Comparative analysis of four hop cultivars grown in Brazil and the USA by GC-MS-based metabolomics

Guilherme Silva Dias; Marilia Elias Gallon; Leonardo Gobbo-Neto

doi:10.58430/jib.v130i4.62

Authors

Guilherme Silva Dias University of São Paulo https://orcid.org/0000-0002-3311-6785
Marilia Elias Gallon University of São Paulo https://orcid.org/0000-0002-7458-0883
Leonardo Gobbo-Neto University of São Paulo https://orcid.org/0000-0002-0133-6142

DOI:

https://doi.org/10.58430/jib.v130i4.62

Keywords:

chemical profile, metabolic fingerprinting, Humulus lupulus, cultivation, geographical origin, secondary metabolite, variability, hops

Abstract

Why was the work done: Although the third largest beer producer in the world, Brazil currently imports the majority of its hops. A recent development is the cultivation of hops (Humulus lupulus L.) in Brazil. In addition to genetic factors, the chemical composition of hops can exhibit variations due to conditions of cultivation. Accordingly, it is of value to characterise and differentiate hop cultivars grown in Brazil with the same cultivars grown in a long established location such as the United States of America.

How was the work done: Centennial, Chinook, Columbus, and Nugget cultivars grown in Brazil or in the USA were compared by metabolomic analyses of the chemical profiles using gas chromatography coupled to mass spectrometry. Principal component analysis showed sample grouping according to where the hops were grown. Partial Least Squares Discriminant Analysis allowed the characterisation of the main metabolites that discriminated hop samples from the two countries. A total of 31 metabolites were putatively identified, including monoterpenes, sesquiterpenes, oxygenated mono- and sesquiterpenes, esters, alcohols, and ketones.

What are the main findings: There were clear metabolic differences between the same hop varieties grown in Brazil or the USA. The metabolites with the greatest discriminating power for Brazilian hops were trans-α-bergamotene, 2-decanone, and ι-gurjunene, while American hops presented β-copaene, humuladienone, and isopentyl isobutyrate. Notably, trans-α-bergamotene was present in Brazilian hops but absent from American hops.

Why is the work important: This study sheds light on the differences in the chemical composition of hops cultivated in Brazil compared those cultivated in the USA. This knowledge may stimulate new producers and contribute to the development of hop cultivation in Brazil.

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References

Abram V, Čeh B, Vidmar M, Hercezi M, Lazić N, Bucik V, Možina S, Košir I, Kač M, Demšar L, Poklar N. 2015. A comparison of antioxidant and antimicrobial activity between hop leaves and hop cones. Ind Crops Prod 64:124–134. DOI: https://doi.org/10.1016/j.indcrop.2014.11.008

Almaguer C, Schönberger C, Gastl M, Arendt E, Becker T. 2014. Humulus lupulus - a story that begs to be told. A review. J Inst Brew 120:289–314. DOI: https://doi.org/10.1002/jib.160

Bauerle WL. 2019. Disentangling photoperiod from hop vernalization and dormancy for global production and speed breeding. Sci Rep 9:1–8. DOI: https://doi.org/10.1038/s41598-019-52548-0

Briggs DE, Boulton CA, Brookes PA, Stevens R. 2004. Brewing Science and Practice, Woodhead Publishing, Cambridge, England. DOI: https://doi.org/10.1201/9780203024195

Bülow N, König WA. 2000. The role of germacrene D as a precursor in sesquiterpene biosynthesis: Investigations of acid catalysed, photochemically and thermally induced rearrangements. Phytochemistry 55:141–168. DOI: https://doi.org/10.1016/S0031-9422(00)00266-1

Chadwick LR, Pauli GF, Farnsworth NR. 2006. The pharmacognosy of Humulus lupulus L. (hops) with an emphasis on estrogenic properties. Phytomedicine 13:119–131. DOI: https://doi.org/10.1016/j.phymed.2004.07.006

Chan WK, Tan LTH, Chan KG, Lee LH, Goh BH. 2016. Nerolidol: A sesquiterpene alcohol with multi-faceted pharmacological and biological activities. Molecules 21:529. DOI: https://doi.org/10.3390/molecules21050529

Dabbous‐Wach A, Rodolfi M, Paolini J, Costa J, Ganino T. 2021. Characterization of wild Corsican hops and assessment of the performances of German hops in Corsican environmental conditions through a multidisciplinary approach. Appl Sci 11:3756. DOI: https://doi.org/10.3390/app11093756

Dieckmann RH, Palamand SR. 1974. Autoxidation of some constituents of hops. I. The monoterpene hydrocarbon, myrcene. J Agric Food Chem 22:498–503. DOI: https://doi.org/10.1021/jf60193a033

van Den Dool H, Dec Kratz P. 1963. A generalization of the retention index system including linear temperature programmed gas-liquid partition chromatography. J Chromatogr A 11:463–471. DOI: https://doi.org/10.1016/S0021-9673(01)80947-X

Dresel M, Praet T, Van Opstaele F, Van Holle A, Naudts D, De Keukeleire D, De Cooman L, Aerts G. 2015. Comparison of the analytical profiles of volatiles in single-hopped worts and beers as a function of the hop variety. BrewSci 68:8-28.

Eßlinger HM. 2009. Handbook of Brewing: Processes, Technology, Markets, Wiley-VCH: Weinheim, Alemanha. DOI: https://doi.org/10.1002/9783527623488

Eyres G, Dufour J P. 2008. Hop essential oil: Analysis, chemical composition and odour characteristics. in Beer in Health and Disease Prevention 239–254. DOI: https://doi.org/10.1016/B978-0-12-373891-2.00022-5

Fix GJ. 1999. Principles of Brewing Science: a Study of Serious Brewing Issues. Brewers Publications, Brewers Association, Colorado.

Hieronymus S. 2012. For the Love of Hops: The Practical Guide to Aroma, Bitterness, and the Culture of Hops. Brewers Publications, Brewers Association, Colorado.

van Holle A, Muylle H, Haesaert G, Naudts D, de Keukeleire D, Roldán-Ruiz I, van Landschoot A. 2021. Relevance of hop terroir for beer flavour. J Inst Brew 127: 238–247. DOI: https://doi.org/10.1002/jib.648

Inui T, Tsuchiya F, Ishimaru M, Oka K, Komura H. 2013. Different beers with different hops. Relevant compounds for their aroma characteristics. J Agric Food Chem 61:4758–4764. DOI: https://doi.org/10.1021/jf3053737

Jastrombek JM, Faguerazzi MM, de Cássio Pierezan H, Rufato L, Sato AJ, da Silva Ricce W, Marques VV, Leles NR, Roberto SR. 2022. Hop: An emerging crop in subtropical areas in Brazil. Horticulturae 8:393. DOI: https://doi.org/10.3390/horticulturae8050393

Karabin M, Hudcova T, Jelinek L, Dostalek P. 2014. Biotransformation and biological activities of hop flavonoids. Biotechnol Adv 33:1063–1090. DOI: https://doi.org/10.1016/j.biotechadv.2015.02.009

King AJ, Dickinson JR. 2003. Biotransformation of hop aroma terpenoids by ale and lager yeasts. FEMS Yeast Res 3:53–62. DOI: https://doi.org/10.1016/S1567-1356(02)00141-1

Kishimoto T, Wanikawa A, Kono K, Shibata K. 2006. Comparison of the odour-active compounds in unhopped beer and beers hopped with different hop varieties. J Agric Food Chem 54:8855–8861. DOI: https://doi.org/10.1021/jf061342c

Lafontaine S, Varnum S, Roland A, Delpech S, Dagan L, Vollmer D, Kishimoto T, Shellhammer T. 2019. Impact of harvest maturity on the aroma characteristics and chemistry of Cascade hops used for dry-hopping. Food Chem 278:228–239. DOI: https://doi.org/10.1016/j.foodchem.2018.10.148

Lafontaine SR, Shellhammer TH. 2019. How hoppy beer production has redefined hop quality and a discussion of agricultural and processing strategies to promote It. Tech Q Master Brew Assoc Am 56:1–12.

Likens ST, Nickerson GB. 1967. Identification of hop varieties by gas chromatographic analysis of their essential oils. Constancy of oil composition under various environmental influences. J Agric Food Chem 15:525–530. DOI: https://doi.org/10.1021/jf60151a009

Liu Z, Wang L, Liu Y. 2018. Rapid differentiation of Chinese hop varieties (Humulus lupulus) using volatile fingerprinting by HS-SPME-GC–MS combined with multivariate statistical analysis. J Sci Food Agric 98:3758–3766. DOI: https://doi.org/10.1002/jsfa.8889

Machado JC, Faria MA, Ferreira IMPLVO. 2019. Hops: new perspectives for an old beer ingredient. Natural Beverages 267–301. DOI: https://doi.org/10.1016/B978-0-12-816689-5.00010-9

Matsui H, Inui T, Oka K, Fukui N. 2016. The influence of pruning and harvest timing on hop aroma, cone appearance, and yield. Food Chem 202:15–22. DOI: https://doi.org/10.1016/j.foodchem.2016.01.058

Moir M. 2000. Hops - A Millennium review. J Am Soc Brew Chem 58:131–146 DOI: https://doi.org/10.1094/ASBCJ-58-0131

Mongelli A, Rodolfi M, Ganino T, Marieschi M, Caligiani A, Dall’Asta C, Bruni R. 2016. Are Humulus lupulus L. ecotypes and cultivars suitable for the cultivation of aromatic hop in Italy? A phytochemical approach. Ind Crops Prod 83: 693–700. DOI: https://doi.org/10.1016/j.indcrop.2015.12.046

Mosher M, Trantham K. 2017. Brewing Science: A Multidisciplinary Approach. Springer International Publishing. DOI: https://doi.org/10.1007/978-3-319-46394-0

Naya Y, Kotake M. 1972. The constituents of hops (Humulus lupulus L.). VII. The rapid analysis of volatile components. Bull Chem Soc Jpn 45:2887–2891. DOI: https://doi.org/10.1246/bcsj.45.2887

Neve R A. 1991. Hops. Dordrecht: Springer Netherlands. DOI: https://doi.org/10.1007/978-94-011-3106-3

van Opstaele F, Praet T, Aerts G, De Cooman L. 2013. Characterization of novel single-variety oxygenated sesquiterpenoid hop oil fractions via headspace solid-phase microextraction and gas chromatography-mass spectrometry/olfactometry. J Agric Food Chem 61:10555–10564. DOI: https://doi.org/10.1021/jf402496t

Paguet AS, Siah A, Lefèvre G, Sahpaz S, Rivière C. 2022. Agronomic, genetic and chemical tools for hop cultivation and breeding. Phytochem Rev 21:667–708. DOI: https://doi.org/10.1007/s11101-022-09813-4

Patzak J, Nesvadba V, Henychová A, Krofta K. 2010. Assessment of the genetic diversity of wild hops (Humulus lupulus L.) in Europe using chemical and molecular analyses. Biochem Syst Ecol 38:136–145. DOI: https://doi.org/10.1016/j.bse.2009.12.023

Perpète P, Mélotte L, Dupire S, Collin S. 1998. Varietal discrimination of hop pellets by essential oil analysis I. Comparison of fresh samples. J Am Soc Brew Chem 56:104–108. DOI: https://doi.org/10.1094/ASBCJ-56-0104

Praet T, Van Opstaele F, Jaskula-Goiris B, Aerts G, De Cooman L. 2012. Biotransformations of hop-derived aroma compounds by Saccharomyces cerevisiae upon fermentation. Cerevisia 36:125–132. 5 DOI: https://doi.org/10.1016/j.cervis.2011.12.005

Rettberg N, Biendl M, Garbe L A. 2018. Hop aroma and hoppy beer flavour: Chemical backgrounds and analytical tools—A review. J Am Soc Brew Chem 76:1–20. DOI: https://doi.org/10.1080/03610470.2017.1402574

Rodolfi M, Chiancone B, Liberatore C M, Fabbri A, Cirlini M, Ganino T. 2019. Changes in chemical profile of Cascade hop cones according to the growing area. J Sci Food Agric 99:6011–6019. DOI: https://doi.org/10.1002/jsfa.9876

Roland A, Delpech S, Dagan L. 2017. A powerful analytical indicator to drive varietal thiols release in beers: The ‘thiol potency’. BrewSci 70:170–175.

da Rosa Almeida A, Maciel MVOB, Cardoso GGB, Machado MH, Teixeira GL, Bertoldi FC, Noronha CM, Vitali L, Block JM, Barreto PLM. 2020. Brazilian grown Cascade Hop (Humulus lupulus L.): LC-ESI-MS-MS and GC-MS analysis of chemical composition and antioxidant activity of extracts and essential oils. J Am Soc Brew Chem 79:156–166. DOI: https://doi.org/10.1080/03610470.2020.1795586

Sharp DC, Townsend MS, Qian Y, Shellhammer T. 2014. Effect of harvest maturity on the chemical composition of Cascade and Willamette hops. J Am Soc Brew Chem 72:231–238. DOI: https://doi.org/10.1094/ASBCJ-2014-1002-01

Sharp DC, Qian Y, Shellhammer G, Shellhammer T. 2017. Contributions of select hopping regimes to the terpenoid content and hop aroma profile of ale and lager beers. J Am Soc Brew Chem 75:93–100. DOI: https://doi.org/10.1094/ASBCJ-2017-2144-01

Sharpe FR, Laws DRJ. 1981. The essential oil of hops a review. J Inst Brew. 87:96–107. DOI: https://doi.org/10.1002/j.2050-0416.1981.tb03996.x

Su X, Yin Y. 2021. Aroma characterization of regional Cascade and Chinook hops (Humulus lupulus L.). Food Chem 364:130410. DOI: https://doi.org/10.1016/j.foodchem.2021.130410

Sumner LW, Amberg A, Barrett D, Beale MH, Beger R, Daykin CA, Fan TWM, Fiehn O, Goodacre R, Griffin JL, Hankemeier T, Hardy N, Harnly J, Higashi R, Kopka J, Lane AN, Lindon JC, Marriott P, Nicholls AW, Reily MD, Thaden JJ, Viant MR. 2007. Proposed minimum reporting standards for chemical analysis: Chemical Analysis Working Group (CAWG) Metabolomics Standards Initiative (MSI). Metabolomics 3:211–221. DOI: https://doi.org/10.1007/s11306-007-0082-2

Takoi K, Itoga Y, Koie K, Kosugi T, Shimase M, Katayama Y, Nakayama Y, Watari J. 2010. The contribution of geraniol metabolism to the citrus flavour of beer: synergy of geraniol and β-citronellol under coexistence with excess linalool. J Inst Brew 116:251–260. DOI: https://doi.org/10.1002/j.2050-0416.2010.tb00428.x

Verzele M, de Keukeleire D. 1991. Chemistry and Analysis of Hop and Beer Bitter Acids. Developments in Food Science 27. Elsevier, Amsterdam.

Yan DD, Wong YF, Shellie RA, Marriott PJ, Whittock SP, Koutoulis A. 2019. Assessment of the phytochemical profiles of novel hop (Humulus lupulus L.) cultivars: A potential route to beer crafting. Food Chem 275:15–23. DOI: https://doi.org/10.1016/j.foodchem.2018.09.082

Zanoli P, Zavatti M. 2008. Pharmacognostic and pharmacological profile of Humulus lupulus L. J Ethnopharmacol 116:383–396. DOI: https://doi.org/10.1016/j.jep.2008.01.011