Chemical Papers

, Volume 71, Issue 1, pp 41–48 | Cite as

Secondary metabolites, antioxidant and anti-proteinase activities of methanolic extracts from cones of hop (Humulus lupulus L.) cultivars

  • Tibor Maliar
  • Peter Nemeček
  • Eva Ürgeová
  • Mária Maliarová
  • Vladimír Nesvadba
  • Karel Krofta
  • Katarína Vulganová
  • Erik Krošlák
  • Ján KraicEmail author
Original Paper


Contents of polyphenols, flavonoids, bitter acids, α-bitter acids, xanthohumol, desmethylxanthohumol, essential oils, antioxidant activities, and inhibitory activities against trypsin, thrombin, urokinase, and papain were analysed in methanolic extracts prepared from the hope cones. Significant differences between extracts from eight hop cultivars in all measured parameters were found. Two cultivars—Agnus and Vital—could be designated as the very special, all possessing high content of bitter acids, α-acids, essential oils, xanthohumol, and desmethylxanthohumol. The other two cultivars—Bohemie and Sládek—had interesting inhibitory activities against analysed proteinases. Differences between cultivars were also in content of total polyphenols, total flavonoids, as well as in antioxidant activity. All analysed hop cultivars developed originally for brewing contained also secondary metabolites with valuable biological activities related to health conditions associated with antioxidant status and some pathophysiological agents of proteinase character.


Humulus lupulus Secondary metabolites Polyphenols Flavonoids Antioxidant activity Proteinase inhibition 



This work was supported by the Grant No. VEGA 1/0635/13 “Hop as an important source of phytomedically active substances” supported by the Scientific Grant Agency of the Slovak Academy of Sciences and Ministry of Education, Science, Research and Sport of the Slovak Republic.


  1. Analytica EBC, European Brewery Convention (1998) Fachverlag Hans Carl: Nűrmberg, Germany, 5th edn 1998, Section 7Google Scholar
  2. Benelli R, Venè R, Ciarlo M, Carlone S, Barbieri O, Ferrari N (2012) The AKT/NF-κB inhibitor xanthohumol is a potent anti-lymphocytic leukemia drug overcoming chemoresistance and cell infiltration. Biochem Pharmacol 83:1634–1642. doi: 10.1016/j.bcp.2012.03.006 CrossRefGoogle Scholar
  3. Brand-Williams W, Cuvelier ME, Berset C (1995) Use of a free radical method to evaluate antioxidant activity. LWT Food Sci Technol 28:25–30. doi: 10.1016/S0023-6438(95)80008-5 CrossRefGoogle Scholar
  4. 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: 10.1016/j.phymed.2004.07.006 CrossRefGoogle Scholar
  5. De Keukeleire J, Ooms G, Heyerick A, Roldan-Ruiz I, Van Bockstaele E, De Keukeleire D (2003) Formation and accumulation of alpha-acids, beta-acids, desmethylxanthohumol, and xanthohumol during flowering of hops (Humulus lupulus L.). J Agric Food Chem 47:1145–1698. doi: 10.1021/jf034263z Google Scholar
  6. Delmulle L, Bellahcène A, Dhooge W, Comhaire F, Roelens F, Huvaere K, Heyerick A, Castronovo V, De Keukeleire D (2006) Anti-proliferative properties of prenylated flavonoids from hops (Humulus lupulus L.) in human prostate cancer cell lines. Phytomedicine 13:732–734. doi: 10.1016/j.phymed.2006.01.001 CrossRefGoogle Scholar
  7. Feng Y, Ni L, Wang Q (2013) Administration of cathepsin B inhibitor CA-074Me reduces inflammation and apoptosis in polymyositis. J Dermatol Sci 72:158–167. doi: 10.1016/j.jdermsci.2013.06.014 CrossRefGoogle Scholar
  8. Ferri M, Gianotti A, Tassoni A (2013) Optimisation of assay conditions for the determination of antioxidant capacity and polyphenols in cereal food components. J Food Compos Anal 30:94–101. doi: 10.1016/j.jfca.2013.02.004 CrossRefGoogle Scholar
  9. Jayaprakasha GK, Singh RP, Sakariah KK (2001) Antioxidant activity of grape seed (Vitis vinifera) extracts on peroxidation models in vitro. Food Chem 73:285–290. doi: 10.1016/S0308-8146(00)00298-3 CrossRefGoogle Scholar
  10. Jelínek L, Šneberger M, Karabín M, Dostálek P (2010) Comparison of Czech hop cultivars based on their contents of secondary metabolites. Czech J Food Sci 28:309–316Google Scholar
  11. Kähkönen MP, Hopia AI, Vuorela HJ, Rauha JP, Pihlaja K, Kujala TS, Heinonen M (1999) Antioxidant activity of plant extracts containing phenolic compounds. J Agric Food Chem 47:3954–3962. doi: 10.1021/jf990146l CrossRefGoogle Scholar
  12. Karabín M, Hudcová T, Jelínek L, Dostálek P (2016) Biologically active compounds from hops and prospects for their use. Compr Rev Food Sci Food Saf 15:542–567. doi: 10.1111/1541-4337.12201 CrossRefGoogle Scholar
  13. Kovačevič M, Kač M (2001) Solid-phase microextraction of hop volatiles: potential use for determination and verification of hop varieties. J Chromatogr A 918:159–167. doi: 10.1016/S0021-9673(01)00719-1 CrossRefGoogle Scholar
  14. Kowalczyk D, Świeca M, Cichocka J, Gawlik-Dziki U (2013) The phenolic content and antioxidant activity of the aqueous and hydroalcoholic extracts of hops and their pellets. J Inst Brew 119:103–110. doi: 10.1002/jib.73 Google Scholar
  15. Krofta K, Mikyška A, Hašková D (2008) Antioxidant characteristics of hops and hop products. J Inst Brew 114:160–166. doi: 10.1002/j.2050-0416.2008.tb00321.x CrossRefGoogle Scholar
  16. Lee Y-M, Hsieh K-H, Lu W-J, Chou H-C, Chou D-S, Lien L-M, Sheu J-R, Lin K-H (2012) Xanthohumol, a prenylated flavonoid from hops (Humulus lupulus), prevents platelet activation in human platelets. Evid-Based Complementary Altern Med (Article ID 852362):10. doi:  10.1155/2012/852362
  17. Maliar T, Jedinák A, Kadrabová J, Šturdík E (2004) Structural aspects of flavonoids as trypsin inhibitors. Eur J Med Chem 39:241–248. doi: 10.1016/j.ejmech.2003.12.003 CrossRefGoogle Scholar
  18. Maliar T, Drobná J, Kraic J, Maliarová M, Jurovatá J (2011) Proteinase inhibition and antioxidant activity of selected forage crops. Biologia 66:96–103. doi: 10.2478/s11756-010-0149-9 CrossRefGoogle Scholar
  19. Martorell L, Rodriguez C, Calvayrac O, Gentile M, Badimon L (2008) Thrombin and protease-activated receptors (PARs) in atherothrombosis. Thromb Haemost 99:305–315. doi: 10.1160/TH07-08-0481 Google Scholar
  20. Nesvadba V, Krofta K (2009) Variability in the contents of important compounds for pharmaceutical and brewing industries within hop gene pool. Agriculture 55:10–16Google Scholar
  21. Nesvadba V, Krofta K, Polončíková Z (2011) Hop (Humulus lupulus L.) breeding aimed at high content of desmethylxanthohumol (DMX). Agriculture 57:105–109. doi: 10.2478/v10207-011-0011-2 Google Scholar
  22. Nesvadba V, Polončíková Z, Henychová A (2012) Hop breeding in the Czech Republic. Kvasný Průmysl 58:36–39CrossRefGoogle Scholar
  23. Pšenáková I, Hetešová L, Nemeček P, Faragó J, Kraic J (2010) Genotype and seasonal variation n antioxidant activity of hop extracts. Agriculture 56:106–113Google Scholar
  24. Rakotoarison D, Greissier B, Trotin F, Brunet C, Dine T, Luycky M, Vasseur J, Cazin M, Cazin JC, Pinkas M (1997) Antioxidant activities of polyphenolic extracts from flowers, in vitro callus and cell suspension cultures of Crataegus monogyna. Pharmazia 1:60–64Google Scholar
  25. Silbernagl S, Lang F (2009) Color atlas of pathophysiology, 2nd edn. Georg Thieme, StuttgartGoogle Scholar
  26. Slinkard K, Singleton VL (1977) Total phenol analysis: automation and comparison with manual methods. Am J Enol Vitic 28:49–55Google Scholar
  27. Steenackers B, De Cooman L, De Vos D (2015) Chemical transformations of characteristic hop secondary metabolites in relation to beer properties and the brewing process: a review. Food Chem 172:742–756. doi: 10.1016/j.foodchem.2014.09.139 CrossRefGoogle Scholar
  28. Stevens JF, Ivancic M, Hsu VL, Deinzer ML (1997) Prenylflavonoids from Humulus lupulus. Phytochemistry 44:1575–1585. doi: 10.1016/S0031-9422(96)00744-3 CrossRefGoogle Scholar
  29. Stevens JF, Taylor AW, Deinzer ML (1999) Quantitative analysis of xanthohumol and related prenylflavonoids in hops and beer by liquid chromatography-tandem mass spectrometry. J Chromatogr A 832:97–107. doi: 10.1016/S0021-9673(98)01001-2 CrossRefGoogle Scholar
  30. Stratil P, Klejdus B, Kubáň V (2007) Determination of phenolic compounds and their antioxidant activity in fruits and cereals. Talanta 71:1741–1751. doi: 10.1016/j.talanta.2006.08.012 CrossRefGoogle Scholar
  31. Tabata N, Ito M, Tomoda H, Omura S (1997) Xanthohumols, diacylglycerol acyltransferase inhibitors, from Humulus lupulus. Phytochemistry 46:683–687. doi: 10.1016/S0031-9422(97)00157-X CrossRefGoogle Scholar
  32. Tapiero H, Tew KD, Ba GN, Mathé G (2002) Polyphenols: do they play a role in the prevention of human pathologies? Biomed Pharmacother 56:200–207. doi: 10.1016/S0753-3322(02)00178-6 CrossRefGoogle Scholar
  33. Ulisse S, Baldini E, Sorrenti S, D’Armiento M (2009) The urokinase plasminogen activator system: a target for anti-cancer therapy. Curr Cancer Drug Targets 9:32–71. doi: 10.2174/156800909787314002 CrossRefGoogle Scholar
  34. Ürgeová E, Polívka Ľ (2009) Secondary metabolites with antibacterial effects from leaves of different cultivars during vegetal period. Nova Biotechnologica 9:327–332Google Scholar
  35. Van Cleemput M, Cattoor K, De Bosscher K, Haegeman G, De Keukeleire D, Heyerick A (2009) Hop (Humulus lupulus)-derived bitter acids as multipotent bioactive compounds. J Nat Prod 72:1220–1230. doi: 10.1021/np800740m CrossRefGoogle Scholar
  36. Volf I, Ignat I, Neamtu M, Popa VI (2014) Thermal stability, antioxidant activity, and photo-oxidation of natural polyphenols. Chem Pap 68:121–129. doi: 10.2478/s11696-013-0417-6 CrossRefGoogle Scholar
  37. Zanoli P, Zavatti M (2008) Pharmacognostic and pharmacological profile of Humulus lupulus L. J Ethnopharmacol 116:383–396. doi: 10.1016/j.jep.2008.01.011

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2016

Authors and Affiliations

  • Tibor Maliar
    • 1
  • Peter Nemeček
    • 2
  • Eva Ürgeová
    • 3
  • Mária Maliarová
    • 2
  • Vladimír Nesvadba
    • 4
  • Karel Krofta
    • 4
  • Katarína Vulganová
    • 5
  • Erik Krošlák
    • 1
  • Ján Kraic
    • 1
    Email author
  1. 1.Department of Biotechnology, Faculty of Natural SciencesUniversity of SS. Cyril and MethodiusTrnavaSlovak Republic
  2. 2.Department of Chemistry, Faculty of Natural SciencesUniversity of SS. Cyril and MethodiusTrnavaSlovak Republic
  3. 3.Department of Biology, Faculty of Natural SciencesUniversity of SS. Cyril and MethodiusTrnavaSlovak Republic
  4. 4.Hop Research Institute, Co., Ltd.ŽatecCzech Republic
  5. 5.Institute the Physiotherapy, Balneology and Therapeutic RehabilitationUniversity of SS, Cyril and MethodiusTrnavaSlovak Republic

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