{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2026,5,12]],"date-time":"2026-05-12T00:56:45Z","timestamp":1778547405876,"version":"3.51.4"},"reference-count":33,"publisher":"MDPI AG","issue":"3","license":[{"start":{"date-parts":[[2015,8,14]],"date-time":"2015-08-14T00:00:00Z","timestamp":1439510400000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/"}],"content-domain":{"domain":[],"crossmark-restriction":false},"short-container-title":["Antioxidants"],"abstract":"<jats:p>A simple and reliable method for the simultaneous determination of nine phenolic compounds in barley and malted barley was established, using liquid chromatography-diode array detection-electrospray ionization tandem mass spectrometry (HPLC-DAD-ESI-MS\/MS). The phenolic compounds can be easily detected with both systems, despite significant differences in sensitivity. Concentrations approximately 180-fold lower could be achieved by mass spectrometry analysis compared to diode array detection, especially for the flavan-3-ols (+)-catechin and (\u2212)-epicatechin, which have poor absorptivity in the UV region. Malt samples were characterized by higher phenolic content comparing to corresponding barley varieties, revealing a significant increase of the levels of (+)-catechin and (\u2212)-epicatechin during the malting process. Moreover, the industrial malting is responsible for modification on the phenolic profile from barley to malt, namely on the synthesis or release of sinapinic acid and epicatechin. Accordingly, the selection of the malting parameters, as well as the barley variety plays an important role when considering the quality and antioxidant stability of beer.<\/jats:p>","DOI":"10.3390\/antiox4030563","type":"journal-article","created":{"date-parts":[[2015,8,18]],"date-time":"2015-08-18T02:36:16Z","timestamp":1439865376000},"page":"563-576","update-policy":"https:\/\/doi.org\/10.3390\/mdpi_crossmark_policy","source":"Crossref","is-referenced-by-count":80,"title":["Determination of Phenolic Content in Different Barley Varieties and Corresponding Malts by Liquid Chromatography-diode Array Detection-Electrospray Ionization Tandem  Mass Spectrometry"],"prefix":"10.3390","volume":"4","author":[{"given":"Daniel","family":"Carvalho","sequence":"first","affiliation":[{"name":"REQUIMTE\/LAQV\u2014Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal"}]},{"given":"Andreia","family":"Curto","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV\u2014Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9441-7867","authenticated-orcid":false,"given":"Lu\u00eds","family":"Guido","sequence":"additional","affiliation":[{"name":"REQUIMTE\/LAQV\u2014Departamento de Qu\u00edmica e Bioqu\u00edmica, Faculdade de Ci\u00eancias, Universidade do Porto, Rua do Campo Alegre 687, 4169-007 Porto, Portugal"}]}],"member":"1968","published-online":{"date-parts":[[2015,8,14]]},"reference":[{"key":"ref_1","doi-asserted-by":"crossref","first-page":"300","DOI":"10.1002\/j.2050-0416.2008.tb00773.x","article-title":"The effect of hydroxycinnamic acids and volatile phenols on beer quality","volume":"114","author":"Iyuke","year":"2008","journal-title":"J. Inst. Brew."},{"key":"ref_2","doi-asserted-by":"crossref","first-page":"89","DOI":"10.1002\/j.2050-0416.1999.tb00011.x","article-title":"Identification of the polyphenols in barley and beer by HPLC\/MS and HPLC\/electrochemical detection","volume":"105","author":"Whittle","year":"1999","journal-title":"J. Inst. Brew."},{"key":"ref_3","doi-asserted-by":"crossref","first-page":"602","DOI":"10.1021\/jf0346556","article-title":"Ferulic acid release and 4-vinylguaiacol formation during brewing and fermentation: Indications for feruloyl esterase activity in Saccharomyces cerevisiae","volume":"52","author":"Coghe","year":"2004","journal-title":"J. Agric. Food. Chem."},{"key":"ref_4","doi-asserted-by":"crossref","first-page":"150","DOI":"10.1002\/j.2050-0416.2008.tb00320.x","article-title":"Comparison of antioxidant activity of barley (Hordeum vulgare L.) and malt extracts with the content of free phenolic compounds measured by high performance liquid chromatography coupled with coularray detector","volume":"114","author":"Douanier","year":"2008","journal-title":"J. Inst. Brew."},{"key":"ref_5","doi-asserted-by":"crossref","first-page":"8068","DOI":"10.1021\/jf051410f","article-title":"Antioxidant properties of kilned and roasted malts","volume":"53","author":"Samaras","year":"2005","journal-title":"J. Agric. Food Chem."},{"key":"ref_6","doi-asserted-by":"crossref","first-page":"336","DOI":"10.1016\/j.foodchem.2014.07.154","article-title":"A comprehensive characterisation of beer polyphenols by high resolution mass spectrometry (LC\u2013ESI-LTQ-Orbitrap-MS)","volume":"169","author":"Estruch","year":"2015","journal-title":"Food Chem."},{"key":"ref_7","doi-asserted-by":"crossref","first-page":"1","DOI":"10.1016\/j.chroma.2004.09.024","article-title":"Free and bound phenolic compounds in barley (Hordeum vulgare L.) flours: Evaluation of the extraction capability of different solvent mixtures and pressurized liquid methods by micellar electrokinetic chromatography and spectrophotometry","volume":"1057","author":"Bonoli","year":"2004","journal-title":"J. Chromatogr. A"},{"key":"ref_8","doi-asserted-by":"crossref","first-page":"5195","DOI":"10.1021\/jf040075c","article-title":"Antioxidant phenols in barley (Hordeum vulgare L.) flour:\u2009 Comparative spectrophotometric study among extraction methods of free and bound phenolic compounds","volume":"52","author":"Bonoli","year":"2004","journal-title":"J. Agric. Food Chem."},{"key":"ref_9","doi-asserted-by":"crossref","first-page":"27","DOI":"10.1002\/j.2050-0416.2008.tb00302.x","article-title":"Antioxidant properties of free, soluble ester and insoluble-bound phenolic compounds in different barley varieties and corresponding malts","volume":"114","author":"Guido","year":"2008","journal-title":"J. Inst. Brew."},{"key":"ref_10","doi-asserted-by":"crossref","first-page":"119","DOI":"10.1016\/S0308-8146(02)00213-3","article-title":"Detection of bound phenolic acids: Prevention by ascorbic acid and ethylenediaminetetraacetic acid of degradation of phenolic acids during alkaline hydrolysis","volume":"79","author":"Nardini","year":"2002","journal-title":"Food Chem."},{"key":"ref_11","doi-asserted-by":"crossref","first-page":"137","DOI":"10.1016\/S0308-8146(03)00257-7","article-title":"Determination of free and bound phenolic acids in beer","volume":"84","author":"Nardini","year":"2004","journal-title":"Food Chem."},{"key":"ref_12","doi-asserted-by":"crossref","first-page":"14","DOI":"10.1016\/j.jnutbio.2005.03.026","article-title":"Phenolic acids from beer are absorbed and extensively metabolized in humans","volume":"17","author":"Nardini","year":"2006","journal-title":"J. Nutr. Biochem."},{"key":"ref_13","doi-asserted-by":"crossref","first-page":"1941","DOI":"10.1016\/j.ejca.2005.04.012","article-title":"Beer constituents as potential cancer chemopreventive agents","volume":"41","year":"2005","journal-title":"Eur. J. Cancer"},{"key":"ref_14","doi-asserted-by":"crossref","first-page":"238","DOI":"10.1006\/fstl.1996.0035","article-title":"Antioxidant activity of barley and malt: Relationship with phenolic content","volume":"29","author":"Maillard","year":"1996","journal-title":"LWT\u2014Food Sci. Technol."},{"key":"ref_15","doi-asserted-by":"crossref","first-page":"10994","DOI":"10.1021\/jf0722710","article-title":"Evolution of phenolic compounds and antioxidant activity during malting","volume":"55","author":"Lu","year":"2007","journal-title":"J. Agric. Food Chem."},{"key":"ref_16","doi-asserted-by":"crossref","first-page":"1625","DOI":"10.1002\/(SICI)1097-0010(199909)79:12<1625::AID-JSFA411>3.0.CO;2-8","article-title":"Antioxidant composition and activity of barley (Hordeum vulgare) and malt extracts and of isolated phenolic compounds","volume":"79","author":"Goupy","year":"1999","journal-title":"J. Sci. Food Agric."},{"key":"ref_17","doi-asserted-by":"crossref","first-page":"732","DOI":"10.1016\/j.foodchem.2006.06.051","article-title":"Antioxidant activities of barley seeds extracts","volume":"102","author":"Liu","year":"2007","journal-title":"Food Chem."},{"key":"ref_18","doi-asserted-by":"crossref","first-page":"4802","DOI":"10.1021\/jf0701943","article-title":"Relationship between phenolic compounds, anthocyanins content and antioxidant activity in colored barley germplasm","volume":"55","author":"Kim","year":"2007","journal-title":"J. Agric. Food Chem."},{"key":"ref_19","doi-asserted-by":"crossref","first-page":"2253","DOI":"10.1021\/jf052394p","article-title":"Flavanol and bound phenolic acid contents in different barley varieties","volume":"54","author":"Kinitz","year":"2006","journal-title":"J. Agric. Food Chem."},{"key":"ref_20","doi-asserted-by":"crossref","first-page":"398","DOI":"10.1016\/j.chroma.2007.10.080","article-title":"Characterization of monomeric and oligomeric flavan-3-ols from barley and malt by liquid chromatography-ultraviolet detection-electrospray ionization mass spectrometry","volume":"1189","author":"Dvorakova","year":"2008","journal-title":"J Chromatogr. A"},{"key":"ref_21","doi-asserted-by":"crossref","first-page":"318","DOI":"10.1016\/j.jcs.2012.01.002","article-title":"Fate of polyphenols and antioxidant activity of barley throughout malting and brewing","volume":"55","author":"Leitao","year":"2012","journal-title":"J. Cereal Sci."},{"key":"ref_22","doi-asserted-by":"crossref","first-page":"9335","DOI":"10.1021\/jf201253t","article-title":"Effect of modification of the kilning regimen on levels of free ferulic acid and antioxidant activity in malt","volume":"59","author":"Inns","year":"2011","journal-title":"J. Agric. Food Chem."},{"key":"ref_23","doi-asserted-by":"crossref","first-page":"6539","DOI":"10.1021\/jf0710231","article-title":"Effect of heat treatment on the antioxidant activity, color, and free phenolic acid profile of malt","volume":"55","author":"Inns","year":"2007","journal-title":"J. Agric. Food Chem."},{"key":"ref_24","doi-asserted-by":"crossref","unstructured":"Haynes, W.M. (2013). CRC Handbook of Chemistry and Physics, CRC Press. [94th ed.].","DOI":"10.1201\/b17118"},{"key":"ref_25","doi-asserted-by":"crossref","first-page":"117","DOI":"10.12921\/cmst.2012.18.02.117-128","article-title":"Quantum-chemical calculations of the antioxidant properties of trans-p-coumaric acid and trans-sinapinic acid","volume":"18","author":"Urbaniak","year":"2012","journal-title":"Comput. Methods Sci. Tech."},{"key":"ref_26","first-page":"109","article-title":"Use of RP-HPLC-ESI (\u2013)-MS\/MS to differentiate various proanthocyanidin isomers in lager beer extracts","volume":"6","author":"Callemien","year":"2008","journal-title":"J. Am. Soc. Brew. Chem."},{"key":"ref_27","doi-asserted-by":"crossref","first-page":"1139","DOI":"10.1021\/jf00019a010","article-title":"Improved HPLC determination of hydroxycinnamic acids in orange juice using solvents containing THF","volume":"40","author":"Rouseff","year":"1992","journal-title":"J. Agric. Food Chem."},{"key":"ref_28","doi-asserted-by":"crossref","first-page":"359","DOI":"10.1016\/S0021-9673(01)00913-X","article-title":"Analysis of phenolic constituents of biological interest in red wines by high-performance liquid chromatography","volume":"922","author":"Orte","year":"2001","journal-title":"J Chromatogr. A"},{"key":"ref_29","doi-asserted-by":"crossref","first-page":"351","DOI":"10.1016\/j.foodres.2010.10.008","article-title":"Influence of malt on the xanthohumol and isoxanthohumol behavior in pale and dark beers: A micro-scale approach","volume":"44","author":"Almeida","year":"2011","journal-title":"Food Res. Int."},{"key":"ref_30","doi-asserted-by":"crossref","first-page":"3283","DOI":"10.1021\/jf0527504","article-title":"Antioxidant properties of pearled barley fractions","volume":"54","author":"Madhujith","year":"2006","journal-title":"J. Agric. Food Chem."},{"key":"ref_31","doi-asserted-by":"crossref","first-page":"1019","DOI":"10.1007\/s00216-011-5703-y","article-title":"A novel application of microwave-assisted extraction of polyphenols from brewer\u2019s spent grain with HPLC-DAD-MS analysis","volume":"403","author":"Moreira","year":"2012","journal-title":"Anal. Bioanal. Chem."},{"key":"ref_32","doi-asserted-by":"crossref","first-page":"388","DOI":"10.1007\/s00217-002-0498-x","article-title":"Identification of a new flavanol glucoside from barley (Hordeum vulgare L.) and malt","volume":"214","author":"Friedrich","year":"2002","journal-title":"Eur. Food Res. Technol."},{"key":"ref_33","doi-asserted-by":"crossref","first-page":"673","DOI":"10.1016\/j.foodchem.2009.10.059","article-title":"Antioxidant and polyphenol oxidase activity of germinated barley and its milling fractions","volume":"120","author":"Sharma","year":"2010","journal-title":"Food Chem."}],"container-title":["Antioxidants"],"original-title":[],"language":"en","link":[{"URL":"https:\/\/www.mdpi.com\/2076-3921\/4\/3\/563\/pdf","content-type":"unspecified","content-version":"vor","intended-application":"similarity-checking"}],"deposited":{"date-parts":[[2025,10,11]],"date-time":"2025-10-11T20:50:40Z","timestamp":1760215840000},"score":1,"resource":{"primary":{"URL":"https:\/\/www.mdpi.com\/2076-3921\/4\/3\/563"}},"subtitle":[],"short-title":[],"issued":{"date-parts":[[2015,8,14]]},"references-count":33,"journal-issue":{"issue":"3","published-online":{"date-parts":[[2015,9]]}},"alternative-id":["antiox4030563"],"URL":"https:\/\/doi.org\/10.3390\/antiox4030563","relation":{},"ISSN":["2076-3921"],"issn-type":[{"value":"2076-3921","type":"electronic"}],"subject":[],"published":{"date-parts":[[2015,8,14]]}}}