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Ferulic acid is one of the main [[phenolic compounds|phenolic]] acids in [[barley]], [[wheat]], and [[rye]] grains (365 to 605 µg/g in barley).<ref name=egi/> It is an effective [[antioxidants|antioxidant]], it  retards the degradation of iso-α-acids, and it is a potent UV light absorber.<ref name=habkos>Habschied K, Košir IJ, Krstanović V, Kumrić G, Mastanjević K. [https://www.mdpi.com/2306-5710/7/2/38 Beer polyphenols—bitterness, astringency, and off-flavors.] ''Beverages.'' 2021;7(2):38.</ref><ref name=bsp/><ref name=Siqueira/> Ferulic acid exists mainly ester-bound to [[arabinoxylans]]; only a minor part of ferulic acid is present in malts in free forms.<ref name=Siqueira>Siqueira PB, Bolini H, Macedo GA. [https://www.researchgate.net/publication/49599952_O_PROCESSO_DE_FABRICACAO_DA_CERVEJA_E_SEUS_EFEITOS_NA_PRESENCA_DE_POLIFENOIS O processo de fabricação da cerveja e seus efeitos na presença de polifenóis. (The beer manufacturing process and its effects on the presence of polyphenols.)] ''Alimentos e nutrição.'' 2008;19(4):491–498.</ref> Some additional ferulic acid can be released from the arabinoxylans by [[enzymes]] during [[mashing]].<ref name=Szwajgier>Szwajgier D. [https://onlinelibrary.wiley.com/doi/pdf/10.1002/j.2050-0416.2011.tb00505.x Dry and wet milling of malt. A preliminary study comparing fermentable sugar, total protein, total phenolics and the ferulic acid content in non-hopped worts.] ''J Inst Brew.'' 2011;117(4):569–577.</ref><ref name=bsp>Briggs DE, Boulton CA, Brookes PA, Stevens R. [[Library|''Brewing Science and Practice.'']] Woodhead Publishing Limited and CRC Press LLC; 2004.</ref><ref name=egi>Egi A, Speers RA, Schwarz PB. [https://www.mbaa.com/publications/tq/tqPastIssues/2004/Abstracts/0803-01.htm Arabinoxylans and their behavior during malting and brewing.] ''Tech Q Master Brew Assoc Am.'' 2004;41(3):248–267.</ref><ref name=vanvan/><ref name=wangas/><ref name=zhao/><ref name=sibpla/> Release is driven by cinnamoyl esterase, an enzyme that is most effective during an extended rest at 40–45°C and pH 5.2–6.6.<ref name=cargui/><ref name=wangas/><ref name=vanvan/><ref name=schwarz/> Enzymatic release declines with increasing temperature up to about 65°C where there is none; at this point the amount of phenolic acid extracted is solely dependent on the free form created during malting.<ref name=vanvan/><ref name=cargui/>
Ferulic acid is one of the main [[phenolic compounds|phenolic]] acids in [[barley]], [[wheat]], and [[rye]] grains (365 to 605 µg/g in barley).<ref name=egi/> It is an effective [[antioxidants|antioxidant]], it  retards the degradation of iso-α-acids, and it is a potent UV light absorber.<ref name=habkos>Habschied K, Košir IJ, Krstanović V, Kumrić G, Mastanjević K. [https://www.mdpi.com/2306-5710/7/2/38 Beer polyphenols—bitterness, astringency, and off-flavors.] ''Beverages.'' 2021;7(2):38.</ref><ref name=bsp/><ref name=Siqueira/> Ferulic acid exists mainly ester-bound to [[arabinoxylans]]; only a minor part of ferulic acid is present in malts in free forms.<ref name=Siqueira>Siqueira PB, Bolini H, Macedo GA. [https://www.researchgate.net/publication/49599952_O_PROCESSO_DE_FABRICACAO_DA_CERVEJA_E_SEUS_EFEITOS_NA_PRESENCA_DE_POLIFENOIS O processo de fabricação da cerveja e seus efeitos na presença de polifenóis. (The beer manufacturing process and its effects on the presence of polyphenols.)] ''Alimentos e nutrição.'' 2008;19(4):491–498.</ref> Some additional ferulic acid can be released from the arabinoxylans by [[enzymes]] during [[mashing]].<ref name=Szwajgier>Szwajgier D. [https://onlinelibrary.wiley.com/doi/pdf/10.1002/j.2050-0416.2011.tb00505.x Dry and wet milling of malt. A preliminary study comparing fermentable sugar, total protein, total phenolics and the ferulic acid content in non-hopped worts.] ''J Inst Brew.'' 2011;117(4):569–577.</ref><ref name=bsp>Briggs DE, Boulton CA, Brookes PA, Stevens R. [[Library|''Brewing Science and Practice.'']] Woodhead Publishing Limited and CRC Press LLC; 2004.</ref><ref name=egi>Egi A, Speers RA, Schwarz PB. [https://www.mbaa.com/publications/tq/tqPastIssues/2004/Abstracts/0803-01.htm Arabinoxylans and their behavior during malting and brewing.] ''Tech Q Master Brew Assoc Am.'' 2004;41(3):248–267.</ref><ref name=vanvan/><ref name=wangas/><ref name=zhao/><ref name=sibpla/> Release is driven by cinnamoyl esterase, an enzyme that is most effective during an extended rest at 40–45°C and pH 5.2–6.6.<ref name=cargui/><ref name=wangas/><ref name=vanvan/><ref name=schwarz/> Enzymatic release declines with increasing temperature up to about 65°C where there is none; at this point the amount of phenolic acid extracted is solely dependent on the free form created during malting.<ref name=vanvan/><ref name=cargui/><ref name=schwarz>Schwarz KJ, Boitz LI, Methner FJ. [https://www.tandfonline.com/doi/abs/10.1094/ASBCJ-2012-1011-02 Release of phenolic acids and amino acids during mashing dependent on temperature, pH, time, and raw materials.] ''J Am Soc Brew Chem.'' 2012;70(4):290–295.</ref>


Ferulic acid itself is generally flavorless, having a flavor threshold in beer as high as 600 ppm.<ref name=vanvan/> However, it is notable as a precursor to the more flavor-active 4-vinyl guaiacol (4VG). Ferulic acid is transformed into 4VG by decarboxylation, which occurs during boiling to a small extent, but mostly by the enzymes present in many wild microbes and certain strains of brewers yeast, deemed phenolic off-flavor positive (POF+).<ref name=bsp/><ref name=vansai>Vanbeneden N, Saison D, Delvaux F, Delvaux FR. [https://pubs.acs.org/doi/abs/10.1021/jf8019453 Decrease of 4-vinylguaiacol during beer aging and formation of apocynol and vanillin in beer.] ''J Agric Food Chem.'' 2008;56(24):11983–11988.</ref> 4VG gives a spicy clove flavor that is usually undesirable, but is crucial to the flavor profile of some specialty beers. The flavor threshold of 4VG in blond specialty beers is quite low, 0.37 ppm.<ref name=vanvan/>
Ferulic acid itself is generally flavorless, having a flavor threshold in beer as high as 600 ppm.<ref name=vanvan/> However, it is notable as a precursor to the more flavor-active 4-vinyl guaiacol (4VG). Ferulic acid is transformed into 4VG by decarboxylation, which occurs during boiling to a small extent, but mostly by the enzymes present in many wild microbes and certain strains of brewers yeast, deemed phenolic off-flavor positive (POF+).<ref name=bsp/><ref name=vansai>Vanbeneden N, Saison D, Delvaux F, Delvaux FR. [https://pubs.acs.org/doi/abs/10.1021/jf8019453 Decrease of 4-vinylguaiacol during beer aging and formation of apocynol and vanillin in beer.] ''J Agric Food Chem.'' 2008;56(24):11983–11988.</ref> 4VG gives a spicy clove flavor that is usually undesirable, but is crucial to the flavor profile of some specialty beers. The flavor threshold of 4VG in blond specialty beers is quite low, 0.37 ppm.<ref name=vanvan/>


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The maximal release of FA occurs in the range of 45-50°C. Within the range of 25 to 60°C, a longer mashing-in time leads to a higher detachment of ferulic acid. Above 65°C, the mashing-in time has no more influence on the release. In this temperature range, most of the FA degrading enzymes are denatured. Consequently, the released amount of ferulic acid corresponds with the unbound water-soluble fraction in malt.<ref name=schwarz>Schwarz KJ, Boitz LI, Methner FJ. [https://www.tandfonline.com/doi/abs/10.1094/ASBCJ-2012-1011-02 Release of phenolic acids and amino acids during mashing dependent on temperature, pH, time, and raw materials.] ''J Am Soc Brew Chem.'' 2012;70(4):290–295.</ref>


The maximal release of free FA occurs at 40°C and pH of 5.8, and the level reaches a plateau after around 2 hours, although the mash reaches a maximal level only after temp is increased to 65°C or higher in order to extract the remaining water-soluble portion.<ref name=vanvan>Vanbeneden N, Van Roey T, Willems F, Delvaux F, Delvaux FR. [https://www.sciencedirect.com/science/article/abs/pii/S0308814608003348 Release of phenolic flavour precursors during wort production: Influence of process parameters and grist composition on ferulic acid release during brewing.] ''Food Chem.'' 2008;111(1):83–91.</ref> Even at optimal enzyme activity, no more than ~23% of the total wort FA is extracted. Within the optimal ranges of cinnamoyl esterase, stirring the mash significantly increases the extraction of ferulic acid because stirring increases the amount of arabinoxylan extraction.
The maximal release of free FA occurs at 40°C and pH of 5.8, and the level reaches a plateau after around 2 hours, although the mash reaches a maximal level only after temp is increased to 65°C or higher in order to extract the remaining water-soluble portion.<ref name=vanvan>Vanbeneden N, Van Roey T, Willems F, Delvaux F, Delvaux FR. [https://www.sciencedirect.com/science/article/abs/pii/S0308814608003348 Release of phenolic flavour precursors during wort production: Influence of process parameters and grist composition on ferulic acid release during brewing.] ''Food Chem.'' 2008;111(1):83–91.</ref> Even at optimal enzyme activity, no more than ~23% of the total wort FA is extracted. Within the optimal ranges of cinnamoyl esterase, stirring the mash significantly increases the extraction of ferulic acid because stirring increases the amount of arabinoxylan extraction.

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Ferulic acid is one of the main phenolic acids in barley, wheat, and rye grains (365 to 605 µg/g in barley).[1] It is an effective antioxidant, it retards the degradation of iso-α-acids, and it is a potent UV light absorber.[2][3][4] Ferulic acid exists mainly ester-bound to arabinoxylans; only a minor part of ferulic acid is present in malts in free forms.[4] Some additional ferulic acid can be released from the arabinoxylans by enzymes during mashing.[5][3][1][6][7][8][9] Release is driven by cinnamoyl esterase, an enzyme that is most effective during an extended rest at 40–45°C and pH 5.2–6.6.[10][7][6][11] Enzymatic release declines with increasing temperature up to about 65°C where there is none; at this point the amount of phenolic acid extracted is solely dependent on the free form created during malting.[6][10][11]

Ferulic acid itself is generally flavorless, having a flavor threshold in beer as high as 600 ppm.[6] However, it is notable as a precursor to the more flavor-active 4-vinyl guaiacol (4VG). Ferulic acid is transformed into 4VG by decarboxylation, which occurs during boiling to a small extent, but mostly by the enzymes present in many wild microbes and certain strains of brewers yeast, deemed phenolic off-flavor positive (POF+).[3][12] 4VG gives a spicy clove flavor that is usually undesirable, but is crucial to the flavor profile of some specialty beers. The flavor threshold of 4VG in blond specialty beers is quite low, 0.37 ppm.[6]

The maximal release of free FA occurs at 40°C and pH of 5.8, and the level reaches a plateau after around 2 hours, although the mash reaches a maximal level only after temp is increased to 65°C or higher in order to extract the remaining water-soluble portion.[6] Even at optimal enzyme activity, no more than ~23% of the total wort FA is extracted. Within the optimal ranges of cinnamoyl esterase, stirring the mash significantly increases the extraction of ferulic acid because stirring increases the amount of arabinoxylan extraction.

the content of each phenolic acid increases during kilning up to 80°C. Above 80°C, the content of hydroxycinnamic acids decreases. The phenolic acid content increases during kilning up to 80°C, which was partly attributed to the enhanced extractability of the drying tissue and partly to enzymatic release. During malting, phenolic acids are partly released due to the degradation of complex barley components.[7] However, cinnamoyl esterases, which are able to release hydroxycinnamic acids from cinnamoylated saccharides, have also been found in barley and barley malt.

ferulic acid esterase enzyme is active (during kilning) at temperatures between 45 and 65 °C and it releases bound phenolic acids.[7] At higher temperatures (up to 75°C), the further increase in ferulic acid content was attributed to better extractability followed by a decrease due to thermal degradation. Specifically, ferulic acid reacts with proline-glucose Maillard reaction intermediates upon heating.

rapid increases of bound ferulic acid concentration in the early stages of wort production were observed. The free ferulic acid concentration in wort without any preparations increased until the heating at 75°C step. After boiling the wort with hops, the stabilization of free ferulic acid content was observed, and after 14 days of main fermentation only a slight (3%) decrease of free ferulic acid was observed. During the 28 days of beer maturation the free ferulic acid concentration decreased about 14% in comparison to the same beer after the main fermentation. A further decrease in free ferulic concentration of 30 mg/hL after beer storage (1 month) was also observed compared to the fresh beer levels. The percent decrease of free ferulic acid content in beer after storage, in comparison to the maximal concentration which was obtained in wort heated at 75°C, was about 35%.[13]

During wort boiling, the free wort Ferulic acid (FA) concentration increased by 10%. This net increase was the result of several factors. During wort boiling, thermal decarboxylation of FA will lead to the formation of 4VG. At the end of the boiling process, 0.14 ppm 4VG was found in the wort. This thermal decarboxylation caused the wort FA concentration to diminish by 9%. However, during wort boiling, the wort volume will decrease by 7–8% due to evaporation. This will cause an apparent increase in FA content. Finally, the addition of hop pellets will cause a real increase in wort FA content by 7–11% (based on results obtained in laboratory hop addition experiments). Taking into account these three factors, a net increase of the wort FA content during wort boiling will occur. The reassociation or coprecipitation of free FA with AX, polyphenols or proteins was negligible. Otherwise, no net increase in free FA content would occur during pilot-scale wort boiling. This was confirmed during laboratory-scale wort boiling experiments under reflux (no evaporation) without hop addition. During these experiments, the increase in 4VG corresponded with the decrease in FA.[6]


  • Graf, E. Antioxidant potential of ferulic acid. Free Radic. Biol. Med. 13:435-448, 1992.
  • Kikuzaki, H., Hisamoto, M., Hirose, K., Akiyama, K., and Taniguchi, H. Antioxidant properties of ferulic acid and its related compounds. J. Agric. Food Chem. 50:2161-2168, 2002.

See also

References

  1. ↑ a b Egi A, Speers RA, Schwarz PB. Arabinoxylans and their behavior during malting and brewing. Tech Q Master Brew Assoc Am. 2004;41(3):248–267.
  2. ↑ Habschied K, Košir IJ, Krstanović V, Kumrić G, Mastanjević K. Beer polyphenols—bitterness, astringency, and off-flavors. Beverages. 2021;7(2):38.
  3. ↑ a b c Briggs DE, Boulton CA, Brookes PA, Stevens R. Brewing Science and Practice. Woodhead Publishing Limited and CRC Press LLC; 2004.
  4. ↑ a b Siqueira PB, Bolini H, Macedo GA. O processo de fabricação da cerveja e seus efeitos na presença de polifenóis. (The beer manufacturing process and its effects on the presence of polyphenols.) Alimentos e nutrição. 2008;19(4):491–498.
  5. ↑ Szwajgier D. Dry and wet milling of malt. A preliminary study comparing fermentable sugar, total protein, total phenolics and the ferulic acid content in non-hopped worts. J Inst Brew. 2011;117(4):569–577.
  6. ↑ a b c d e f g Vanbeneden N, Van Roey T, Willems F, Delvaux F, Delvaux FR. Release of phenolic flavour precursors during wort production: Influence of process parameters and grist composition on ferulic acid release during brewing. Food Chem. 2008;111(1):83–91.
  7. ↑ a b c d Wannenmacher J, Gastl M, Becker T. Phenolic substances in beer: Structural diversity, reactive potential and relevance for brewing process and beer quality. Compr Rev Food Sci Food Saf. 2018;17(4):953–988.
  8. ↑ Cite error: Invalid <ref> tag; no text was provided for refs named zhao
  9. ↑ Cite error: Invalid <ref> tag; no text was provided for refs named sibpla
  10. ↑ a b Cite error: Invalid <ref> tag; no text was provided for refs named cargui
  11. ↑ a b Schwarz KJ, Boitz LI, Methner FJ. Release of phenolic acids and amino acids during mashing dependent on temperature, pH, time, and raw materials. J Am Soc Brew Chem. 2012;70(4):290–295.
  12. ↑ Vanbeneden N, Saison D, Delvaux F, Delvaux FR. Decrease of 4-vinylguaiacol during beer aging and formation of apocynol and vanillin in beer. J Agric Food Chem. 2008;56(24):11983–11988.
  13. ↑ Szwajgier D, Pielecki J, Targoński Z. The release of ferulic acid and feruloylated oligosaccharides during wort and beer production. J Inst Brew. 2005;111(4):372–379.
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