Differentiation of young red wines based on cultivar and geographical origin with application of chemometrics of principal polyphenolic constituents

Nineteen major polyphenolic phytochemicals including hydroxycinnamate derivatives, flavanols, flavonols, and anthocyanins, were determined in 40 experimental red wines employing HPLC-DAD. All wines analysed were young (non-aged), produced, and stored under identical conditions, in an effort to minimize the effect of oak wood and vinification technology. The data obtained from this examination composed the matrix for the implementation of chemometrics, which aimed at differentiating the wine samples on the basis of cultivar and geographical region of origin. Discriminant analysis performed at a 95% significance level revealed a very satisfactory categorization of the samples both in terms of cultivar and region of origin, thus illustrating the validity of major phenolic phytochemicals for studies pertaining to wine quality and authenticity.     

Direct characterization of aqueous extract of Hibiscus sabdariffa using HPLC with diode array detection coupled to ESI and ion trap MS

The phenolic fraction and other polar compounds of the Hibiscus sabdariffa were separated and identified by HPLC with diode array detection coupled to electrospray TOF and IT tandem MS (DAD‐HPLC‐ESI‐TOF‐MS and IT‐MS). The H. sabdariffa aqueous extract was filtered and directly injected into the LC system. The analysis of the compounds was carried out by RP HPLC coupled to DAD and TOF‐MS in order to obtain molecular formula and exact mass. Posterior analyses with IT‐MS were performed and the fragmentation pattern and confirmation of the structures were achieved. The H. sabdariffa samples were successfully analyzed in positive and negative ionization modes with two optimized linear gradients. In positive mode, the two most representative anthocyanins and other compounds were identified whereas the phenolic fraction, hydroxycitric acid and its lactone were identified using the negative ionization mode.     

Redox Behavior of Anthocyanins Present in Vitis vinifera L.

Voltammetric techniques were employed to study the electrochemical behavior of several anthocyanins. The redox behavior of anthocyanins with the same basic structure, the influence of glycosylation on the redox behavior of anthocyanins derived from different anthocyanidins, and the influence of methoxylation were investigated. The anthocyanins used in this study were malvidin‐3‐O‐glucoside chloride, malvidin‐3,5‐di‐O‐glucoside chloride, cyanidin‐3‐O‐glucoside chloride, cyanidin‐3,5‐di‐O‐glucoside chloride, peonidin‐3‐O‐glucoside chloride, delphinidin‐3‐O‐glucoside chloride and the anthocyanidin petunidin chloride, all of them present in Vitis vinifera L. All hydroxyl groups of the anthocyanins can be electrochemically oxidized and the anthocyanins studied revealed a complex and pH dependent oxidation process, with the occurrence of adsorption and of oxidation products blocking the electrode surface.     

The Chemistry of Rose Pigments

In this article we present a survey of the pigments found in the flowers and fruits of old and modern varieties of roses. The yellow colors are produced by carotenoids, the reds by anthocyanins, and the modern oranges by a mixture of the two. The great structural diversity of the carotenoids contrasts with a surprisingly small number of anthocyanins. For the carotenoids found in roses, a clear correspondence exists between the structure and the breeding partners used; the old yellow roses, which arose from crosses with Chinese varieties, mainly contain carotenoids from early stages in the biosynthesis, while in the modern yellow roses, which are descended from Central Asian foetida types, hydroxylations, epoxidations, and epoxide transformations readily occur. A recently elucidated carotenoid degradation sequence follows the scheme C₄₀ → C₁₃ + C₂₇ → C₁₃ + C₁₄. The C₁₃ compounds are odoriferous substances that contribute to the scent of roses. In the physiological pH region, copigmentation with flavonol glycosides is crucial for stabilization of the anthocyanin chromophores. Many roses, including the “apothecary's rose”, which was once used medicinally, contain large amounts of strongly astringent ellagitannins, monosaccharide esters of gallic acid.     

Determination of Anthocyanins and Flavonols in Paeonia delavayi by High-Performance Liquid Chromatography with Diode Array and Mass Spectrometric Detection

The colors of the leaves in Paeonia delavayi may be pure green, green-red, or dark red according to their habitat. The goal of this study was to compare the type and the total concentrations of anthocyanins and flavonols in red and green P. delavayi. The constituents and concentration of anthocyanins and flavonols were identified and determined by high-performance liquid chromatography with diode array detection and mass spectrometry. Cyanidin-3, 5-di-O-glucoside, cyanidin-3-O-glucoside, and peonidin-3-O-glucoside were first determined in red P. delavayi. There were no anthocyanins in green P. delavayi. Seven flavonols were identified in both red and green P. delavayi with differences in their concentrations. The concentrations of total anthocyanins and flavonoids were determined at 525 and 360?nm using the external standard method. The total anthocyanins in red P. delavayi were 152.24?mg/100?g in leaves and 78.92?mg/100?g in stems. The total flavonoids were 805.4?mg/100?g in leaves and 438.3?mg/100?g in stems, which were much higher than in green P. delavayi for both leaves and stems. This study reports composition and concentration differences in red and green P. delavayi based on ecological habitat.     

Three-way chemometric method study and UV-Vis absorbance for the study of simultaneous degradation of anthocyanins in flowers of the Hibiscus rosa-sinensys species

Ultraviolet-visible spectra of flower extracts of the Hibiscus rosa-sinensys L. var. regius maximus species have been measured between 240.02 and 747.97 nm at pH values ranging from 1.1 to 13.0. Deconvolution of these spectra using the Parallel Factor Analysis (PARAFAC) model permitted the study of anthocyanin systems without isolation and purification of the individual species. Seven species were identified: flavilium cation, carbinol, quinoidal base, and E and Z-chacone and their ionized forms. The concentration changes of flavilium cation, quinoidal basen, and E and Z ionized chalcones were determined as function of pH at the different wavelengths. The flavilium cation, quinoidal base, and ionized E-clacone are involved in tho stage kinetic processes, a fast one followed by a slower one. Ionized Z-chalcone obeys a simple first-order processes. The spectral profiles recovered by PARAFAC model are in excellent agreement with bands of experimental spectra reported in the literature for the individual species measured at specific pH values. These results complement those obtained using chemical and simple mathematical techniques and demonstrate how chemometric methods can resolve problems for complex systems.     

Anthocyanic composition of Tannat grapes from the south region of Uruguay

The anthocyanic composition of Tannat grapes produced in different vineyards in the south region of Uruguay was studied. Two training systems (vertical trellis and lyre) and two pruning methods (Guyot and Royat cordon) in the lyre were considered. A follow-up was carried out, considering 60 plants per treatment, and the vintage was determined according to the traditional indices of maturity. At the moment of the harvest, samples of grapes were taken in duplicate in each treatment and the soluble solids, total acidity, pH, phenolic richness, total potential in anthocyanins and extractable anthocyanin contents were determined. Grapes were frozen and later analysed; skin extractions over 24 h with a solution of 12% ethanol and pH 3.2 were carried out. The anthocyanic contents of the extracts obtained were determined by liquid chromatography. The total potential in anthocyanins of the grapes from the lyre with cordon pruning was significantly higher than the others, whereas the grapes from the cane pruning presented the highest extractable anthocyanins contents. The phenolic richness of the grapes from the lyre (with both pruning systems) was significantly higher than in the vertical trellis. Significant differences in the contents of the anthocyanins and in the anthocyanic profiles of the grapes of each treatment were found. Grapes from the vertical trellis system presented significantly higher proportions of malvidin, coumarylic and acetyl anthocyanins. Grapes from the lyre with cordon pruning presented significantly higher proportions of delphinidin, cyanidin, petunidin and peonidin, and non-acylated glucosides. It can be concluded that the yields and the environmental conditions given by the different vineyards determined important differences in the phenolic composition of Tannat grapes. The anthocyanic profiles of the grapes presented significant differences that might determine important variations in the colour and composition of the respective wines.     

Identification of anthocyanins in wines by liquid chromatography, liquid chromatography-mass spectrometry and nuclear magnetic resonance

Liquid chromatography (LC) was used for the fractionation of particular anthocyanins in glycoside form from methanol extracts of red grape skins and solid phase extracts of red wine. By the combination of nuclear magnetic resonance spectroscopy and LC-mass spectroscopy the identification of 13 anthocyanins in a particular LC fraction and hence the in particular peaks in chromatograms were obtained. Peaks areas in the chromatograms obtained under the semi-quantitaive conditions of the solid phase extracts of red wines Pinot Noir, Cabernet Sauvignon and Merlot from the Coastal wine-growing region in Slovenia, produced in 1999, were used as input data in chemometric analysis. The chemometric methods used were hierarchical clustering analysis and regularised discriminant analysis. The results of both methods give 100% correct classification of wines regarding the vine variety.     

Electrophoretic methods in the analysis of beverages

A review of the applications of electrophoresis to the determination of various compounds in beverage samples, namely beer, hard drinks, juice, milk, soft drinks, tea and wine, is presented.     

Thin-layer chromatography and densitometry of anthocyanins in the petals of red poppy during development of the flowers

Summary The variation in anthocyanins content of the petals of red poppy (Papaver, Rhoeas) during development of the flower from the closed bud stage have been investigated. Six-stage gradient thin-layer chromatography of the polyzonalstepwise type was used, starting from ethyl acetate, the last eluent fraction being isopropanol-water-acetic acid (65323). Silica Si 60 was used as adsorbent. The densitograms were recorded at 465 nm; they show gradually increasing peaks of red anthocyanins in the petals of closed buds, partly opened buds and fully developed flower and changes in the proportions of several anthocyanins, with various R_F values, during the growth of the flower.Editor's note: see also J. P. Goiffon, M. Brun and M.-J. Bourrier, J. Chromatogr.517, 101 (1991)