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The present research focused on the analysis of European beech (Fagus sylvatica L.) wood polyphenols in respect to red heartwood formation, which is a significant color and technological defect of the species. For the first time, high-performance liquid chromatography/tandem mass spectrometry and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF) were applied for the investigation of the structure and the radial distribution of polyphenols. Altogether 125 compounds were characterized by their MSn spectra, of which 71 were tentatively identified, including procyanidins (dimers to pentamers), flavonoids (taxifolin, naringenin, isorhamnetin, (epi)afzelechin), (+)-catechin, (−)-epicatechin) and their glycoside conjugates, phenolic acids (gallic acid, vanillic acid, syringic acid) and their glycosides as well as gallic acid derivatives, many of which were identified for the first time in beech wood. It was found that the concentration of many compounds increased at the color boundary. In situ polyphenol synthesis and metabolism were clearly evidenced at the color boundary. Red heartwood contained only free aglycones (syringic acid, taxifolin, naringenin, isorhamnetin, naringenin, syringic acid). Contrary to earlier assumptions, the MALDI-TOF analysis did not indicate the presence of oxidized high-molecular-weight polymeric polyphenols in the red heartwood tissues. The role of individual compounds in the formation of the red heartwood chromophores are discussed.

Liquid Chromatographic/Mass Spectrometric Study on the Role of Beech (Fagus sylvatica L.) Wood Polyphenols in Red Heartwood Formation