Abstract
The conversion of dihydroquercetin to catechin and procyanidin was studied in maturing wild type barley (Hordeum vulgare L., cv. Nordal) seeds and proanthocyanidin free mutants blocked in four different genes,ant 13, ant 17, ant 18 andant 19. In the wild type barley grown under controlled conditions, maximal rate of synthesis of catechin, procyanidin B3 and procyanidin C2 occurred 8–16 days after flowering. Dihydroquercetin was radioactively labelled by feeding (1-14C)-acetate and (2-14C)-acetate to flowerbuds of a petunia mutant accumulating this flavonoid. When fed to pericarp-testa tissue of wild type barley labelled catechin, procyanidin B3 and procyanidin C2 were synthesized establishing dihydroquercetin as a precursor of these compounds. In addition labelled 2,3-trans-3,4-cis-leucocyanidin was synthesized indicating that this compound is an intermediate. The leucocyanidin was identified by co-chromatography with an authentic standard prepared chemically by reduction of dihydroquercetin with NaBH4. The major product of this reduction, however, was the 2,3-trans-3,4-trans-leucocyanidin. Only mutantant 18-102 accumulated dihydroquercetin in the seeds. Feeding (14C)-dihydroquercetin to pericarp-testa tissue from the mutants revealed thatant 17-139 was capable of synthesizing significant amounts of labelled catechin and procyanidin, whereasant 13-101,ant 13-152,ant 18-102 andant 19-109 synthesized none or only very small amounts of these compounds. It is concluded that (i)ant 18 controls the reduction of dihydroquercetin to 2,3-trans-3,4-cis-leucocyanidin, (ii)ant 19 controls the reduction of the leucocyanidin to catechin, and (iii)ant 13 andant 17 control unidentified steps prior to dihydroquercetin.
Article PDF
Similar content being viewed by others
Abbreviations
- BAW:
-
n-butanol-acetic acid-water
- BW:
-
n-butanol-water
- CAW:
-
chloroform-acetic acid-water
- H NMR:
-
proton nuclear magnetic resonance
- HOAc:
-
acetic acid
- HPLC:
-
high pressure liquid chromatography
- MS:
-
massspectroscopy
- sBAWC:
-
s-butanol-acetic acid-water-chloroform
- 3,4-cis-diol:
-
(2R,3S,4S)-3,4,5,7,3′,4′-hexahydroxyflavan
- 3,4-trans-diol:
-
(2R,3S,4R)-3,4,5,7,3′,4′-hexahydroxyflavan
- TLC:
-
thin layer chromatography
- UV:
-
ultra violet
- WsB:
-
water saturated s-butanol
References
Aastrup, S., H. Outtrup &K. Erdal: Location of the proanthocyanidins in the barley grain. Carlsberg Res. Commun. 49, 105–109 (1984)
Baig, M.I., J.W. Clark-Lewis &M.J. Thompson: Flavan derivatives XXVII. Synthesis of a new racemate of leucocyanidin tetramethyl ether (2,3-cis-3,4-trans-isomer): N.M.R. spectra of the four racemates of leucocyanidin tetramethyl ether (5,7,3′,4′-tetramethoxyflavan-3,4-diol). Aust. J. Chem. 22, 2645–2650 (1969)
Barz, W. &W. Hosel: Metabolism of flavonoids. In: The Flavonoids. J.B. Harborne, T.J. Mabry & H. Mabry, eds., Chapman & Hall, London, pp. 916–969 (1975)
Botha, J.J., D. Ferreira &D.G. Roux: Synthesis of condensed tannins. Part 4. A direct biomimetic approach to (4,6)-and (4,8)-biflavanoids. J. Chem. Soc. Perkin Trans. I, 1235–1245 (1981)
Brandon, M.J., L.Y. Foo, L.J. Porter &P. Meredith: Proanthocyanidins of barley and sorghum: Composition as a function of maturity of barley ears. Phytochemistry 21, 2953–2957 (1982)
Britsch, L., W. Heller &H. Grisebach: Conversion of flavanone to flavone, dihydroflavonol and flavonol with an enzyme system from cell cultures of parsley. Z. Naturforsch. 36c, 742–750 (1981)
Clark-Lewis, J.W.: Flavan derivatives XXV. Mass spectra of 3-hydroxyflavanones, flavan-3-ols, and flavan-3,4-diols. Aust. J. Chem. 21, 3025–3054 (1968)
Creasy, L.L. &T. Swain: Structure of condensed tannins. Nature 208, 151–153 (1965)
Delcour, J.A., D. Ferreira &D.G. Roux: Synthesis of condensed tannins. Part 9. The condensation sequence of leucocyanidin with (+)-catechin and with the resultant procyanidins. J. Chem. Soc. Perkin Trans. I, 1711–1717 (1983)
Ebel, J. &K. Hahlbrock: Biosynthesis. In: The Flavonoids: Advances in Research. J.B. Harborne & T.J. Mabry, eds., Chapman & Hall, London. pp. 641–679 (1982)
Fonknechten, G., M. Moll, D. Cagniant, G. Kirsch &J.F. Muller: Synthesis and characterisation of dimers of catechin and epicatechin. J. Inst. Brew. 89, 424–431 (1983)
Forkmann, G., W. Heller &H. Grisebach: Anthocyanin biosynthesis in flowers of Matthiola incana. Flavanone 3- and flavonoid 3′-hydroxylases. Z. Naturforsch. 35c, 691–695 (1980)
Fritsch, H. &H. Grisebach: Biosynthesis of cyanidin in cell cultures of Haplopappus gracilis. Phytochemistry 14, 2437–2442 (1975)
Gerats, A.G.M., P. de Vlaming, M. Doodeman, B. Al &A.W. Schram: Genetic control of the conversion of dihydroflavonols into flavonols and anthocyanins in flowers of Petunia hybrida. Planta 155, 364–368 (1982)
Glennie, C.W.: Preharvest changes in polyphenols, peroxidase, and polyphenol oxidase in sorghum grain. J. Agric. Food Chem. 29, 33–36 (1981)
Glennie, C.W., W.Z. Kaluza &P.J. van Niekerk: High-performance liquid chromatography of procyanidins in developing sorghum grain. J. Agric. Food Chem. 29, 965–968 (1981)
Goldstein, J.L. &T. Swain: Changes in tannins in ripening fruits. Phytochemistry 2, 371–383 (1963)
Grisebach, H. &W. Barz: Biochemie der Flavonoide. Naturwissenschaften 56, 538–544 (1969)
Gupta, R.K. &E. Haslam: Plant proanthocyanidins. Part 5. Sorghum polyphenols. J. Chem. Soc. Perkin Trans. I, 892–896 (1978)
Hahlbrock, K. &H. Grisebach: Biosynthesis of flavonoids. In: The Flavonoids. J.B. Harborne, T.J. Mabry & H. Mabry, eds., Chapman & Hall, London, pp. 866–915 (1975)
Haslam, E.: Natural proanthocyanidins. In: The Flavonoids. J.B. Harborne, T.J. Mabry & H. Mabry, eds., Chapman & Hall, London, pp. 505–559 (1975)
Haslam, E.: symmetry and promiscuity in procyanidin biosynthesis. Phytochemistry 16, 1625–1640 (1977)
Haslam, E.: Proanthocyanidins. In: The Flavonoids: Advances in Research. J.B. Harborne & T.J. Mabry, eds., Chapman & Hall, London. pp. 417–447 (1982)
Hemingway, R.W., L.Y. Foo &L.J. Porter: Linkage isomerism in trimeric and polymeric 2,3-cis-procyanidins. J. Chem. Soc. Perkin Trans. I, 1209–1216 (1982)
Hemingway R.W. & L.Y. Foo: Condensed tannins: Quinone methide intermediates in procyanidin synthesis J. Chem. Soc. Chem. Commun., 1035–1036 (1983)
Jacques, D., C.T. Opie, L.J. Porter &E. Haslam: Plant proanthocyanidins. Part 4. Biosynthesis of procyanidins and observations on the metabolism of cyanidin in plants. J. Chem. Soc. Perkin Trans. I, 1637–1643 (1977)
Jende-Strid, B.: Mutations affecting flavonoid synthesis in barley. Carlsberg Res. Commun. 43, 265–273 (1978)
Jende-Strid, B.: Characterization of mutants in barley affecting flavonoid synthesis. In: Barley Genetics IV. Proc. 4th Int. Barley Genet. Symp., pp. 631–634 (1981)
Jende-Strid, B. &B.L. Møller: Analysis of proanthocyanidins in wild type and mutant barley (Hordeum vulgare L.). Carlsberg Res. Commun. 46, 53–64 (1981)
Karl, C., G. Muller &P.A. Pedersen: Ein neues Catechinglykosid aus Polypodium vulgare. Z. Naturforsch. 37c, 148–151 (1982)
Kho, K.F.F., G.J.H. Bennink &H. Wiering: Anthocyanin synthesis in a white flowering mutant of Petunia hybrida by a complementation technique. Planta 127, 271–279 (1975)
Markham, K.R.: Techniques of flavonoid identification. Academic Press, London, (1982)
Outtrup, H.: Structure of prodelphinidins in barley. Eur. Brewery Conv., Congr., Proc. Copenhagen 1981, 323–333 (1981)
Outtrup, H. &K. Schaumburg: Structure elucidation of some proanthocyanidins in barley by1H 270 MHz NMR spectroscopy. Carlsberg Res. Commun. 46, 43–52 (1981)
Patschke, L. &H. Grisebach: 4,2′, 4′,6′-Tetrahydroxychalcon-2′-glucosid-(β-14C) als Vorstufe für Catechine im Tee. Z. Naturforsch. 20b, 399 (1965)
Porter, I.J. &L.Y. Foo: Leucocyanidin: Synthesis and properties of (2R,3S,4R)-(+)-3,4,5,7,3′,4′-hexahydroxyflavan. Phytochemistry 21, 2947–2952 (1982)
Stafford, H.A.: Enzymic regulation of procyanidin biosynthesis, lack of a flav-3-en-3-ol intermediate. Phytochemistry 22, 2643–2646 (1983)
Stafford, H.A. &H.H. Lester: Procyanidins (condensed tannins) in green cell suspension cultures of Douglas fir compared with those in strawberry and avocado leaves by means of C18-reversed-phase chromatography. Plant Physiol. 66, 1085–1090 (1980)
Stafford, H.A. &H.H. Lester: Proanthocyanindins and potential precursors in needles of Douglas fir and in cell suspension cultures derived from seedling shoot tissues. Plant Physiol. 68, 1035–1040 (1981)
Stafford, H.A., M. Shimamoto &H.H. Lester: Incorporation of (14C)-phenylalanine into flavan-3-ols and procyanidins in cell suspension cultures of Douglas fir. Plant Physiol. 69, 1055–1059 (1982)
Stafford, H.A. &H.H. Lester: Enzymic and nonenzymic reduction of (+)-dihydroquercetin to its 3,4-diol. Plant Physiol. 70, 695–698 (1982)
Tanaka, T., G-I. Nonaka &I. Nishioka: 7-O-galloyl-(+)-catechin and 3-O-galloylprocyanidin B-3 from Sanguisorba officinalis. Phytochemistry 22, 2575–2578 (1983)
Wettstein, D. von, B. Jende-Strid, B. Ahrenst-Larsen &K. Erdal: Proanthocyanidin free barley prevents the formation of beer haze. MBAA Technical Quarterly 17, 16–23 (1980)
Zaprometov, M. &H. Grisebach: Dihydrokaempferol as precursor for catechins in the tea plant. Z. Naturforsch 28c, 113–115 (1973)
Author information
Authors and Affiliations
Additional information
Accepted by:H. Klenow, E. Lund & S.O. Andersen
Rights and permissions
About this article
Cite this article
Kristiansen, K.N. Biosynthesis of proanthocyanidins in barley: Genetic control of the conversion of dihydroquercetin to catechin and procyanidins. Carlsberg Res. Commun. 49, 503 (1984). https://doi.org/10.1007/BF02907552
DOI: https://doi.org/10.1007/BF02907552
