The polyphenolic pigments of black tea include the theaflavins (TF), the flavonol glycosides (FG) and a group of uncharacterised brown pigments referred to as thearubigins (TR). The TR are shown to be a complex, heterogeneous group of compounds, the majority of which are unresolvable by reverse phase HPLC. Fractionation procedures have been modified, developed, combined and applied to black tea liquor, to improve the separation of black tea components and to allow fractions of less complexity be obtained. A degree of resolution has been achieved for TR fractions, unresolvable with reverse phase HPLC, using size exclusion HPLC. Calibration of the column suggested there may be little material above 2,000 daltons associated with the TR. Two heterogeneous TR fractions have been subjected to Porter's autoxidative assay for proanthocyanidins. The resulting solutions were analysed by reverse phase HPLC and shown to contain proanthocyanidins (9.4 and 16.1 %) and galloyl ester (7.1 and 7.4 %), some 73 and 84 % remains uncharacterised. A novel group of yellow pigments has been isolated for which the name theacitrins (TC) has been proposed. Data are presented that suggest the TC are possibly derived from the TF by oxidative opening of the dihydroxybenzene ring associated with the benztropolone structure. The contribution of the phenolic pigments to tea cream was investigated using reversed phase HPLC and found to be ? 86 % TR, 12 % TF and 2 % FG. Evidence is also presented for a synergistic interaction between TF and TR during cream formation. A method has been developed, using caffeine precipitation, for the isolation of TR material that is free from TF and FG Tea pigments have been stored in aqueous solutions to evaluate their potential for use as commercial colourants. The TF and TC were found to possess poor stability. The FG exhibited greater stability but possess low tinctoral power and poor water solubility. Many of the stability trials exhibited a darkening of colour associated with an increase in unresolvable TR material. Storage of an aqueous solution of a TF enriched fraction at 37 °C resulted in the production of unresolvable (TR-like) material. This material was found to possess molecular weights in excess of 2,000, indicating polymerisation. Evidence is presented to suggest the involvement of galloyl groups in the formation of non-hydrolysable bonds within this polymeric material.

Mit den vorgestellten Untersuchungen sollten das Potential der in Europa vorkommenden Echten Goldrute für den Anbau evaluiert und der Einfluß von Erntetermin, Schnitthöhe und Düngungsmaßnahmen sowie der abiotischen Umweltfaktoren Licht und Wasser auf den Ertrag und den Inhaltsstoffgehalt von Solidago virgaurea L. geprüft werden. In vier Feldversuchen wurden Inhaltsstoffgehalte, Ertragsparameter, Entwicklungsstadien sowie morphologische Merkmale untersucht. Die Gehalte an Flavonolglycosiden, Phenolglucosiden und Kaffeesäurederivaten wurden mittels HPLC und nachfolgender DAD-Detektion bestimmt. 45 Akzessionen aus dem europäischen Verbreitungsgebiet wurden anhand ihres Blühtermines gegliedert, den Unterarten virgaurea und minuta zugeordnet, und mit Hilfe von 33 morphologischen Merkmalen charakterisiert. Die Analyse von 452 Einzelpflanzen ergab Spannweiten von 0.4 bis 2.4 % Flavonolglycosiden, 0.7 bis 4.6 % Kaffeesäurederivaten und 0 bis 1.6 % Phenolglucosiden. Die phytochemische Zusammensetzung war innerhalb der einzelnen Akzessionen, insbesondere in der Unterart virgaurea hoch variabel. In einer anbaubezogenen Gesamtbewertung der Akzessionen erwiesen sich Herkünfte der Unterart virgaurea aufgrund hoher Drogenerträge von maximal 109 dt/ha und eines ausgewogenen Inhaltsstoffspektrums als die Wertvollsten. Im Lauf der Ontogenese stieg der Drogenertrag der Echten Goldrute an, während die Inhaltsstoffgehalte schwankten (Kaffeesäurederivate, Flavonolglycoside) oder relativ kontinuierlich absanken (Phenolglucoside). Eine gehaltsorientierte Ernte müßte daher zum relativ frühen Zeitpunkt des mittleren Knospenstadiums erfolgen. Hohe Masse- und Inhaltsstofferträge sind in einem Ernteverfahren mit niedrigen Schnitthöhen von 15 bis 30 cm erreichbar. In voll besonnten Pflanzen wurde im Vergleich zu schattierten eine höhere Anreicherung von Flavonolglycosiden und Kaffeesäurederivaten festgestellt, die durch die UV-Schutzfunktion dieser Stoffgruppen erklärbar ist. Daher muß angenommen werden, daß ontogenetisch bedingte Gehaltsveränderungen der Flavonolglycoside und Kaffeesäurederivate durch unterschiedliche Strahlungsverhältnisse überlagert werden können. Stickstoffdüngung verursachte neben der erwarteten ertragssteigernden Wirkung Unterschiede im Inhaltsstoffgehalt. In der ungedüngten Variante wurden jeweils die höchsten Flavonolglycosidgehalte bestimmt, gefolgt von der organischen Düngung sowie der Mehrnährstoff- und Stickstoffdüngung. Während die ermittelten Stickstoff- (maximal 96 kg/ha N) und Phosphorentzüge (maximal 39 kg/ha P2O5) vergleichsweise gering waren, wurden Kaliumentzüge (maximal 172 kg/ha K2O) festgestellt, die auch im Vergleich zu anderen Blatt- und Krautdrogen relativ hoch ausfielen. Im Gesamtüberblick aller Einflüsse wurde deutlich, daß Flavonolglycoside, gefolgt von Kaffeesäurederivaten am empfindlichsten auf Umwelteinflüsse wie Lichteinstrahlung und Nährstoffverfügbarkeit reagierten, während die Gruppe der Phenolglucoside nur geringe Schwankungen zeigte. Die Ergebnisse aller Versuchsfragen spiegeln das Spannungsfeld von landwirtschaftlichem Ertrag und pharmazeutisch geforderter Qualität wider, die häufig negativ korreliert sind. Bei der Produktion der Droge von Echter Goldrute muß daher eine Balance zwischen beiden Zielgrößen gefunden werden. / The aim of the presented studies was to evaluate the potential for cultivation of the European Goldenrod (Solidago virgaurea L.) and to examine the influences of harvesting date, cutting height, fertilization and of the abiotic environmental factors light and water on drug yield and compound content of the plant. In four field trials a fingerprint of 10 constituents, several parameters of drug yield, development stages and morphological traits were examined. The contents of flavonol glycosides, phenolic glucosides and caffeic acid derivatives were determined by HPLC and UV-detection by DAD. 45 european accession were sorted by their dates of anthesis and subdivided into the subspecies virgaurea and minuta and thereafter characterized by 33 morphological traits. The analysis of 452 individual plants showed ranges of 0.4 to 2.4 % flavonol glycosides, 0.7 to 4.6 % caffeic acid derivatives and 0.0 to 1.6 % phenolic glucosides. Within the examined accessions, especially subspecies virgaurea, a high variability of the phytochemical composition was observed. In an evaluation, accessions of subspecies virgaurea turned out to be most suitable for cultivation due to high drug yields up to 106 dt per ha and well-balanced spectra of constituents. During ontogenesis the drug yield of S. virgaurea increased, while compound contents varied (caffeic acid derivatives, flavonol glycosides) or decreased continuously (phenolic glucosides). Therefore a harvest aiming at high compound contents has to be carried out at a early development stage of mid budding. High mass and constituent yields can be obtained by a harvesting method with low cutting heights of 15 to 30 cm above ground. Plants in a sunny environment accumulated significantly higher amounts of flavonol glycosides and caffeic acid derivatives than shaded plants, which can be explained by the UV-protective function of these compound groups. Therefore it can be concluded that phytochemical variations during ontogenesis could be modified by different light conditions. Beside the expected drug yield increase, fertilization with nitrogen caused differences in the compound contents. The highest flavonol glycosides contents were observed in the unfertilized treatment, followed by treatments with organic fertilization, multinutrient fertilizer and calcium ammonium nitrate. While the nitrogen uptake by the plant (maximal 96 kg/ha N) and phosphorus (maximal 39 kg/ha P2O5) were relatively low, contrary potassium uptake (maximal 172 kg/ha K2O) was relatively high compared to other herbal drugs. In an overview of all influences it became obvious that the reaction of flavonol glycosides and caffeic acid derivatives were relatively sensitive to environmental influences such as light conditions and nutrient availability, while the group of phenolic glucosides showed low variations. The results of all field trials reflect the conflict between agricultural yield and pharmaceutical quality which are frequently negatively correlated. Therefore a balance between these two goals has to be found during drug production of S. virgaurea.