spectroscopy. Analytical separation of the quinoxalines from the epimeric glucose-derived quinoxalines of 3-deoxyglucosone (3-DG) and glucosone was achieved by RP-HPLC on an RP-phenyl column. This method was used to study the relevance of galactose-derived 1,2-dicarbonyl compounds in a variety of foods. 3-DG and 3-DGal were quantified besides 3-deoxypentosone, methylglyoxal, and glyoxal after derivatization with o-phenylenediamine in lactose-hydrolyzed UHT milk, ranging from 2.5 to 18 mg/L and from 2.0 to 11 mg/L, respectively. The concentrations of both compounds tended to be higher in other lactose-hydrolyzed food items as well. During storage of lactose-hydrolyzed milk, the concentrations of the 3-deoxyhexosones first increased, but especially the concentration of 3-DGal tended to decrease on prolonged storage, pointing to lower stability of the compound. 3-DGal was also detected in galactose-free food items such as apple juice and beer. The possible formation of 3-DGal from 3-DG by 3,4-dideoxyglucosone-3-ene as an intermediate is discussed. Compared to the relatively high concentrations of 3-DG and 3-DGal, 3-deoxypentosone, methylglyoxal, and glyoxal were of only minor quantitative importance in all foods studied.

Identification and quantification of six major α-dicarbonyl process contaminants in high-fructose corn syrup

“…Therefore, the sum of both isomers reflects the 3,4-DGE concentration in the product. 3-DGal, a diastereomer of 3-DG, has initially been reported as a degradation product of galactose, which is formed analogously to 3-DG from glucose [16]. However, it has been shown, in the meantime, that 3-DGal is also an important glucose degradation product that is generated by the addition of water to 3,4-DGE [16,24].…”

“…The product was recrystallized once from 100% ethanol and dried overnight in a desiccator. This intermediate product was used to synthesize 3-DGal according to literature with minor modifications [16]. Five grams of 3-deoxy-D-erythro-hexos-2-ulose bis(benzoylhydrazone) was suspended in 400 mL 37.5% ethanol and 22 mL acetic acid.…”

“…In foods, α-DCs have been identified in lactose-hydrolyzed ultra-high-temperature milk, honey, beer, wine, coffee, and soft drinks [16][17][18][19][20][21][22]. Lo et al identified and quantified glyoxal (GO), methylglyoxal (MGO), and 3-deoxy-D-erythro-hexos-2-ulose (3-deoxyglucosone (3-DG)) in several HFCS samples [20].…”

Quantification of 3-deoxyglucosone (3DG) as an aging marker in natural and forced aged wines

“…Moreover, the production of Amadori compounds in wines has already been described by Hashiba 1978, and more recently several Maillard-like compounds have been identified in typical and ageing aromas of champagne wines (thiazoles and oxazoles like: 2,4-dimethylthiazole, 4-methylthiazole, 2-acetylthiazole, 2-acetyl-2-thiazoline, or 2,4,5-trimethyloxazole; and furanthiols like furan-2-yl-methanethiol) (Keim, de Revel, Marchand, & Bertrand, 2002;Tominaga, Guimbertau, & Dubourdieu, 2003) Formation of 3DG has been evaluated in model systems (Usui et al, 2007;Fiedler & Kroh, 2007;Golon & Kuhnert, 2013), biological samples (Hoffman, Kappler, Passmore, & Mehta, 2003;Hurtado-Sanchez, Espinosa-Mansilla, Rodrıguez-Caceres, Martın-Tornero & Durán-Merás, 2012), and food products such as: sake (Oka, 1969), soy sauce (Hashiba, 1976;Kim & Lee, 2008), balsamic vinegars (Daglia, Amoroso, Rossi, Mascherpa, & Maga, 2013), carbonated soft drinks (Gensberger, Glomb, & Pischetsrieder, 2013), milk products (Hellwig, Degen, & Henle, 2010), high-fructose corn syrups (Lo et al, 2008;Gensberger, Mittelmaier, Glomb, & Pischetsrieder, 2012;RuizMatute, Vazquez, Hernández-Hernández, Sanza, & Martínez-Castro, 2015), beers (Bravo et al, 2008;Hellwig, Nobis, Witte, & Henle, 2016), commercial honey samples (Weigel, Opitz, & Henle, 2004;Mavric, Wittmann, Barth, & Henle, 2008;Marceau & Yaylayan, 2009;Ruiz-Matute et al, 2015), bee feeds (Ruiz-Matute et al, 2015), coffee substitutes (Ruiz-Matute et al, 2015), baby foods (Kocadağlı & Gökmen, 2014) and wines (in nonsweet wines: 2.2 to 13.5 mg·L -1 ; and in sweet wines: 39 to 133 mg·L -1 ) ( Therefore, dry white and sweet red Port wines were derivatized with orthophenylenediamine and the corresponding 3DG quinoxalines determined by HPLC with photodiode array detector (HPLC-DAD) coupled to tandem mass spectrometry (MS n ). In orde...…”

Proteomic characterization of intermediate and advanced glycation end-products in commercial milk samples

“…glyoxal (G), methylglyoxal (MG), 3-deoxyglucosone (3-DG), 3-deoxygalactosone (3-DGal), 3-deoxypentosone (3-DPen) ( Supplementary Fig. S1) [6][7][8][9]. When model peptides/proteins were treated with these dicarbonyl compounds, the formation of the AGEs mentioned above and of: i) G-, MG-, 3-DG-and 3-DGal-derived hemiaminals (G-He, MG-He, 3-DG-He, and 3-DGal-He), ii) G-, MG-, 3-DG-and 3-DGal-derived dihydroxyimidazolines (G-DH, MG-DH, 3-DG-DH, and 3-DGal-DH), iii) G-, MG-, 3-DG-, and 3-DGal-derived hydroimidazolones (G-H, MG-H, 3-DG-H, and 3-DGal-H), iv) di-and tetra-hydropyrimidines (DHP and THP) was ascertained ( Supplementary Fig.…”