Browse > Article

Characterization of Low Molecular Weight Polyphenols from Pine (Pinus radiata) Bark  

Mun, Sung-Phil (Division of Forest Science, College of Agriculture and Life Sciences, Chonbuk National University)
Ku, Chang-Sub (Department of Advanced Organic Materials Engineering, Chonbuk National University)
Publication Information
Food Science and Biotechnology / v.15, no.3, 2006 , pp. 424-430 More about this Journal
Abstract
Low molecular weight polyphenols were isolated from hot water extracts of radiata pine (Pinus radiata) bark using a Sephadex LH-20 column and characterized by $^1H$ and $^{13}C$ NMR, UV, FT-IR, and GC-MS analyses. Major compounds isolated and identified were protocatechuic acid, trans-taxifolin, and quercetin. Trans-taxifolin, an important intermediate in biosynthetic route of proanthocyanidin (PA), was isolated in large quantities and indicates that PA is a major component of radiata pine bark. Small amounts of polyphenols were identified by GC-MS analysis. The presence of p-hydroxybenzoic acid, vanillic acid, protocatechuic acid, cis- and trans-feruic acid, p-coumaric acid, trans-caffeic acid, (-)-epicatechin, (+)-catechin, trans- and cis-taxifolin, (+)-gallocatechin, and quercetin was confirmed by comparison of mass fragmentation patterns and retention times (RT) with authentic samples. In addition, the presence of astringenin, astringenin glycoside, trans- and cis-leucodelphinidin was strongly assumed from characteristic mass fragment ions due to their conjugated structure and retro Diels-Alder reaction, and also from biosynthetic route of PA. GC-MS analysis allowed us to detect small amounts of phenolic acids and flavonoids and eventually discriminate trans- and cis-configuration in the identified polyphenols.
Keywords
Pinus radiata bark; polyphenols; trans-taxifolin; quercetin; protocatechuic acid;
Citations & Related Records
Times Cited By KSCI : 1  (Citation Analysis)
Times Cited By Web Of Science : 8  (Related Records In Web of Science)
연도 인용수 순위
1 Packer L, Rimbach G, Virgili F. Antioxidant activity and biologic properties of a proanthocyanidin-rich extract from pine (Pinus maritima) bark, pycnogenol. Free Radical Bio. Med. 27: 704-724 (1999)   DOI   ScienceOn
2 Ku CS, Mun SP. Identification and characterization of hot water extracts trom Pinus radiata bark and their potential bioactivity (abstract no P61530). In: Abstracts: 55th Annual Meeting of the Japan Wood Research Society. March 16-18, Kyoto University Yoshida-south Campus Clock Tower Centennial Hall, Kyoto, Japan. Japan Wood Research Society, Kyoto, Japan (2005)
3 Owen RW, Haubner R, Hull WE, Erben G, Spiegelhalder B, Bartsch H, Haber B. Isolation and structure elucidation of the major individual polyphenols in carob fibre. Food Chem. Toxicol. 41: 1727-1738 (2003)   DOI   ScienceOn
4 Tokusoglu MK, Ytldtrum Z. HPLC-UV and GC-MS characterization of the flavonol aglycones quercetin, kaempferol, and myrcetin in tomato pastes and other tomato-based products. Acta Chromatogr. 13: 196-207 (2003)
5 Duenas M, Estrella I, Hernandez T. Occurrence of phenolic compounds in the seed coat and the cotyledon of peas (Pisum sativum L.). Eur. Food Res. Technol. 219: 116-123 (2004)
6 Le Nest G, Caille O, Woudstra M, Roche S, Guerlesquin F, Lexa D. Zn-polyphenol chelation: complexes with quercetin, (+)-catechin, and derivatives: I optical and NMR studies. Inorgan. Chim. Acta 357: 775-784 (2004)   DOI   ScienceOn
7 Dellus V, Mila I, Scalbert A, Menard C, Michon V, Herve du Penhoat CLM. Douglas-fir polyphenols and heartwood formation. Phytochemitry 45: 1573-1578 (1997)   DOI   ScienceOn
8 Mabry TJ, Markham KR, Thomas MB. The systematic identification of flavonoids. Springer, New York, NY, USA. pp. 35-61 (1970)
9 Harborne JB, Mabry TJ. The flavonoids: advances in research. Chapman and Hall, New York, NY, USA. pp. 417-446 (1982)
10 Li TM, Li WK, Yu JG. Flavonoids from Artabotrys hexapetalus. Phytochemistry 45: 831-833 (1997)   DOI   ScienceOn
11 Re R, Pellegrini N, Proteggente A, Pannala A, Yang M, Rice-Evans C. Antioxidant activity applying an improved ABTS radical cation decolorization assay. Free Radical Bio. Med. 26: 1231-1237 (1999)   DOI   ScienceOn
12 Ku CS, Mun SP. Anti-oxidative potential of hot water extracts obtained from different species of pine bark (abstract no PP004). In: Abstracts: 54th Annual Meeting of the Japan Wood Research Society. August 3-5, Sapporo convention center, Sapporo, Japan. Japan Wood Research Society, Sapporo, Japan (2004)
13 Gonthier MP, Cheynier V, Donovan JL, Manach C, Morand G, Mila I, Lapierre C, Remesy C. Microbial aromatic acid metabolites formed in the gut account for a major fraction of the polyphenols excreted in urine of rats fed red wine polyphenols. Nutr. Metabol. 461-467 (2003)
14 Bergeron C, Marston A, Antus S, Gauthier R, Hostettmann K. Flavonoids from Pyrola elliptica. Phytochemistry 49: 233-236 (1998)   DOI   ScienceOn
15 Marfak A, Trouillas P, Allais DP, Calliste CA, Cook-Moreau J, Duroux JL. Reactivity of flavonoids with 1-hydroxyethyl radical: a ${\gamma}$-radiolysis study. Biochim. Biophy. Acta 1670: 28-39 (2004)   DOI   ScienceOn
16 Martens DA. Division S-3 - Soil biology & biochemistry: identification of phenolic acid composition of alkali-extracted plants and soils. Soil Sci. Soc. Am. J. 66: 1240-1248 (2002)   DOI   ScienceOn
17 Dubeler A, Voltmer G, Gora V, Lunderstadt J, Zeeck A. Phenols from Fagus sylvatica and their role in defence against Cyptococcus fagisuga. Phytochemistry 45: 51-57 (1997)   DOI   ScienceOn
18 Trouillas P, Fagnere C, Lazzaroni R, Calliste C, Marfak A, Duroux JL. A theoretical study of the conformational behavior and electronic structure of taxifolin correlated with the free radical-scavenging activity. Food Chem. 88: 571-582 (2004)   DOI   ScienceOn
19 Hassan EBM, Mun SP. Liquefaction of pine bark using phenol and lower alcohols with methanesultonic acid catalyst. J. Ind. Eng. Chem. 8: 359-364 (2002)
20 Peng X, Misawa N, Harayama S. Isolation and characterization of thermophilic bacilli degrading cinnamic, 4-coumaric, and ferulic acids. Appl. Environ. Microbiol. 69: 1417-1427 (2003)   DOI
21 Luximon-Ramma A, Bahorun T, Crozier A, Zbarsky V, Datla KP, Dexter DT, Aruoma OI. Characterization of the antioxidant functions of flavonoids and proanthocyanidins in Mauritian black teas. Food Res. Int. 38: 357-367 (2005)   DOI   ScienceOn
22 Kennedy JF, Methacanon P, Lloyd LL. The identification and quantitation of the hydroxycinnamic acid substituents of a polysaccharide extracted from maize bran. J. Sci. Food Agric. 79: 464-470 (1999)   DOI   ScienceOn
23 Moran JF, Klucas RV, Grayer RJ, Abian J, Harborne JB, Becana M. Characterization of phenolic glucosides from soybean root nodules by ion-exchange high performance liquid chromatography, ultraviolet spectroscopy and electrospray mass spectrometry. Phytochem. Anal. 9: 171-176 (1998)   DOI   ScienceOn
24 Boudet AC, Cornard JP, Merlin JC. Conformational and spectroscopic investigation of 3-hydroxyflavone-aluminium chelates. Spectrochim. Acta Part A 56: 829-839 (2000)   DOI   ScienceOn
25 van den Berg R, Haenen GRMM, van den Berg H, Bast A. Applicability of an improved Trolox equivalent antioxidant capacity (TEAC) assay for evaluation of antioxidant capacity measurements of mixtures. Food Chem. 66: 511-517 (1999)   DOI   ScienceOn
26 Couladis M, Baziou P, Verykokidou E, Loukis A. Antioxidant activity of polyphenols from Hypericum triquetrifolium Turra. Phytother. Res. 16: 769-770 (2002)   DOI   ScienceOn
27 Lu Y, Sun Y, Foo LY, McNabb WC, Molan AL. Phenolic glycosides of forage legume Onobrychis viciifolia. Phytochemistry 55: 67-75 (2000)   DOI   ScienceOn
28 Seog HM, Jung CH, Kim YS, Park HS. Phenolic acids and antioxidant activities of wild ginseng (Panax ginseng C. A. Meyer) leaves. Food Sci. Biotechnol. 14: 371-374 (2005)
29 Watson DG, Pitt AR. Analysis of flavonoids in tablets and urine by gas chromatography/mass spectrometry and liquid chromatography/mass spectrometry. Rapid Commun. Mass Sp. 12: 153-156 (1998)   DOI   ScienceOn
30 Franke R, Humphreys JM, Hemm MR, Denault JW, Ruegger MO, Cusumano JC, Chapple C. The Arabidopsis REF8 gene encodes the 3-hydroxylase of phenylpropanoid metabolism. Plant J. 30: 33-45 (2002)   DOI   ScienceOn
31 Zhang K, Zuo Y. GC-MS determination of flavonoids and phenolic and benzoic acids in human plasma after consumption of cranberry juice. J. Agric. Food Chem. 52: 222-227 (2004)   DOI   ScienceOn
32 Stevens JF, Hart H, Elema ET, Bolck A. Flavonoid variation in Eurasian Sedum and Sempervivum. Phytochemistry 41: 503-512 (1996)   DOI   ScienceOn
33 Lewis CE, Walker JRL, Lancaster JE, Sutton KH. Determination of anthocyanins, flavonoids and phenolic acids in potatoes. I: Coloured cultivars of Solanum tuberosum L. J. Sci. Food Agric. 77: 45-57 (1998)   DOI   ScienceOn
34 Cornard JP, Boudet AC, Merlin JC. Complexes of Al(III) with 3'4'-dihydroxy-flavone: characterization, theoretical and spectroscopic study. Spectrochim. Acta Part A 57: 591-602 (2001)   DOI   ScienceOn
35 Lee JY, Moon SO, Kwon YJ, Rhee SJ, Park HR, Choi SW. Identification and quantification of anthocyan ins and flavonoids in mulberry (Morus sp.) cultivars. Food Sci. Biotechnol. 13:176-184 (2004)
36 Markham KR. Flavones, flavonols and their glycosides. In: Methods in Plant Biochemistry, Plant Phenolics. Harborne JB (ed). Academic Press, New York, NY, USA. pp. 197-235 (1989)
37 Rauha JP, Remes S, Heinonen M, Hopia A, Kahkonen M, Kujala T, Pihlaja K, Vuorela H, Vuorela P. Antimicrobial effects of Finnish plant extracts containing flavonoids and other phenolic compounds. Int. J. Food Microbiol. 56: 3-12 (2000)   DOI   ScienceOn
38 Rice-Evans CA, Miller NJ, Paganaga G. Structure-antioxidant activity relationships of flavonoids and phenolic acids. Free Radical Bio. Med. 20: 933-956 (1996)   DOI   ScienceOn
39 Karonen M, Loponen J, Ossipov V, Pihlaja K. Analysis of procyanidins in pine bark with reversed-phase and normal-phase high-pertormance liquid chromatography-electro spray ionization mass spectrometry. Anal. Chim. Acta 522: 105-112 (2004)   DOI   ScienceOn
40 Kim YM, Wang MH, Rhee HI. A novel a-glucosidase inhibitor from pine bark. Carbohyd. Res. 339: 715-717 (2004)   DOI   ScienceOn
41 Gombau L, Garcia F, Lahoz A, Fabre M, Roda-Navarro P, Majano P, Alonso-Lebrero JL, Pivel JP, Castell JV, Gomez-Lechon MJ, Gonzalez S. Polypodium leucotomos extract: antioxidant activity and disposition. Toxicol. In Vitro 20: 464-471 (2006)   DOI   ScienceOn
42 Virgili F, Pagana G, Bourne L, Rimbach G, Natella F, Rice-Evans C, Packer L. Ferulic acid excretion as a marker of consumption of a French maritina pine (Pinus Maritima) bark extract. Free Radical Bio. Med. 28: 1249-1256 (2000)   DOI   ScienceOn
43 Peng ZF, Strack D, Baumert A, Subramaniam R, Goh NK, Chia TF, Tan SN, Chia LS. Antioxidant flavonoids from leaves of Polygonum hydropiper L. Phytochemistry 62: 219-228 (2003)   DOI   ScienceOn