The headspace volatiles produced from a phosphate-buffered solution (pH 5) of cysteine and a 1 + 1 mixture of ribose and [(13)C(5)]ribose, heated at 95 degrees C for 4 h, were examined by headspace SPME in combination with GC-MS. MS data indicated that fragmentation of ribose did not play a significant role in the formation of the sulfur aroma compounds 2-methyl-3-furanthiol, 2-furfurylthiol, and 3-mercapto-2-pentanone in which the carbon skeleton of ribose remained intact. The methylfuran moiety of 2-methyl-3-(methylthio)furan originated from ribose, whereas the methylthio carbon atoms came partly from ribose and partly from cysteine. In 3-mercapto-2-butanone one carbon unit was split from the ribose chain. On the other hand, all carbon atoms in 3-thiophenethiol stemmed from cysteine. In another trial cysteine, 4-hydroxy-5-methyl-3(2H)-furanone and [(13)C(5)]ribose were reacted under the same conditions. The resulting 2-methyl-3-furanthiol was mainly (13)C(5)-labeled, suggesting that it stems from ribose and that 4-hydroxy-5-methyl-3(2H)-furanone is unimportant as an intermediate. Whereas 2-mercapto-3-pentanone was found unlabeled and hence originated from 4-hydroxy-5-methyl-3(2H)-furanone, its isomer 3-mercapto-2-pentanone was formed from both 4-hydroxy-5-methyl-3(2H)-furanone and ribose. A new reaction pathway from ribose via its 1,4-dideoxyosone is proposed, which explains both the formation of 2-methyl-3-furanthiol without 4-hydroxy-5-methyl-3(2H)-furanone as an intermediate and a new way to form 3-mercapto-2-pentanone.
Reversed-phase liquid chromatography (RPLC) is commonly used to analyze nonvolatile components in food. However, polar low-molecular-weight compounds such as hydrophilic amino acids, di- and tripeptides, and organic acids are often not sufficiently retained and represent a challenge for RPLC. Hydrophilic interaction liquid chromatography in combination with electrospray mass spectrometry (HILIC-ESI-MS) on a carbamoyl-derivatized stationary phase was successfully employed to separate free amino acids and small polar peptides in complex food matrixes such as wheat gluten hydrolysate and Parmesan cheese. Glutamyl dipeptides were separated in a sequence-specific order with peptides with N-terminal glutamic acid residues eluting prior to their reverse sequence analogues. ESI-MSn detection in the positive ionization mode provided the necessary information to unambiguously identify isobaric peptides due to their characteristic fragmentation patterns. The technique also proved useful to separate and identify glycoconjugates between amino acids and reducing sugars (Amadori compounds). The investigation of organic acids present in food used a mobile phase comprising ammonium acetate buffer at pH 7 and mass spectrometric detection in the negative ionization mode.
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