Skip to main content
SpringerLink
Log in

Clustering analysis of different hop varieties according to their essential oil composition measured by GC/MS

  • Original Paper
  • Published:
Chemical Papers Aims and scope Submit manuscript

Abstract

This study describes the analysis of total hops essential oils from 18 cultivated varieties of hops, five of which were bred in Lithuania, and 7 wild hop forms using gas chromatography-mass spectrometry. The study sought to organise the samples of hops into clusters, according to 72 semi-volatile compounds, by applying a well-known method, k-means clustering analysis and to identify the origin of the Lithuanian hop varieties. The bouquet of the hops essential oil was composed of various esters, terpenes, hydrocarbons and ketones. Monoterpenes (mainly β-myrcene), sesquiterpenes (dominated by β-caryophyllene and α-humulene) and oxygenated sesquiterpenes (mainly caryophyllene oxide and humulene epoxide II) were the main compound groups detected in the samples tested. The above compounds, together with a-muurolene, were the only compounds found in all the samples. Qualitative and quantitative differences were observed in the composition of the essential oils of the hop varieties analysed. For successful and statistically significant clustering of the data obtained, expertise and skills in employing chemometric analysis methods are necessary. The result is also highly dependent on the set of samples (representativeness) used for segmentation into groups, the technique for pre-processing the data, the method selected for partitioning the samples according to the similarity measures chosen, etc. To achieve a large and representative data set for clustering analysis from a small number of measurements, numerical simulation was applied using the Monte Carlo method with normal and uniform distributions and several relative standard deviation values. The grouping was performed using the k-means clustering method, employing several optimal number of clusters evaluation techniques (Davies-Bouldin index, distortion function, etc.) and different data pre-processing approaches. The hop samples analysed were separated into 3 and 5 clusters according to the data filtering scenario used. However, the targeted Lithuanian hop varieties were clustered identically in both cases and fell into the same group together with other cultivated hop varieties from Ukraine and Poland.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Similar content being viewed by others

References

  • Berrueta, L. A., Alonso-Salces, R. M., & Héberger, K. (2007). Supervised pattern recognition in food analysis. Journal of Chromatography A, 1158, 196–214. DOI: 10.1016/j.chroma.2007.05.024.

    Article  CAS  Google Scholar 

  • Chadwick, L. R., Pauli, G. F., & Farnsworth, N. R. (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.

    Article  CAS  Google Scholar 

  • Cruz, A. G., Cadena, R. S., Alvaro, M. B. V. B., Sant’Ana, A. S., Oliveira, C. A. F., Faria, J. A. F., Bolini, H. M. A., & Ferreira, M. M. C. (2013). Assessing the use of different chemometric techniques to discriminate low-fat and full-fat yogurts. LWT–Food Science and Technology, 50, 210–214. DOI: 10.1016/j.lwt.2012.05.023.

    CAS  Google Scholar 

  • Eβlinger, H. M., & Narziβ, L. (2009). Ullmann’s Encyclopedia of Industrial Chemistry, 5, 177–221. DOI: 10.1002/14356007. a03_421.pub2.

    Google Scholar 

  • Gromski, P. S., Correa, E., Vaughan, A. A., Wedge, D. C., Turner, M. L., & Goodacre, R. (2014). A comparison of different chemometrics approaches for the robust classification of electronic nose data. Analytical and Bioanalytical Chemistry, 406, 7581–7590. DOI: 10.1007/s00216-014-8216-7.

    Article  CAS  Google Scholar 

  • Hornsey, I. S. (2003). A history of beer and brewing. Cambridge, UK: RSC. DOI: 10.1039/9781847550026.

    Google Scholar 

  • Jelínek, L., Šneberger, M., Karabín, M., & Dostálek, P. (2010). Comparison of Czech hop cultivars based on their contents of secondary metabolites. Czech Journal of Food Sciences, 28, 309–316.

    Google Scholar 

  • Kaškonienė, V., Kaškonas, P., Maruška, A., & Kubiliene, L. (2014). Chemometric analysis of volatiles of propolis from different regions using static headspace GC-MS. Central European Journal of Chemistry, 12, 736–746. DOI: 10.2478/s11532-014-0521-7.

    Article  Google Scholar 

  • Kaškonienė, V., Stankevicius, M., Drevinskas, T., Akuneca, I., Kaškonas, P., Bimbiraite-Surviliene, K., Maruška, A., Ragažinskiene, O., Kornyšova, O., Briedis, V., & Ugenskiene, R. (2015a). Evaluation of phytochemical composition of fresh and dried raw material of introduced Chamerion angustifolium L. using chromatographic, spectrophotometric and chemometric techniques. Phytochemistry, 115, 184–193. DOI: 10.1016/j.phytochem.2015.02.005.

    Article  Google Scholar 

  • Kaškonienė, V., Kaškonas, P., & Maruška, A. (2015b). Volatile compounds composition and antioxidant activity of bee pollen collected in Lithuania. Chemical Papers, 69, 291–299. DOI: 10.1515/chempap-2015-0033.

    Google Scholar 

  • Kralj, D., Zupanec, J., Vasilj, D., Kralj, S., & Pšeničnik, J. (1991). Variability of essential oils of hops, Humulus lupulus L. Journal of the Institute of Brewing, 97, 197–206. DOI: 10.1002/j. 2050-0416.1991.tb01066.x.

    Article  CAS  Google Scholar 

  • Kovačevič, M., & Kač, M. (2002). Determination and verification of hop varieties by analysis of essential oils. Food Chemistry, 77, 489–494. DOI: 10.1016/s0308-8146(02)00114-0.

    Article  Google Scholar 

  • Larson, A. E., Yu, R. R. Y., Lee, O. A., Price, S., Haas, G. J., & Johnson, E. A. (1996). Antimicrobial activity of hop extracts against Listeria monocytogenes in media and in food. International Journal of Food Microbiology, 33, 195–207. DOI: 10.1016/0168-1605(96)01155-5.

    Article  CAS  Google Scholar 

  • Leonardi, M., Skomra, U., Agacka, M., Stochmal, A., Ambryszewska, K. E., Oleszek, W., Flamini, G., & Pistelli, L. (2013). Characterisation of four popular Polish hop cultivars. International Journal of Food Science & Technology, 48, 1770–1774. DOI: 10.1111/ijfs.12150.

    Article  CAS  Google Scholar 

  • Li, L. P., Weinberg, C. R., Darden, T. A., & Pedersen, L. G. (2001). Gene selection for sample classification based on gene expression data: Study of sensitivity to choice of parameters of the GA/KNN method. Bioinformatics, 17, 1131–1142. DOI: 10.1093/bioinformatics/17.12.1131.

    Article  CAS  Google Scholar 

  • Ligor, M., Stankevičius, M., Wenda-Piesik, A., Obelevičius, K., Ragažinskiene, O., Stanius, Z., Maruška, A., & Buszewski, B. (2014). Comparative gas chromatographic–mass spectro-metric evaluation of hop (Humulus lupulus L.) essential oils and extracts obtained using different sample preparation methods. Food Analytical Methods, 7, 1433–1442. DOI: 10.1007/s12161-013-9767-5.

    Article  Google Scholar 

  • Luykx, D. M. A. M., & Van Ruth, S. M. (2008). An overview of analytical methods for determining the geographical origin of food products. Food Chemistry, 107, 897–911. DOI: 10.1016/j.foodchem.2007.09.038.

    Article  CAS  Google Scholar 

  • Marini, F. (2010). Classification methods in chemometrics. Current Analytical Chemistry, 6, 72–79. DOI: 10.2174/15734111 0790069592.

    Article  CAS  Google Scholar 

  • Monakhova, Y. B., Mushtakova, S. P., Kolesnikova, S. S., & Astakhov, S. A. (2010). Chemometrics-assisted spectropho-tometric method for simultaneous determination of vitamins in complex mixtures. Analytical and Boanalytical Chemistry, 397, 1297–1306. DOI: 10.1007/s00216-010-3623-x.

    Article  CAS  Google Scholar 

  • Obelevičius, K. (2003). Influence of meteorological conditions upon the Humulus lupulus cultivar yield and its quality. Botanica Lithuanica, Suppl. 5, 87–95.

    Google Scholar 

  • Parker, M., Pollnitz, A. P., Cozzolino, D., Francis, I. L., & Herderich, M. J. (2007). Identification and quantification of a marker compound for ‘pepper’ aroma and flavor in Shiraz grape berries by combination of chemometrics and gas chromatography–mass spectrometry. Journal of Agricultural and Food Chemistry, 55, 5948–5955. DOI: 10.1021/jf0705320.

    Article  CAS  Google Scholar 

  • Pham, D. T., Dimov, S. S., & Nguyen, C. D. (2005). Selection of k in k-means clustering. Proceedings of the Institution of Mechanical Engineers, Part C, 219, 103–119. DOI: 10.1243/095440605x8298.

    Google Scholar 

  • Praet, T., Van Opstaele, F., Steenackers, B., De Brabanter, J., De Vos, D., Aerts, G., & De Cooman, L. (2015). Changes in the hop-derived volatile profile upon lab scale boiling. Food Research International, 75, 1–10. DOI: 10.1016/j.foodres. 2015.05.022.

    Article  CAS  Google Scholar 

  • Salanţă, L. C., Tofană, M., Socaci, S., Mudura, E., Pop, C., Pop, A., & Fărcaş, A. (2016). Determination of volatiles in hops from Romania by solid phase fiber microextraction and gas chromatography–mass spectrometry. Analytical Letters, 49, 477–487. DOI: 10.1080/00032719.2015.1075129.

    Article  Google Scholar 

  • Sharpe, F. R., & Laws, R. J. (1981). The essential oil of hops: A review. Journal of the Institute of Brewing, 87, 96–107. DOI: 10.1002/j.2050-0416.1981.tb03996.x.

    Article  CAS  Google Scholar 

  • Shellie, R. A., Poynter, S. D. H., Li, J. F., Gathercole, J. L., Whittock, S. P., & Koutoulis, A. (2009). Varietal characterization of hop (Humulus lupulus L.) by GC–MS analysis of hop cone extracts. Journal of Separation Science, 32, 3720–3725. DOI: 10.1002/jssc.200900422.

    Article  CAS  Google Scholar 

  • Stenroos, L. E., & Siebert, K. J. (1984). Application of pattern-recognition techniques to the essential oil of hops. Journal of the American Society of Brewing Chemists, 42, 54–61. DOI: 10.1094/asbcj-42-0054.

    CAS  Google Scholar 

  • Šuštar-Vozlič, J., & Javornik, B. (1999). Genetic relationships in cultivars of hop, Humulus lupulus L., Determined by RAPD analysis. Plant Breeding, 118, 175–181. DOI: 10.1046/j.1439-0523.1999.118002175.x.

    Article  Google Scholar 

  • 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 spectrome-try/olfactometry. Journal of Agricultural and Food Chemistry, 61, 10555–10564. DOI: 10.1021/jf402496t.

    Article  Google Scholar 

  • Villalobos-Delgado, L. H., Caro, I., Blanco, C., Bodas, R., Andrés, S., Giráldez, F. J., & Mateo, J. (2015). Effect of the addition of hop (infusion or powder) on the oxidative stability of lean lamb patties during storage. Small Ruminant Research, 125, 73–80. DOI: 10.1016/j.smallrumres.2015.02.008.

    Article  Google Scholar 

  • Yamaguchi, N., Satoh-Yamaguchi, K., & Ono, M. (2009). In vitro evaluation of antibacterial, anticollagenase and antiox-idant activities of hop components (Humulus lupulus) addressing acne vulgaris. Phytomedicine, 16, 369–376. DOI: 10.1016/j.phymed.2008.12.021.

    Article  CAS  Google Scholar 

  • Woodske, D. (2012). Hop variety handbook: Learn more about hop…create better beer. USA: CreateSpace.

    Google Scholar 

  • Zanoli, P., & Zavatti, M. (2008). Pharmacognostic and pharmacological profile of Humulus lupulus L. Journal of Ethnopharmacology, 116, 383–396. DOI: 10.1016/j.jep.2008.01.011.

    Article  CAS  Google Scholar 

  • Zielinski, A. A. F., Haminiuk, C. W. I., Nunes, C. A., Schnitzler, E., van Ruth, S. M., & Granato, D. (2014). Chemical composition, sensory properties, provenance and bioactivity of fruit juices as assessed by chemometrics: A critical review and guideline. Comprehensive Reviews in Food Science and Food Safety, 13, 300–316. DOI: 10.1111/1541-4337.12060.

    Article  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Institute of Metrology, Kaunas University of Technology, Studentu̧ str. 50, Kaunas, LT-51368, Lithuania

    Paulius Kaškonas & Vilma Kaškonienė

  2. Faculty of Natural Sciences, Vytautas Magnus Universit, Vileikos str. 8, Kaunas, LT-44404, Lithuania

    Žydrūmas Stanius & Audrius Maruška

  3. Kaunas Botanical Garden of Vytautas Magnus University, #x017D;.E.Žilibero str. 6, Kaunas, LT-46324, Lithuania

    Kęstutis Obelevičius & Ona Ragažinskineė

  4. Institute of Mathematics and Informatics, Vilnius University, Akademijos str. 4, Vilnius, LT-08663, Lithuania

    Antanas žilinskas

Authors
  1. Paulius Kaškonas
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Žydrūmas Stanius
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Vilma Kaškonienė
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Kęstutis Obelevičius
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Ona Ragažinskineė
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. Antanas žilinskas
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. Audrius Maruška
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Vilma Kaškonienė.

Electronic supplementary material

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Kaškonas, P., Stanius, Ž., Kaškonienė, V. et al. Clustering analysis of different hop varieties according to their essential oil composition measured by GC/MS. Chem. Pap. 70, 1568–1577 (2016). https://doi.org/10.1515/chempap-2016-0092

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1515/chempap-2016-0092

Keywords

Search

Navigation