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Study of Electrochemical Oxidation of Xanthohumol by Ultra-Performance Liquid Chromatography Coupled to High Resolution Tandem Mass Spectrometry and Ion Mobility Mass Spectrometry

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Abstract

Electrochemically assisted oxidation off-line combined with UPLC/ESI–MS and ion mobility mass spectrometry enabled us to gain insight into the oxidation mechanisms of xanthohumol. Several types of monomeric oxidation products were identified, i.e., monohydroxylated and dehydrogenated derivatives and related quinones. Besides, high contents of dimers were observed. The structures of four main oxidative condensation products of two xanthohumol molecules were proposed based on combination of retention time, exact mass measurement, fragmentation pattern, data from on-line ion mobility mass spectrometric experiments and with the support of independent electrochemical experiments. To the best of our knowledge, this is the first evidence on formation of xanthohumol dimers. The effect of the pH on the generation of oxidation products was further investigated. The monomeric and dimeric oxidation products are favored at pH of 5.5 and 4.5, respectively.

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References

  1. Gerhäuser C (2005) Beer constituents as potential cancer chemopreventive agents. Eur J Cancer 41:1941–1954

    Article  Google Scholar 

  2. Stevens JF, Page JE (2004) Xanthohumol and related prenylflavonoids from hops and beer: to your good health! Phytochemistry 65:1317–1330

    Article  CAS  Google Scholar 

  3. Magalhães PJ, Carvalho DO, Cruz JM, Guido LF, Barros AA (2009) Fundamentals and health benefits of xanthohumol, a natural product derived from hops and beer. Nat Prod Commun 4:591–610

    Google Scholar 

  4. Monteiro R, Faria A, Azevedo I, Calhau C (2007) Modulation of breast cancer cell survival by aromatase inhibiting hop (Humulus lupulus L.) flavonoids. J Steroid Biochem Mol Biol 105:124–130

    Article  CAS  Google Scholar 

  5. Pan L, Becker H, Gerhauser C (2005) Xanthohumol induces apoptosis in cultured 40-16 human colon cancer cells by activation of the death receptor- and mitochondrial pathway. Mol Nutr Food Res 49:837–843

    Article  CAS  Google Scholar 

  6. Gonçalves P, Araujo JR, Pinho MJ, Martel F (2011) In vitro studies on the inhibition of colon cancer by butyrate and polyphenolic compounds. Nutr Cancer 63:282–294

    Article  Google Scholar 

  7. Zajc I, Filipic M, Lah TT (2012) Xanthohumol induces different cytotoxicity and apoptotic pathways in malignant and normal astrocytes. Phytother Res 26:1709–1713

    Article  CAS  Google Scholar 

  8. Drenzek JG, Seiler NL, Jaskula-Sztul R, Rausch MM, Rose SL (2011) Xanthohumol decreases Notch1 expression and cell growth by cell cycle arrest and induction of apoptosis in epithelial ovarian cancer cell lines. Gynecol Oncol 122:396–401

    Article  CAS  Google Scholar 

  9. Lust S, Vanhoecke B, Janssens A, Philippe J, Bracke M, Offner F (2005) Xanthohumol kills B-chronic lymphocytic leukemia cells by an apoptotic mechanism. Mol Nutr Food Res 49:844–850

    Article  CAS  Google Scholar 

  10. Harikumar KB, Kunnumakkara AB, Ahn KS, Anand P, Krishnan S, Guha S, Aggarwal BB (2009) Modification of the cysteine residues in IkappaBalpha kinase and NF-kappaB (p65) by xanthohumol leads to suppression of NF-kappaB-regulated gene products and potentiation of apoptosis in leukemia cells. Blood 113:2003–2013

    Article  CAS  Google Scholar 

  11. Colgate EC, Miranda CL, Stevens JF, Bray TM, Ho E (2007) Xanthohumol, a prenylflavonoid derived from hops induces apoptosis and inhibits NF-kappaB activation in prostate epithelial cells. Cancer Lett 246:201–209

    Article  CAS  Google Scholar 

  12. Deeb D, Gao X, Jiang H, Arbab AS, Dulchavsky SA, Gautam SC (2010) Growth inhibitory and apoptosis-inducing effects of xanthohumol, a prenylated chalone present in hops, in human prostate cancer cells. Anticancer Res 30:3333–3339

    CAS  Google Scholar 

  13. Vene R, Benelli R, Minghelli S, Astigiano S, Tosetti F, Ferrari N (2012) Xanthohumol impairs human prostate cancer cell growth and Invasion and diminishes the incidence and progression of advanced tumors in TRAMP mice. Mol Med 18:1292–1302

    Article  CAS  Google Scholar 

  14. Gerhäuser C, Alt A, Heiss E, Gamal-Eldeen A, Klimo K, Knauft J, Neumann I, Scherf HR, Frank N, Bartsch H, Becker H (2002) Cancer chemopreventive activity of Xanthohumol, a natural product derived from hop. Mol Cancer Ther 1:959–969

    Google Scholar 

  15. Negrao R, Costa R, Duarte D, Gomes TT, Coelho P, Guimaraes JT, Guardao L, Azevedo I, Soares R (2012) Xanthohumol-supplemented beer modulates angiogenesis and inflammation in a skin wound healing model. Involvement of local adipocytes. J Cell Biochem 113:100–109

    Article  CAS  Google Scholar 

  16. Legette L, Ma L, Reed RL, Miranda CL, Christensen JM, Rodriguez-Proteau R, Stevens JF (2012) Pharmacokinetics of xanthohumol and metabolites in rats after oral and intravenous administration. Mol Nutr Food Res 56:466–474

    Article  CAS  Google Scholar 

  17. Yilmazer M, Stevens JF, Deinzer ML, Buhler DR (2001) In vitro biotransformation of xanthohumol, a flavonoid from hops (Humulus lupulus), by rat liver microsomes. Drug Metab Dispos 29:223–231

    CAS  Google Scholar 

  18. Yilmazer M, Stevens JF, Buhler DR (2001) In vitro glucuronidation of xanthohumol, a flavonoid in hop and beer, by rat and human liver microsomes. FEBS Lett 491:252–256

    Article  CAS  Google Scholar 

  19. Nikolic D, Li YM, Chadwick LR, Grubjesic S, Schwab P, Metz P, van Breemen RB (2004) Metabolism of 8-prenylnaringenin, a potent phytoestrogen from hops (Humulus lupulus), by human liver microsomes. Drug Metab Dispos 32:272–279

    Article  CAS  Google Scholar 

  20. Nikolic D, Li YM, Chadwick LR, Pauli GF, van Breemen RB (2005) Metabolism of xanthohumol and isoxanthohumol, prenylated flavonoids from hops (Humulus lupulus L.), by human liver microsomes. J Mass Spectrom 40:289–299

    Article  CAS  Google Scholar 

  21. Jirasko R, Holcapek M, Vrublova E, Ulrichova J, Simanek V (2010) Identification of new phase II metabolites of xanthohumol in rat in vivo biotransformation of hop extracts using high-performance liquid chromatography electrospray ionization tandem mass spectrometry. J Chromatogr A 1217:4100–4108

    Article  CAS  Google Scholar 

  22. Jirovsky D, Bednar P, Myjavcova R, Bartosova Z, Skopalova J, Tvrdonova M, Lemr K (2011) Study of electrochemical oxidation of cyanidin glycosides by online combination of electrochemistry with electrospray ionization tandem mass spectrometry. Monatsh Chem 142:1211–1217

    Article  CAS  Google Scholar 

  23. Jahn S, Karst U (2012) Electrochemistry coupled to (liquid chromatography/) mass spectrometry-current state and future perspectives. J Chromatogr A 1259:16–49

    Article  CAS  Google Scholar 

  24. Bamforth C (2003) Beer-tap into the art and science of brewing. Oxford University Press, Oxford

    Google Scholar 

  25. Marken F, Neudeck A, Bond AM (2010) Cyclic voltammetry. In: Scholz F (ed) Electroanalytical methods. Guide to experiments and applications. Springer, Berlin

    Google Scholar 

  26. Magalhães PJ, Dostalek P, Cruz JM, Guido LF, Barros AA (2008) The impact of a xanthohumol-enriched hop product on the behavior of xanthohumol and isoxanthohumol in pale and dark beer: a pilot scale approach. J Inst Brew 114:246–256

    Article  Google Scholar 

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Acknowledgments

This work received financial support from the European Union (FEDER funds) under the framework of QREN through Project NORTE-07-0124-FEDER-000069). LFG wishes to thank Foundation for Science and Technology (FCT) for his Sabbatical Leave Grant (SFRH/BSAB/1272/2012). DOC wishes to acknowledge FCT for his Ph.D. studentship (SFRH/BD/79939/2011). Authors thank to the project of Ministry of Education, Youth and Sports (Project LO1305), European Social Fund OP—Education for Competitiveness (Project CZ.1.07/2.3.00/30.0041) and Grant Agency of Czech Republic (Project P206/12/1150).

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Authors and Affiliations

  1. Regional Centre of Advanced Technologies and Materials, Department of Analytical Chemistry, Faculty of Science, Palacky University, 17. Listopadu 12, 77146, Olomouc, Czech Republic

    Luís F. Guido, Jakub Taborsky, Jana Skopalova, Helena M. E. B. Saldanha & Petr Bednar

  2. REQUIMTE - Departamento de Química e Bioquímica, Faculdade de Ciências, Universidade do Porto, Porto, Portugal

    Luís F. Guido & Daniel O. Carvalho

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  1. Luís F. Guido
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  2. Daniel O. Carvalho
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  3. Jakub Taborsky
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  4. Jana Skopalova
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  5. Helena M. E. B. Saldanha
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  6. Petr Bednar
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Correspondence to Petr Bednar.

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Guido, L.F., Carvalho, D.O., Taborsky, J. et al. Study of Electrochemical Oxidation of Xanthohumol by Ultra-Performance Liquid Chromatography Coupled to High Resolution Tandem Mass Spectrometry and Ion Mobility Mass Spectrometry. Chromatographia 78, 1233–1243 (2015). https://doi.org/10.1007/s10337-015-2954-3

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