Studies on the Chemical Decomposition of Simple Sugars. XII. Mechanism of the Acetol Formation

Hayami, Jun-ichi

doi:10.1246/bcsj.34.927

Cited by 35 publications

(31 citation statements)

References 11 publications

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“…The same mechanism was proposed also for the formation of glyceric acid from 2-deoxyhexo-3,4-diulose (Yang & Montgomery 1996a). The splitting of β-dicarbonyl sugar intermediates was first proposed by Hayami (1961) and later confirmed by Weenen (1998), explaining the formation of acetol and glyceric acid from pentose and hexose sugars. The recent in-depth mechanistic study of Davídek et al (2006a, b) employing labelled compounds (various 13 C-labeled glucose isotopomers, 18 O 2 , H 2 17 O) represents a breakthrough in the understanding of the mechanisms involved in the acid formation.…”

mentioning

confidence: 54%

Formation of carboxylic acids during degradation of monosaccharides

Novotny¹,

Cejpek²,

Velı́šek³

2008

Czech J. Food Sci.

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Novotný O., Cejpek K., Velíšek J. The formation of low molecular carboxylic and hydroxycarboxylic acids as well as sugar and deoxysugar acids from monosaccharides (d-glucose, d-fructose, d-arabinose, dl-glyceraldehyde, and 1,3-dihydroxyacetone) was studied in three different model systems: aqueous and alkaline solutions of potassium peroxodisulfate (K 2 S 2 O 8 ), and sodium hydroxide solution. In total, 3 low molecular carboxylic acids (formic, acetic and propionic), 24 hydroxycarboxylic acids, and 12 corresponding lactones were identified and quantified by GC/MS. Formic, acetic, and propionic acids were isolated by extraction with diethyl ether and directly analysed by GC/MS; hydroxycarboxylic acids and their lactones were monitored as their trimethylsilylated derivatives using the same method. Formic, acetic, l-lactic, glycollic, dl-2,4-dihydroxybutanoic acids and aldonic acids derived from the parent sugars were the most abundant compounds in all model systems. Within the models investigated, the yield of carboxylic acids and hydroxycarboxylic acids (together with their lactones) ranged between 9.3-22.2% (n/n) and between 3.6-116.9% (n/n), respectively. The amount of acids was significantly lower in aqueous solutions of K 2 S 2 O 8 than in the alkaline solutions. The data obtained indicate that lower carboxylic acids are formed by both subsequent reactions (oxidation and/or intramolecular Cannizzaro reaction) of the sugar fragmentation products and direct decomposition of some intermediates such as uloses or hydroperoxides derived from the parent sugars. The acids possessing the original sugar skeleton are formed as a result of sugar oxidation or benzilic acid type rearrangement of deoxyuloses. Lower acids may also be formed by a recombination of free radicals.

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mentioning

confidence: 54%

Formation of carboxylic acids during degradation of monosaccharides

Novotny¹,

Cejpek²,

Velı́šek³

2008

Czech J. Food Sci.

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“…Hydrolytic β-dicarbonyl cleavage of sugars was already mentioned in 1961 as an alternative fragmentation pathway to retro-aldol reactions [71]. Again, Davidek et al were the first to perform detailed mechanistic studies [72,73].…”

Section: Hydrolytic β-Cleavagementioning

confidence: 99%

Pathways of the Maillard reaction under physiological conditions

2016

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Initially investigated as a color formation process in thermally treated foods, nowadays, the relevance of the Maillard reaction in vivo is generally accepted. Many chronic and age-related diseases such as diabetes, uremia, atherosclerosis, cataractogenesis and Alzheimer's disease are associated with Maillard derived advanced glycation endproducts (AGEs) and α-dicarbonyl compounds as their most important precursors in terms of reactivity and abundance. However, the situation in vivo is very challenging, because Maillard chemistry is paralleled by enzymatic reactions which can lead to both, increases and decreases in certain AGEs. In addition, mechanistic findings established under the harsh conditions of food processing might not be valid under physiological conditions. The present review critically discusses the relevant α-dicarbonyl compounds as central intermediates of AGE formation in vivo with a special focus on fragmentation pathways leading to formation of amide-AGEs.

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“…The observed products (and/or inferred precursors) will be discussed in order of increasing numbers of carbon atoms: C 3 products: acrolein (5), propionaldehyde (6), pyruvaldehyde (2-oxopropanal or methylglyoxal) (7), acetone (8), hydroxyacetone (acetol) (9), and 1,3-dihydroxyacetone (10) [versus glyceraldehyde (11)] ( Table 1); C 4 products: 3-buten-2-one (methyl vinyl ketone) (12), 2-butanone (methyl ethyl ketone) (13), diacetyl (2,3-butanedione) (14), and 1-hydroxy-2,3-butanedione (''methyl reductone'') (15) ( Table 2) and hydroxymethyl vinyl ketone (16), Ecrotonaldehyde (17), Z-crotonaldehyde (18), and methacrolein (19) (Table 3). 3-Cyclopentene-1,2-dione (23) will be discussed in Table 5.…”

Section: Overview Of D-glucose Fragmentationmentioning

confidence: 99%

“…Hayami et al [16][17][18] had found that most acetol originated from the first three carbons, or, to a somewhat lesser extent, from the last three carbons, with C-1 and C-6 providing the methyl groups. Hayami's work was done in aqueous phosphate buffer.…”

Section: Overview Of D-glucose Fragmentationmentioning

confidence: 99%