New identification of proanthocyanidins in cinnamon (Cinnamomum zeylanicum L.) using MALDI-TOF/TOF mass spectrometry
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The inner bark of Ceylon cinnamon (Cinnamomum zeylanicum L.) is commonly used as a spice and has also been widely employed in the treatment and prevention of disease. The positive health effects associated with the consumption of cinnamon could in part be due to its phenolic composition; proanthocyanidins (PA) are the major polyphenolic component in commercial cinnamon. We present a thorough study of the PA profile of cinnamon obtained using matrix-assisted laser desorption/ionization tandem time-of-flight (MALDI-TOF/TOF) mass spectrometry. In addition to the advantages of MALDI-TOF as a sensitive technique for the analysis of high-molecular-weight compounds, the tandem arrangement allows the identification of the compounds through their fragmentation patterns from MS/MS experiments. This is the first time that this technique has been used to analyze polymeric PA. The results show that cinnamon PA are more complex than was previously thought. We show here for the first time that they contain (epi)gallocatechin and (epi)catechingallate units. As gallates (galloyl moieties) and the pyrogallol group in gallocatechins have been related to the biological activity of grape and tea polyphenols, the presence of these substructures may explain some of the properties of cinnamon extracts. MALDI-TOF/TOF reveals that cinnamon bark PA include combinations of (epi)catechin, (epi)catechingallate, (epi)gallocatechin, and (epi)afzelechin, which results in a highly heterogeneous mixture of procyanidins, prodelphinidins, and propelargonidins.
KeywordsMALDI-TOF/TOF Cinnamon Polyphenols Proanthocyanidins Mass spectrometry
This work was supported by the Spanish Ministry of Education and Science (research grants AGL2009-12374-C03-03/ALI). J.P-J thanks the Spanish Ministry of Science and Innovation for granting her a Sara Borrell postdoctoral contract (CD09/00068). Language revision by Christopher Evans is also appreciated.
- 9.Premanathan M, Rajendran S, Ramanathan T, Kathiresan K, Nakashima H, Yamamoto N (2000) A survey of some Indian medicinal plants for anti-human immunodeficiency virus (HIV) activity. Indian J Med Res 112:73–77Google Scholar
- 14.Friedman M, Henika PR, Mandrell RE (2002) Bactericidal activities of plant essential oils and some of their isolated constituents against Campylobacter jejuni, Escherichia coli, Listeria monocytogenes, and Salmonella enterica. J Food Prot 65:1545–1560Google Scholar
- 16.Murcia MA, Egea I, Romojaro F, Parras P, Jiménez AM, Martínez-Tomé M (2004) Antioxidant evaluation in dessert spices compared with common food additives. Influence of irradiation procedure. Am Chem Soc 52:1872–1881Google Scholar
- 18.Preuss HG, Echard B, Polansky MM, Anderson R (2006) Whole cinnamon and aqueous extracts ameliorate sucrose-induced blood pressure elevations in spontaneously hypertensive rats. J Am Coll Nutr 25:144–150Google Scholar
- 24.Touriño S, Fuguet E, Jáuregui O, Saura-Calixto F, Cascante M, Torres JL (2008) High-resolution liquid chromatography/electrospray ionization time-of-flight mass spectrometry combined with liquid chromatography/electrospray ionization tandem mass spectrometry to identify polyphenols from grape antioxidant dietary fiber. Rapid Commun Mass Spectrom 22:3489–3500CrossRefGoogle Scholar
- 31.Déprez S, Brezillon C, Rabot S, Philippe C, Mila I, Lapierre C, Scalbert A (2000) Polymeric proanthocyanidins are catabolized by human colonic microflora into low-molecular-weight phenolic acids. J Nutr 130:2733–2738Google Scholar
- 36.Vivas N, Nonier M-F, Gaulejac NVd, Absalon C, Bertrand A, Mirabel M (2004) Differentiation of proanthocyanidin tannins from seeds, skins and stems of grapes (Vitis vinifera) and heartwood of Quebracho (Schinopsis balansae) by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry and thioacidolysis/liquid chromatography/electrospray ionization mass spectrometry. Anal Chim Acta 513:247–256CrossRefGoogle Scholar
- 44.Touriño S, Lizárraga D, Carreras A, Lorenzo S, Ugartondo V, Mitjans M, Vinardell MP, Juliá L, Cascante M, Torres JL (2008) Highly galloylated tannin fractions from witch hazel (Hamamelis virginiana) bark: electron transfer capacity, in vitro antioxidant activity, and effects on skin-related cells. Chem Res Toxicol 21:696–704CrossRefGoogle Scholar