Synthesis of Wine Thiol Conjugates and Labeled Analogues: Fermentation of the Glutathione Conjugate of 3-Mercaptohexan-1-ol Yields the Corresponding Cysteine Conjugate and Free Thiol

Paris Grant-Preece, Kevin H. Pardon, Dimitra L. Capone, Antonio G. Cordente, Mark A. Sefton, David W. Jeffery, Gordon M. Elsey

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

Synthesis of the putative wine thiol precursor 3-S-glutathionylhexan-1-ol (Glut-3-MH) has been undertaken to provide pure reference materials for the development of HPLC-MS/MS methods for precursor quantitation in grape juice and wine, and for use in fermentation experiments. Labeled thiol conjugates were also prepared for use as internal standards. Purification and fermentation of a single diastereomer of Glut-3-MH with VIN13 (CSL1) yielded not only the (R)-enantiomer of the wine impact odorant 3-mercaptohexan-1-ol (3-MH) but also the cysteine conjugate intermediate as a single (R)-diastereomer, as determined by HPLC-MS/MS. Chiral GC-MS was used to quantify the total amount of (R)-3-MH released from the ferments, resulting in a molar conversion yield of the glutathione conjugate of about 3%. Enzymatic degradation of the single (R)-Glut-3-MH diastereomer with a '-glutamyltranspeptidase confirmed the stereochemical relationship to the related cysteine conjugate. This is the first demonstration that Glut-3-MH can liberate 3-MH under model fermentation conditions, where the cysteine conjugate is also formed in the process. This furthers our understanding of the nature of wine thiol precursors and opens avenues for additional studies into formation and interchange of wine thiols and their precursors.
Original languageEnglish
Pages (from-to)1383-1389
Number of pages7
JournalJournal of Agricultural and Food Chemistry
Volume58
Issue number3
DOIs
Publication statusPublished - Feb 2010

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Wine
thiols
Sulfhydryl Compounds
Fermentation
Glutathione
Cysteine
cysteine
wines
glutathione
diastereomers
fermentation
synthesis
grape juice
enantiomers
High Pressure Liquid Chromatography
odor compounds
Enantiomers
Vitis
Interchanges
3-mercaptohexan-1-ol

Cite this

Grant-Preece, Paris ; Pardon, Kevin H. ; Capone, Dimitra L. ; Cordente, Antonio G. ; Sefton, Mark A. ; Jeffery, David W. ; Elsey, Gordon M. / Synthesis of Wine Thiol Conjugates and Labeled Analogues : Fermentation of the Glutathione Conjugate of 3-Mercaptohexan-1-ol Yields the Corresponding Cysteine Conjugate and Free Thiol. In: Journal of Agricultural and Food Chemistry. 2010 ; Vol. 58, No. 3. pp. 1383-1389.
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abstract = "Synthesis of the putative wine thiol precursor 3-S-glutathionylhexan-1-ol (Glut-3-MH) has been undertaken to provide pure reference materials for the development of HPLC-MS/MS methods for precursor quantitation in grape juice and wine, and for use in fermentation experiments. Labeled thiol conjugates were also prepared for use as internal standards. Purification and fermentation of a single diastereomer of Glut-3-MH with VIN13 (CSL1) yielded not only the (R)-enantiomer of the wine impact odorant 3-mercaptohexan-1-ol (3-MH) but also the cysteine conjugate intermediate as a single (R)-diastereomer, as determined by HPLC-MS/MS. Chiral GC-MS was used to quantify the total amount of (R)-3-MH released from the ferments, resulting in a molar conversion yield of the glutathione conjugate of about 3{\%}. Enzymatic degradation of the single (R)-Glut-3-MH diastereomer with a '-glutamyltranspeptidase confirmed the stereochemical relationship to the related cysteine conjugate. This is the first demonstration that Glut-3-MH can liberate 3-MH under model fermentation conditions, where the cysteine conjugate is also formed in the process. This furthers our understanding of the nature of wine thiol precursors and opens avenues for additional studies into formation and interchange of wine thiols and their precursors.",
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Synthesis of Wine Thiol Conjugates and Labeled Analogues : Fermentation of the Glutathione Conjugate of 3-Mercaptohexan-1-ol Yields the Corresponding Cysteine Conjugate and Free Thiol. / Grant-Preece, Paris; Pardon, Kevin H.; Capone, Dimitra L.; Cordente, Antonio G.; Sefton, Mark A.; Jeffery, David W.; Elsey, Gordon M.

In: Journal of Agricultural and Food Chemistry, Vol. 58, No. 3, 02.2010, p. 1383-1389.

Research output: Contribution to journalArticle

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T2 - Fermentation of the Glutathione Conjugate of 3-Mercaptohexan-1-ol Yields the Corresponding Cysteine Conjugate and Free Thiol

AU - Grant-Preece, Paris

AU - Pardon, Kevin H.

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AU - Elsey, Gordon M.

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AB - Synthesis of the putative wine thiol precursor 3-S-glutathionylhexan-1-ol (Glut-3-MH) has been undertaken to provide pure reference materials for the development of HPLC-MS/MS methods for precursor quantitation in grape juice and wine, and for use in fermentation experiments. Labeled thiol conjugates were also prepared for use as internal standards. Purification and fermentation of a single diastereomer of Glut-3-MH with VIN13 (CSL1) yielded not only the (R)-enantiomer of the wine impact odorant 3-mercaptohexan-1-ol (3-MH) but also the cysteine conjugate intermediate as a single (R)-diastereomer, as determined by HPLC-MS/MS. Chiral GC-MS was used to quantify the total amount of (R)-3-MH released from the ferments, resulting in a molar conversion yield of the glutathione conjugate of about 3%. Enzymatic degradation of the single (R)-Glut-3-MH diastereomer with a '-glutamyltranspeptidase confirmed the stereochemical relationship to the related cysteine conjugate. This is the first demonstration that Glut-3-MH can liberate 3-MH under model fermentation conditions, where the cysteine conjugate is also formed in the process. This furthers our understanding of the nature of wine thiol precursors and opens avenues for additional studies into formation and interchange of wine thiols and their precursors.

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KW - Elution order

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KW - GC-MS

KW - HPLC-MS/MS

KW - Synthesis

KW - Varietal thiols

KW - Wine thiol precursors

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