Difference between revisions of "Tetrahydropyridine"

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Forms of '''Tetrahydropyridines''', specifically 6-Acetyl-2,3,4,5-tetrahydropyridine (ATHP or ACTPY), 2-ethyltetrahydropyridine (ETHP), and 2-acetyl-1-pyrroline (ACPY or APY) <ref name="wikipedia">[http://en.wikipedia.org/wiki/6-Acetyl-2,3,4,5-tetrahydropyridine 6-Acetyl-2,3,4,5-tetrahydropyridine.  Wikipedia.  Retrieved 3/210/2015.]</ref>, which are classified as ketones <ref>[https://www.facebook.com/groups/MilkTheFunk/permalink/1034461653248715/?comment_id=1034611563233724&offset=0&total_comments=29 Humbard, Matt.  Milk The funk Discussion.  3/10/2015.]</ref>, are commonly attributed to the "mousy", "urine" (in high amounts) "cheerios" or "Captain Crunch" (in low amounts), "breakfast cereal", or more generically, "cracker biscuit" flavor in sour beers.  The flavor is detected towards the end of the swallow.  Diacetyl is sometimes mistakenly indicated as a potential cause of this flavor in sour beers.  However, Tetrahydropyridines are the accepted cause.  The flavor tends to age out of sour beers after 2-3 months (it is unknown whether cold or room temperature storage speeds this up), although the exact mechanism for this is not fully understood <ref>[http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/#post6516169 Tonsmeire, Michael.  Homebrewtalk.com post 1.  11/21/2014.  Retrieved 3/10/2015.]</ref>.  Many brewers have noticed that pitching rehydrated wine yeast at bottling reduces the amount/duration of this flavor <ref>[http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/#post6522207 Tonsmeire, Michael.  Homebrewtalk.com post 2.  11/21/2014.  Retrieved 3/10/2015.]</ref>.  
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Forms of '''Tetrahydropyridines''' (THP), specifically 6-Acetyl-2,3,4,5-tetrahydropyridine (ATHP or ACTPY), 2-ethyltetrahydropyridine (ETHP), and 2-acetyl-1-pyrroline (ACPY or APY) <ref name="wikipedia">[http://en.wikipedia.org/wiki/6-Acetyl-2,3,4,5-tetrahydropyridine 6-Acetyl-2,3,4,5-tetrahydropyridine.  Wikipedia.  Retrieved 3/210/2015.]</ref>, which are classified as ketones <ref>[https://www.facebook.com/groups/MilkTheFunk/permalink/1034461653248715/?comment_id=1034611563233724&offset=0&total_comments=29 Humbard, Matt.  Milk The funk Discussion.  3/10/2015.]</ref>, are commonly attributed to the "mousy", "urine" (in high amounts) "cheerios" or "Captain Crunch" (in low amounts), "breakfast cereal", or more generically, "cracker biscuit" flavor in sour beers.  The flavor is detected towards the end of the swallow.  Diacetyl is sometimes mistakenly indicated as a potential cause of this flavor in sour beers.  However, Tetrahydropyridines are the accepted cause.  The flavor tends to age out of sour beers after 2-3 months (it is unknown whether cold or room temperature storage speeds this up), although the exact mechanism for this is not fully understood <ref>[http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/#post6516169 Tonsmeire, Michael.  Homebrewtalk.com post 1.  11/21/2014.  Retrieved 3/10/2015.]</ref>.  Many brewers have noticed that pitching rehydrated wine yeast at bottling reduces the amount/duration of this flavor <ref>[http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/#post6522207 Tonsmeire, Michael.  Homebrewtalk.com post 2.  11/21/2014.  Retrieved 3/10/2015.]</ref>.  
  
 
In food, Tetrahydropyridines are associated with the aroma of baked goods such as white bread, popcorn, and tortillas, and is formed by Maillard reactions during heating.  ATHP and APY have an odor threshold of 0.06ng/l <ref name="wikipedia"></ref>.
 
In food, Tetrahydropyridines are associated with the aroma of baked goods such as white bread, popcorn, and tortillas, and is formed by Maillard reactions during heating.  ATHP and APY have an odor threshold of 0.06ng/l <ref name="wikipedia"></ref>.
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[[File:THP Pathway.JPG|thumb|400|Proposed pathway for THP production by ''Brett'' <ref name="Elsevier">[https://books.google.com/books?hl=en&lr=&id=KJJwAgAAQBAJ&oi=fnd&pg=PA346&dq=brettanomyces+Tetrahydropyridine&ots=ktbn8PR_fF&sig=r3lkcV-gBa-pK86HSOgFDVIJVDk#v=onepage&q=brettanomyces%20Tetrahydropyridine&f=false Managing Wine Quality: Oenology and Wine Quality. A Reynolds Elsevier, Sep 30, 2010. Pg 359.]</ref>]]
 
[[File:THP Pathway.JPG|thumb|400|Proposed pathway for THP production by ''Brett'' <ref name="Elsevier">[https://books.google.com/books?hl=en&lr=&id=KJJwAgAAQBAJ&oi=fnd&pg=PA346&dq=brettanomyces+Tetrahydropyridine&ots=ktbn8PR_fF&sig=r3lkcV-gBa-pK86HSOgFDVIJVDk#v=onepage&q=brettanomyces%20Tetrahydropyridine&f=false Managing Wine Quality: Oenology and Wine Quality. A Reynolds Elsevier, Sep 30, 2010. Pg 359.]</ref>]]
  
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[[Brettanomyces]], [[Lactobacillus]], and [[Pediococcus]] can produce forms of ''Tetrahydropyridine''.  In Brettanomyces, ATHP and ETHP are produced by metabolizing the amino acids L-Lysine and D-Lysine, along with ethanol and a glucose or fructose molecule. Oxygen has a stimulatory effect in it's production, but this is probably because ''Brett'' has a higher biomass formation under aerobic conditions <ref>[http://www.brettanomycesproject.com/dissertation/introduction/ Yakobson, Chad.  The Brettanomyces Project; Introduction.  Retrieved 3/10/2015.]</ref><ref>[http://pubs.acs.org/doi/abs/10.1021/jf071243e The Role of Lysine Amino Nitrogen in the Biosynthesis of Mousy Off-Flavor Compounds by Dekkera anomala.  Paul R. Grbin, Markus Herderich, Andrew Markides, Terry H. Lee, and Paul A. Henschke. J. Agric. Food Chem., 2007.]</ref><ref name="Oelofse">[http://scholar.sun.ac.za/handle/10019.1/8437 Significance of Brettanomyces and Dekkera during Winemaking: A Synoptic Review.  A. Oelofse, I.S. Pretorius, and M. du Toit.  2008.]</ref>.  The level of THP production varies widely between species and strains of ''Brett'', with some strains not producing it at all and some producing very high amounts above taste threshold.  Additionally, THP production appears to require glucose or fructose, which explains why THP may be seen more often in stuck wine fermentations rather than wine that has finished fermenting.  ATHP production by ''Brett'' was observed in wine with glucose or fructose added, along with synthetic growth media, suggesting that the type of growth substrate does not effect production <ref>[http://www.ncbi.nlm.nih.gov/pubmed/18194246 Growth and volatile compound production by Brettanomyces/Dekkera bruxellensis in red wine.  Romano A, Perello MC, de Revel G, Lonvaud-Funel A.  J Appl Microbiol. 2008 Jun.]</ref>.   
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[[Brettanomyces]], [[Lactobacillus]], and [[Pediococcus]] can produce forms of Tetrahydropyridine.  In Brettanomyces, ATHP and ETHP are produced by metabolizing the amino acids L-Lysine and D-Lysine, along with ethanol and a glucose or fructose molecule. Oxygen has a stimulatory effect in it's production, but this is probably because ''Brett'' has a higher biomass formation under aerobic conditions <ref>[http://www.brettanomycesproject.com/dissertation/introduction/ Yakobson, Chad.  The Brettanomyces Project; Introduction.  Retrieved 3/10/2015.]</ref><ref>[http://pubs.acs.org/doi/abs/10.1021/jf071243e The Role of Lysine Amino Nitrogen in the Biosynthesis of Mousy Off-Flavor Compounds by Dekkera anomala.  Paul R. Grbin, Markus Herderich, Andrew Markides, Terry H. Lee, and Paul A. Henschke. J. Agric. Food Chem., 2007.]</ref><ref name="Oelofse">[http://scholar.sun.ac.za/handle/10019.1/8437 Significance of Brettanomyces and Dekkera during Winemaking: A Synoptic Review.  A. Oelofse, I.S. Pretorius, and M. du Toit.  2008.]</ref>.  The level of THP production varies widely between species and strains of ''Brett'', with some strains not producing it at all and some producing very high amounts above taste threshold.  Additionally, THP production appears to require glucose or fructose, which explains why THP may be seen more often in stuck wine fermentations rather than wine that has finished fermenting.  ATHP production by ''Brett'' was observed in wine with glucose or fructose added, along with synthetic growth media, suggesting that the type of growth substrate does not effect production <ref>[http://www.ncbi.nlm.nih.gov/pubmed/18194246 Growth and volatile compound production by Brettanomyces/Dekkera bruxellensis in red wine.  Romano A, Perello MC, de Revel G, Lonvaud-Funel A.  J Appl Microbiol. 2008 Jun.]</ref>.   
  
 
ATHP is further metabolized into 2-ethyltetrahydropyridine (ETHP/ETPY) by Brettanomyces, although not much is known about this metabolic process <ref>[http://ucce.ucdavis.edu/files/repositoryfiles/Joseph_5_Aromatic_Diverswity_of_Brettanomyces-82350.ppt Joseph, C.M. Lucy.  ''Aromatic Diversity of Brettanomyces''.  U.C. Davis.  Retrieved 3/10/2015.]</ref>.  ETHP has a significantly higher taste threshold, and is often not detected in contaminated wine <ref name="Oelofse"></ref>.   
 
ATHP is further metabolized into 2-ethyltetrahydropyridine (ETHP/ETPY) by Brettanomyces, although not much is known about this metabolic process <ref>[http://ucce.ucdavis.edu/files/repositoryfiles/Joseph_5_Aromatic_Diverswity_of_Brettanomyces-82350.ppt Joseph, C.M. Lucy.  ''Aromatic Diversity of Brettanomyces''.  U.C. Davis.  Retrieved 3/10/2015.]</ref>.  ETHP has a significantly higher taste threshold, and is often not detected in contaminated wine <ref name="Oelofse"></ref>.   
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==Discussions==
 
==Discussions==
 
Below is a list of discussions on internet forum threads that may shed light on specific strains and individual experiences.  Keep in mind that many of the opinions and experiences are anecdotal, although commonalities and shared experiences may prove to be useful and accurate.
 
Below is a list of discussions on internet forum threads that may shed light on specific strains and individual experiences.  Keep in mind that many of the opinions and experiences are anecdotal, although commonalities and shared experiences may prove to be useful and accurate.
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* [https://www.facebook.com/groups/MilkTheFunk/permalink/1034461653248715/ Milk The Funk Thread.]
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* [https://www.facebook.com/groups/MilkTheFunk/permalink/1034461653248715/ Milk The Funk Thread on March 10, 2015.]
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* [https://www.facebook.com/groups/MilkTheFunk/permalink/1134644959897050/ milk The Funk Thread on Aug 25, 2015.]
 
* [http://www.homebrewtalk.com/f127/brett-strain-production-athp-449852/#post6752813 Homebrewtalk thread started by "ne0t0ky0".]
 
* [http://www.homebrewtalk.com/f127/brett-strain-production-athp-449852/#post6752813 Homebrewtalk thread started by "ne0t0ky0".]
 
* [http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/ Homebrewtalk thread started by "loctones", comments by Michael Tonsmeire.]
 
* [http://www.homebrewtalk.com/f127/cheerios-character-after-bottling-504468/ Homebrewtalk thread started by "loctones", comments by Michael Tonsmeire.]

Revision as of 11:54, 17 September 2015

Forms of Tetrahydropyridines (THP), specifically 6-Acetyl-2,3,4,5-tetrahydropyridine (ATHP or ACTPY), 2-ethyltetrahydropyridine (ETHP), and 2-acetyl-1-pyrroline (ACPY or APY) [1], which are classified as ketones [2], are commonly attributed to the "mousy", "urine" (in high amounts) "cheerios" or "Captain Crunch" (in low amounts), "breakfast cereal", or more generically, "cracker biscuit" flavor in sour beers. The flavor is detected towards the end of the swallow. Diacetyl is sometimes mistakenly indicated as a potential cause of this flavor in sour beers. However, Tetrahydropyridines are the accepted cause. The flavor tends to age out of sour beers after 2-3 months (it is unknown whether cold or room temperature storage speeds this up), although the exact mechanism for this is not fully understood [3]. Many brewers have noticed that pitching rehydrated wine yeast at bottling reduces the amount/duration of this flavor [4].

In food, Tetrahydropyridines are associated with the aroma of baked goods such as white bread, popcorn, and tortillas, and is formed by Maillard reactions during heating. ATHP and APY have an odor threshold of 0.06ng/l [1].

Traditionally, the mousy/cheerios flavor from THP is considered an off flavor in both wine and sour beer. There is some debate and differing opinions as to whether or not a small amount of THP flavor is allowable (or even enjoyable) in sour beers, however most consider any level to be an off flavor.

Production

Proposed pathway for THP production by Brett [5]

Brettanomyces, Lactobacillus, and Pediococcus can produce forms of Tetrahydropyridine. In Brettanomyces, ATHP and ETHP are produced by metabolizing the amino acids L-Lysine and D-Lysine, along with ethanol and a glucose or fructose molecule. Oxygen has a stimulatory effect in it's production, but this is probably because Brett has a higher biomass formation under aerobic conditions [6][7][8]. The level of THP production varies widely between species and strains of Brett, with some strains not producing it at all and some producing very high amounts above taste threshold. Additionally, THP production appears to require glucose or fructose, which explains why THP may be seen more often in stuck wine fermentations rather than wine that has finished fermenting. ATHP production by Brett was observed in wine with glucose or fructose added, along with synthetic growth media, suggesting that the type of growth substrate does not effect production [9].

ATHP is further metabolized into 2-ethyltetrahydropyridine (ETHP/ETPY) by Brettanomyces, although not much is known about this metabolic process [10]. ETHP has a significantly higher taste threshold, and is often not detected in contaminated wine [8].

The presence of the "mousy off-flavor" caused by THP appears to be temporary in beer. Although not much is known about the degradation or metabolic break down of ATHP/ETHP, it tends to age out of beer after 2-3 months. Another unknown is why Brett produces THP shortly after kegging and force carbonating a beer that has reached final gravity. Pitching fresh Saccharomyces for bottle conditioning a beer with Brett in it has reportedly reduced THP production, perhaps through the quicker metabolism of both the oxygen and sugar that is introduced during packaging time.

Heterofermentative Lactobacillus spp., particularly L. hilgardii and L. brevis, can also produce ATHP and ETHP from Lysine and ethanol [11][12][13][14][15][16]. Most species of Pediococcus do not create THP, although a few species do. In particular, these include P. pentosaceus [17][18], and P. clausenii [19] (note that commercial cultures of Pediococcus are normally P. damnosus). Oenococcus oeni and Leuconostoc mesenteroides have also been associated with creating THP [11].

Thresholds

Editor's note: the following thresholds are from a study on wine, and may not hold true for beer.

  • 2-ethyltetrahydropyridine (ETHP/ETPY)
    • Taste threshold (wine): 150 µg/L
    • Concentration reported in wines exhibiting mousy off-flavour: 2.7-18.7 µg/L
  • 2-acetyltetrahydropyridine (/ATHP/ACTPY) -
    • Odor threshold (water): 1.6 µg/L
    • Concentration reported in wines exhibiting mousy off-flavour: 4.8-106 µg/L
  • 2-acetyl-1-pyrroline (ACPY)
    • Odor threshold (water): 0.1 µg/L
    • Concentration reported in wines exhibiting mousy off-flavour: Tr-7.8 µg/L [20]

Discussions

Below is a list of discussions on internet forum threads that may shed light on specific strains and individual experiences. Keep in mind that many of the opinions and experiences are anecdotal, although commonalities and shared experiences may prove to be useful and accurate.

References

  1. ↑ 1.0 1.1 6-Acetyl-2,3,4,5-tetrahydropyridine. Wikipedia. Retrieved 3/210/2015.
  2. ↑ Humbard, Matt. Milk The funk Discussion. 3/10/2015.
  3. ↑ Tonsmeire, Michael. Homebrewtalk.com post 1. 11/21/2014. Retrieved 3/10/2015.
  4. ↑ Tonsmeire, Michael. Homebrewtalk.com post 2. 11/21/2014. Retrieved 3/10/2015.
  5. ↑ Managing Wine Quality: Oenology and Wine Quality. A Reynolds Elsevier, Sep 30, 2010. Pg 359.
  6. ↑ Yakobson, Chad. The Brettanomyces Project; Introduction. Retrieved 3/10/2015.
  7. ↑ The Role of Lysine Amino Nitrogen in the Biosynthesis of Mousy Off-Flavor Compounds by Dekkera anomala. Paul R. Grbin, Markus Herderich, Andrew Markides, Terry H. Lee, and Paul A. Henschke. J. Agric. Food Chem., 2007.
  8. ↑ 8.0 8.1 Significance of Brettanomyces and Dekkera during Winemaking: A Synoptic Review. A. Oelofse, I.S. Pretorius, and M. du Toit. 2008.
  9. ↑ Growth and volatile compound production by Brettanomyces/Dekkera bruxellensis in red wine. Romano A, Perello MC, de Revel G, Lonvaud-Funel A. J Appl Microbiol. 2008 Jun.
  10. ↑ Joseph, C.M. Lucy. Aromatic Diversity of Brettanomyces. U.C. Davis. Retrieved 3/10/2015.
  11. ↑ 11.0 11.1 Mousy Off-Flavor of Wine:  Precursors and Biosynthesis of the Causative N-Heterocycles 2-Ethyltetrahydropyridine, 2-Acetyltetrahydropyridine, and 2-Acetyl-1-pyrroline by Lactobacillus hilgardii DSM 20176. Peter J. Costello and Paul A. Henschke. 2002.
  12. ↑ Formation of Substituted Tetrahydropyridines by Species of Brettanomyces and Lactobacillus Isolated from Mousy Wines. Tamila Heresztyn. 1986.
  13. ↑ Ability of lactic acid bacteria to produce N-heterocycles causing mousy off-flavour in wine. PETER J. COSTELLO1, TERRY H. LEE1, and PAULA. HENSCHKE. 2008.
  14. ↑ Sparrows, Jeff. Wild Brews. Brewers Publications. 2005. Pg. 112.
  15. ↑ Lahtinen, Ouwehand, Salminen, von Wright. Lactic Acid Bacteria: Microbiological and Functional Aspects, Fourth Edition. Pg 348.
  16. ↑ Heresztyn, Tamila. Formation of Substituted Tetrahydropyridines by Species of Brettanomyces and Lactobacillus Isolated from Mousy Wines.
  17. ↑ UniProt article. Retrieved 3/10/2015.
  18. ↑ UniProt article. Retrieved 3/10/2015.
  19. ↑ UniProt article. Retrieved 3/10/2015.
  20. ↑ Malolactic Fermentation 2005. Geneva on the Lake. Feb 2005. Retrieved 3/10/2015.
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