Anthocyanin composition of cauliflower (Brassica oleracea L. var. botrytis) and cabbage (B. oleracea L. var. capitata) and its stability in relation to thermal treatments

Violet cauliflower and red cabbage were analysed for their anthocyanin profiles before and after thermal treatments. Anthocyanins are well-noted as healthy compounds due to their antioxidant properties. Samples were analysed for total anthocyanin content by using a spectrophotometric differential pH method. An MS-based method, combining high-performance liquid chromatography (HPLC) with quadrupole tandem mass spectrometry (HPLC–MS/MS) was developed, aimed to separate, identify and quantify the main anthocyanin forms. The procedure involves a rapid and efficient pre-treatment of the samples by solid-phase extraction, followed by selective determination of all compounds in a single run analysis using HPLC–MS/MS. Structural information for the identification of compounds was obtained from their fragmentation patterns (MS/MS spectra). The compounds were separated by HPLC and detected in the multiple reaction monitoring mode (MRM), which provides a high level of selectivity for targeting the analytes in vegetables. Cauliflower and red cabbage showed differences in their anthocyanin profiles: cyanidin-3,5-diglucoside was absent in cauliflower, while it was well represented in red cabbage, together with the characteristic anthocyanin of Brassica genus, cyanidin-3-sophoroside-5-glucoside. The p-coumaryl and feruloyl esterified forms of cyanidin-3-sophoroside-5-glucoside were predominant in cauliflower, while the sinapyl one was mostly present in red cabbage. Besides, the stability of cauliflower’s anthocyanin profile was evaluated in relation to thermal pre-treatments. All thermal treatments, except microwave heating, drastically reduced total cauliflower anthocyanin content. The amount of individual anthocyanins was expressed as the percentage with respect to total anthocyanin amount, spectrophotometrically measured. Significant individual changes were observed after different thermal treatment with an isomer formation.     

Anthocyanin pattern of several red grape cultivars and wines made from them

A high-performance liquid chromatography (HPLC) method with in-line photodiode array detection was applied to separate anthocyanins from red grape skin extracts of several Spanish cultivars, before and after winemaking, and from finished red wines. Data show that, for every cultivar studied, the anthocyanin pattern of the three materials considered (fresh grape skins, crushed grape skins after winemaking, and finished red wines) is quite different. These results may be explained by taking into account the different chemical structures of each anthocyanin and the degradation reactions that should take place during winemaking. On the other hand, the HPLC fingerprint of every material (fresh grape skins, crushed grape skins after fermentation, and wines) is related to cultivar characteristics. Thus, HPLC determination of the anthocyanin pattern of wines may be used to predict the grape cultivar from which wine was made.     

Anthocyanin composition of Vranec,Cabernet Sauvignon,Merlot and Pinot Noir grapes as indicator of their varietal differentiation

The anthocyanin composition of red grape varieties Vranec, Cabernet Sauvignon, Merlot and Pinot Noir was determined analyzing the skin extracts of the grape berries. The relative content of the identified anthocyanins was calculated and the obtained anthocyanic profiles were compared in terms of acylation and anthocyanidin distribution. The predominant anthocyanin in all varieties was malvidin-3-glucoside ranging from 35.8% in Cabernet Sauvignon to 67.1% in Pinot Noir. Vranec variety was characterized by high proportions of coumaroyl derivatives (22%) and peonidins (13%). The most pronounced difference among the studied grape cultivars was the relative amount of acetate derivatives accounting 35% in Cabernet Sauvignon, 22% in Merlot and 9% in Vranec. Different relationships among the anthocyanin groups of compounds were calculated and considered as parameters for differentiation of the cultivars. The relationship between coumarates and acetates in Vranec was significantly higher compared with Merlot and Cabernet Sauvignon with obtained values of 2.37 versus 0.63 and 0.56, respectively. Moreover, the ratio between delphinidins and peonidins allows clear discrimination between the studied grape cultivars showing the greatest difference.     

Jam Processing Effect on Phenolics and Antioxidant Capacity in Anthocyanin-rich Fruits: Cherry, Plum, and Raspberry

ABSTRACT: Four cultivars of sour cherries (Balaton, Karneol, Kroeker and Northstar), 2 cultivars of plums (BY 8158.50 and Methley), and 1 red raspberry cv. Prelude were analyzed for total phenolics, antioxidant capacity, and total anthocyanins before and after jam production to evaluate their changes after thermal processing. Fruits had total phenolics ranging from 245.7 to 398.5 mg gallic acid equivalent (GAE)/100 g. Antioxidant capacity of fruits ranged from 354.8 to 692.3 mg/100 g, expressed as vitamin C equivalent antioxidant capacity (VCEAC). Total anthocyanins of fruits ranged from 30.9 to 67.1 mg cyanidin 3-glucoside equivalent (CGE)/100 g. In 100 g of jam, total phenolics varied from 132.9 to 218.9 mg GAE, while antioxidant capacity ranged from 205.6 to 373.5 mg/100 g VCEAC. Jams had total anthocyanins of 5.4 to 30.4 mg CGE/100 g. On the basis of fresh fruit (100 g), the processing and heating during jam making generally decreased the contents of total phenolics, VCEAC, and total anthocyanins. Major losses occurred in anthocyanin content where overall retention varied from 89% to 21%. HPLC analysis of individual anthocyanins from cherry cv. Balaton to its jam showed that processing caused 90% decrease in anthocyanins. The results indicated that more than 73% total phenolics and more than 65% antioxidant capacity were retained after processing fruits into jams. Optimization of food processing would help to conserve the bioactive phenolic compounds in fruits.     

Enhanced Anthocyanin Extraction from Red Cabbage Using Pulsed Electric Field Processing

Abstract: This study was conducted to evaluate the effect of pulsed electric field (PEF) treatment on anthocyanin extraction from red cabbage using water as a solvent. Mashed cabbage was placed in a batch treatment chamber and subjected to PEF (2.5 kV/cm electric field strength; 15 μs pulse width and 50 pulses, specific energy 15.63 J/g). Extracted anthocyanin concentrations (16 to 889 μg/mL) were determined using HPLC. Heat and light stabilities of the control and PEF-treated samples, having approximately the same initial concentrations, were studied. PEF treatments enhanced total anthocyanin extraction in water from red cabbage by 2.15 times with a higher proportion of nonacylated forms than the control (P < 0.05). The heat and light stabilities of the PEF-treated samples and control samples were not significantly different (P > 0.05). Practical Application: An innovative pretreatment technology, pulsed electric field processing, enhanced total anthocyanin extraction in water from red cabbage by 2.15 times. Manufacturers of natural colors can use this technology to extract anthocyanins from red cabbage efficiently.     

Comparison of chromatic properties,stability and antioxidant capacity of anthocyanin-based aqueous extracts from grape pomace obtained from different vinification methods

The chromatic properties of anthocyanin-based aqueous extracts obtained from grape pomace from different vinifications methods (one rosé vinification, 6 h of skin contact time and three red wine vinifications, with 4, 8 and 12 days of skin contact time) have been studied. Differences due to the vinification method from which the pomace was obtained were clearly observed. Extracts from rosé vinifications had the highest content of anthocyanin compounds (measured both spectrophotometrically and by HPLC methods) although the total phenol content did not differ significantly between the different pomace extracts. As regards the stability of the different aqueous extracts under different pH, temperature and light conditions, only small differences were observed. Also, the antioxidant capacity of the extracts was evaluated and no significant differences were found between them; a better correlation being found between antioxidant capacity and estimated total phenol content than with anthocyanin content.     

Quantification of anthocyanins in black carrot extracts (<Emphasis Type="Italic">Daucus carota</Emphasis> ssp.<Emphasis Type="Italic"> sativus</Emphasis> var.<Emphasis Type="Italic"> atrorubens</Emphasis> Alef.) and evaluation of their color properties

Pigment composition of 15 black carrot cultivars (Daucus carota ssp. sativus var. atrorubens Alef.) was screened by HPLC-MS. Up to seven cyanidin glycosides, five of which were acylated with hydroxycinnamic and hydroxybenzoic acids, were identified and quantified in the roots by HPLC-DAD. Contents of individual compounds indicated great differences in the potential of anthocyanin accumulation both between different cultivars and carrots of the same cultivar. Total anthocyanin amounts ranged from 45.4 mg/kg dry matter to 17.4 g/kg dry matter. To the best of our knowledge, this is the first report on the quantification of individual anthocyanins in roots of different black carrot cultivars. The determination of color properties in the extracts under various pH conditions proved black carrot anthocyanins to be applicable as natural food colorants also for low-acid food commodities, whereas a considerable loss of color was noted under nearly neutral conditions. Additionally, relatively high saccharide contents were found in almost all cultivars which may be disadvantageous when coloring concentrates are produced from carrot roots.     

Factors influencing anthocyanin content in red cabbage (Brassica oleracea var capitata L f rubra (L) Thell)

In North and Central Italy an experiment was conducted for two consecutive years to optimise the anthocyanin yield of red cabbage. Two hybrids (‘Roxy’ and ‘Gradur’) were grown under a factorial combination of increasing rates of potassium sulphate (0, 50, 100 kg K ha^?1) and superphosphate (0, 39, 78 kg P ha^?1) applied before planting. Cabbages were transplanted at the beginning of August and harvested in winter. Anthocyanins were extracted from cabbage heads with HCl in methanol (1% v/v solution) and quantified by absorption spectrophotometry at 530 nm. Results showed that red cabbage can give high yields of anthocyanins (more than 90 kg ha^?1) which are characterised by strong acylation and therefore, presumably, by good stability. However, differences over sites and years were marked. In the first year, yields in North Italy were reduced by a heavy infection of soft rot disease. The choice of variety, linked to a different anthocyanin content in the heads, appeared to be the major factor for a successful crop. P and K fertilisation had only a small influence. On clay soils in Central Italy the highest rates of both elements had a negative effect on the anthocyanin concentration in cabbage heads. © 2002 Society of Chemical Industry     

Light and heat sensitivity of red cabbage extract in soft drink model systems

Anthocyanins of red cabbage (Brassica oleracea L.) display colour over a larger range of pH-values than the majority of anthocyanins from other natural sources, being pink at pH 3, violet at pH 5 and blue at pH 7. Using reversed phase high-performance liquid chromatography with diode array detection, cyanidin was found to be the only anthocyanidin of red cabbage extract and, tentatively, identified as cyanidin-3,5-diglucoside and cyanidin-3-sophoroside-5-glucoside, the latter found in various acylated forms. The apparent quantum yield for photobleaching has been determined for red cabbage extract at 25°C in air-saturated McIlvaine buffer, using monochromatic light at each of the irradiation wavelengths, 313, 366, and 436 nm, in continuous photolysis experiments, in order to provide an objective measure for the sensitivity of this food colorant to ultraviolet and visible light. The quantum yield was found to depend on both pH and irradiation wavelength, ranging from 0.2×10⁻⁴ mol einstein⁻¹ for 436 nm light at pH 7.0 to 3.7×10⁻⁴ mol einstein⁻¹ for 366 nm light at pH 5.0. The thermal stability at pH 3.0 in McIlvaine buffer of four different anthocyanin extracts was compared and, for the temperature range investigated (25–80°C) the degree of stability was red cabbage>blackcurrant>grape skin>elderberry. The thermal stability of the same anthocyanin extracts was also compared for a non-carbonated soft drink medium of pH 3.0 yielding the same order of stability but with rates of degradation approximately twice as high as in buffer, which may indicate a detrimental effect of sugar and ascorbic acid. Due to the high thermal stability of red cabbage extract in solution, photobleaching will be the primary destabilising factor for red cabbage anthocyanin-coloured products in display.     

高效液相色谱-电喷雾质谱法分析牡丹花中花色苷类化合物

利用高效液相色谱与二极管阵列检测器/电喷雾质谱联用技术研究了牡丹花中的花色苷类化合物,分离检测了五种花色苷,结合紫外吸收光谱和质谱信息分别鉴定为矢车菊-3,5-O-二葡萄糖苷,矢车菊-3-O-葡萄糖苷、芍药-3,5-O-二葡萄糖苷、芍药-3-O-葡萄糖苷和天竺葵-3,5-O-二葡萄糖苷;比较了六个牡丹品种的花色苷组成。     

HPLC Analysis of Cabernet Sauvignon and Noble Wine Pigment Fractions

Vitis vinifera cv. Cabernet Sauvignon and Vitis rotundifolia cv. Noble wines were made with different skin contact times to investigate the anthocyanin content of fractions isolated from the wines by low pressure column chromatography. The effect of acetaldehyde addition to wine was also investigated. The fractions were analyzed by a modified HPLC procedure using a 3-solvent gradient and a C-18 reverse phase column. Cabernet Sauvignon fractions contained different combinations of anthocyanins; Noble wine fractions contained different ratios of five anthocyanins present in the wines. These differences are hypothesized to influence the long-term stability of the wines.     

Identification and antioxidant activity of anthocyanins extracted from the seed and cob of purple corn (Zea mays L.)

The total anthocyanin content (TAC) and the antioxidant activity of the seed and cob from Chinese purple corn (Zea mays L., cv Zihei) extracts were determined by pH-differential method, and DPPH, FRAP, and TEAC methods, respectively. TAC in purple corn cob anthocyanins (PCCAs) extract was higher than TAC in purple corn seed anthocyanins (PCSAs) extract. Compared to bulylated hydroxytoluene (BHT), PCCAs and PCSAs possessed significantly higher antioxidant activities, according to the DPPH, FRAP and TEAC assays. A satisfactory correlation between TAC and antioxidant activity was observed. Result indicated that cyanidin-3-glucoside, pelargonidin-3-glucoside and peonidin-3-glucoside were components in PCSAs extracts, and seven kinds of anthocyanin had been detected and six kinds of anthocyanin in PCCAs extracts were separated and identified them as cyanidin-3-glucoside, pelargonidin-3-glucoside and peonidin-3-glucoside, and their respective malonated counterparts as their anthocyanins using HPLC–MS analysis.Industrial relevanceIn the last decades, in interest in anthocyanin pigments has increased because of their possible utilization as natural food colorants and especially as antioxidant and anti-inflammatory agents. Purple corn is a pigmented variety of Z. mays L., originally cultivated in Latin America. Now, this corn variety is mainly grown in China, especially in Shanxi and Anhui Province, could be new and interesting sources to obtain extracts rich in anthocyanins for their use in food, pharmaceutical and cosmetic industries. Our results indicated that the seed and cob of purple corn possessed excellent antioxidant activity, which could lead to increased application of these natural food colorants by the food industry.     

EFFECTS OF DIFFERENT MACERATION TIMES AND PECTOLYTIC ENZYME ADDITION ON THE ANTHOCYANIN COMPOSITION OF VITIS VINIFERA CV. KALECIK KARASI WINES

Kalecik karasi is an important red grape cultivar for winemaking in Turkey. The effect of three different maceration times (3, 6 and 12 days) and addition of pectolytic enzyme (2 and 4 g/hL) on the anthocyanin and chemical composition of Kalecik karasi wines were studied. High performance liquid chromatography-mass spectrometry coupled with diode array detection was used for analysis. Fourteen anthocyanin compounds were detected in wines. Major anthocyanins in all wines are malvidin-3-glucoside and its acylated esters. The results showed that increasing maceration time, especially with addition of enzymes, gives significant increases in anthocyanin contents. Moreover, the wines treated with enzymes had higher values in total phenolics, tannins, and color intensity than the control wines.

PRACTICAL APPLICATIONS

Anthocyanins are the most important polyphenols in red grapes and red wines with potential health benefits. Therefore, the first analysis of the anthocyanins contents of wine obtained from important turkish cv. Kalecik karasi using liquid-chromatography-mass spectrometry and the influence of different maceration times and addition of pectolytic enzyme on these important phenolic compounds are of interest for scientific literature, the wine industry as well as for the wine consumer.     

Evolution of polyphenols in red wines from Vitis vinifera L. during aging in the bottle

The evolution of anthocyanins and pyranoanthocyanins (as measured by high-performance liquid chromatography) in young red wines from Vitis vinifera L. cv Tempranillo, Graciano and Cabernet Sauvignon (vintage 2000) from Navarra (Spain) was studied during 26 months of aging in the bottle. For the anthocyanin pigments of grape origin, a progressive decrease in their concentration, corresponding to first-order kinetics, was observed during this period. Independently of the anthocyanin structure studied, grape anthocyanins in Tempranillo wine presented twofold slower kinetics than those in Graciano and Cabernet Sauvignon wines, which exhibited a very similar disappearance rate. Acylated anthocyanins presented a slightly higher disappearance rate than the nonacylated ones, indicating the possible hydrolysis of the former into the latter forms. However, no distinction was observed in the kinetics of the different anthocyanidin forms (delphinidins, petunidins, peonidins and malvidins). These results indicate that during aging under nonoxidative conditions (bottle), the chemical reactivity of grape anthocyanins in wine is influenced by the grape variety, a factor that imposes over the stability associated with the chemical structure of each anthocyanin form. In relation to the evolution of pyranoanthocyanins, anthocyanin–pyruvic acid adducts presented a similar or lower disappearance rate than their corresponding anthocyanin precursors during the first months of aging in the bottle, while anthocyanin–vinylphenol and anthocyanin–vinylflavanol adducts did not exhibit significant variations during the whole period studied.     

5种多酚类化合物提高紫甘蓝花色苷热稳定性及辅色机理初探

该研究选取儿茶素、没食子酸、香兰素、槲皮素、山奈酚五种多酚化合物作为辅色剂对紫甘蓝花色苷进行辅色,结果表明随着浓度增加,儿茶素和没食子酸的辅色作用不断加强,当浓度达到0.01 mol/L时,辅色作用增长缓慢;香兰素浓度达到0.004 mol/L时,辅色作用最强,浓度继续增加辅色作用反而减弱;槲皮素和山奈酚对紫甘蓝花色苷...     

Influence of partial rootzone drying on the composition and accumulation of anthocyanins in grape berries (Vitis vinifera cv. Cabernet Sauvignon)

Background and Aims: The aim of the study was to investigate anthocyanin composition and accumulation in grape berries in response to the partial rootzone drying (PRD) irrigation technique.
Method and Results: The experiment was on Vitis vinifera cv. Cabernet Sauvignon, wherein PRD had a 40% water deficit relative to the control treatment. PRD decreased berry weight compared with the control, but did not influence total anthocyanin concentration. A significant increase in glucosides of delphinidin, cyanidin, petunidin and peonidin was found in response to PRD from the onset of anthocyanin accumulation (veraison), while malvidin-glucosides were unaffected by the irrigation treatment. The PRD treatment did not cause changes in the proportions of acetyl-, 3- p -coumaroyl- and monoglucoside anthocyanins. Wines produced from the treatments showed no difference in total monomeric anthocyanin, but relative increases (15%) in wine colour density, total tannin and polymeric pigment occurred in response to the PRD treatment. The anthocyanin composition of the wines reflected the response shown in the grapes, where the relative contribution of non-malvidin anthocyanins to total anthocyanins was significantly increased in wines from the PRD treatment.
Conclusions: The differences in anthocyanin composition observed in response to PRD could not be accounted for by changes in bunch microclimate, and most likely reflect differences in the methylation step of anthocyanin synthesis.
Significance of the Study: The observed changes in anthocyanin composition under the PRD irrigation system have not been previously reported in response to water deficit, and may reflect a unique response to within-vine signalling induced by PRD.     

HPLC‐MSn Identification of Betalain Profile of Different Beetroot (Beta vulgaris L. ssp. vulgaris) Parts and Cultivars

The distribution of betalains in peel, flesh, and petioles of yellow and red beetroot cultivars has been investigated using an High‐performance liquid chromatography (HPLC) system with electrospray mass spectrometry. Differences in the levels of betacyanins and betaxanthins between different colored cultivars were individually determined for 3 plant parts. The content of almost all analyzed compounds decreased in the following order: peel > flesh > petiole. Betanin/isobetanin pigments comprised a major portion of the relative peak area measured in red beetroot peel. Isobetanin relative peak areas were also high in leaf petioles (68.94% to 74.16%) of red colored cultivars. However, betacyanins were completely absent from the extracts of all analyzed parts of yellow beet. Glutamine‐bx represented a very high relative peak area (59.54% to 64.18%) in flesh of red‐colored cultivars analyzed in the study. Our results indicate that red beet cultivars can be utilized as a potential source of red and yellow natural colorants. However, differences in pigment composition among different beetroot parts must be considered and in order to maximize the pigment yields petioles can also be used as a source rich in specific betalain compounds.     

萝卜花色苷的结构研究

红皮白心萝卜的色素提取物经大孔树脂XAD-7HP和葡聚糖凝胶Sephadex LH-20纯化后,结合半制备色谱制备花色苷单体,最后通过LC-MSn和NMR技术手段对萝卜花色苷单体的结构进行分析。通过LC-MSn鉴定出萝卜皮中主要存在四种主要的花色苷,都是以天竺葵色素为苷元,带一个单糖和一个二糖的花色苷衍生物,即以天竺葵-3-槐糖苷-5-葡糖苷为基本结构,带有一个或是两个酰基化的基团,如丙二酸、阿魏酸或香豆酸。经由1H NMR方法,其中三种花色苷的具体结构鉴定为:3-[6-(对香豆酰)-L-葡萄苷(2→1)-葡糖苷]-5-D-吡喃葡糖苷天竺葵素、3-[6-(阿魏酰)-L-葡萄苷(2→1)-葡糖苷]-5-D-吡喃葡糖苷天竺葵素、3-[6-(对香豆酰)-L-葡萄苷(2→1)-葡糖苷]-5-[(6-丙二酰)-D-吡喃葡糖苷]天竺葵素。通过质谱信息和文献报道,第四种花色苷的结构应为3-[6-(阿魏酰)-L-葡糖苷(2→1)-葡糖苷]-5[-(6-丙二酰)-D-吡喃葡糖苷]天竺葵素。     

Red clover isoflavonoids as anthocyanin color enhancing agents in muscadine wine and juice

Isoflavonoid extracts from red clover (Trifolium pratense) leaves were found to enhance overall color and stability of anthocyanin 3,5-diglucosides present in muscadine grape (Vitis rotundifolia) juice and wine through intermolecular copigmentation reactions. Predominant isoflavonoids present in red clover included formononetin, biochanin A, and prunetin and were the major polyphenolics identified to influence anthocyanin color and stability. Since red clover isoflavonoids have poor water solubility characteristics, this allowed for removal of extraneous non-isoflavonoid compounds using hot water and subsequent extraction with ethanol. Isoflavonoid solubility was evaluated as a function of ethanol concentration with recoveries up to 57% found in 20% solutions. Changes in maximum absorbance, total soluble phenolics, isoflavonoids, and anthocyanins were evaluated in muscadine juice and wine following the addition of isoflavonoid extracts with maximum color enhancement found at an anthocyanin to cofactor ratio of 1:8, after which their solubility was prohibitive. Additionally, dried leaves and ethanolic extracts of red clover were added prior to and following fermentation of muscadine wine (11% ethanol) stimulating the natural copigmentation that takes place during red wine fermentation and aging processes. Once fermentation was complete, finished wines were evaluated over a 9-week storage period at 20 and 37 °C. Despite low levels of isoflavonoids present, color improvement and anthocyanin stability was observed in the wines during storage. Little information is available on copigmentation reactions occurring in actual food systems, yet red clover isoflavonoids proved to be novel and effective color enhancing compounds when used in low concentrations in young muscadine wines.     

Anthocyanin composition and extractability in berry skin and wine of Vitis vinifera L. cv. Aglianico

BACKGROUND: The present article reports the anthocyanin content in the berry skin and wine of the Italian red grape cultivar Aglianico (clone VCR11 grafted onto 1103 Paulsen), one of the most ancient vines and famous for its deep‐red colour. Anthocyanins were extracted from frozen berry skin in an acidified methanol solution. The extraction mixtures, monitored for 120 h, were analysed by high‐performance liquid chromatography. RESULTS: The extraction from berry skin of delphinidin, petunidin and malvidin appeared to be a time‐independent process, whereas the concentration of peonidin increased linearly with time. Peonidin‐O‐acetyl‐glucoside was transferred from skin more slowly than petunidin‐O‐acetyl‐glucoside and malvidin‐O‐acetyl‐glucoside. The anthocyanin composition of the resulting wine showed that the total anthocyanin content was about one‐tenth of the corresponding berry skin content. The ratio acetyl/coumaroyl anthocyanins in the wine was sharply higher than the value in berry skin (0.85 and 0.10, respectively), indicating an enrichment of acetyl derivatives in the wine. CONCLUSION: Levels of single anthocyanins in wine were not always correlated with those detected in grapes, as they were affected by winemaking. The high values of some anthocyanins in Aglianico wine could ameliorate its quality, increasing the chromatic properties, aging stability and product acceptance. Copyright © 2011 Society of Chemical Industry