Anthocyanins in Fruits of Vaccinium oxycoccus L. (Small Cranberry)

Peonidin-3-glucoside (41.9%) and cyanidin-3-glucoside (38.3%) were the main anthocyanins isolated from fruits of Vaccinium oxycoccus L. (Small cranberry). Smaller amounts of the 3-monogalactosides and 3-monoarabinosides of peonidin and cyanidin were found in addition to the 3-monoglucosides of delphinidin, petunidin and malvidin. The total anthocyanin content in the fruit averaged 78 mg/100g fresh fruit. This anthocyanin pattern is different from that of the American cranberry (Vaccinium macrocarpon L.).     

Antioxidant activity of corozo (<Emphasis Type="Italic">Bactris guineensis</Emphasis>) fruit by electron paramagnetic resonance (EPR) spectroscopy

The antioxidant activity of an anthocyanin-rich extract (ARE) of corozo fruit (Bactris guineensis) and its major constituents, cyanidin-3-rutinoside, cyanidin 3-glucoside and peonidin-3-rutinoside, was measured by stabilised free-radical EPR spectroscopy. The ARE of corozo exhibited a higher radical scavenging activity than pure anthocyanins using ABTS and DPPH free radicals. The antioxidant activity values for pure anthocyanins against the two radicals were different; however, a second-order kinetic model was followed in all of the cases. A cooperative effect regarding free-radical scavenging activity among studied anthocyanins was suggested. This study is the starting point to consider the ARE of corozo fruit as promising antioxidant material to be used in food industry.     

基于LC-MS/MS分析‘塔罗科’血橙优系果实花青素组分特征

以‘塔罗科’血橙优系为研究对象，运用液相色谱-串联质谱技术检测其与对照品种‘塔罗科’血橙果实花青素的组分及相对含量，筛选优系差异花青素代谢物。结果表明，‘塔罗科’血橙优系果实中共鉴定出矢车菊素、飞燕草素、芍药花素、天竺葵素、矮牵牛素、锦葵素以及花青素合成前体物质黄酮7 类33 种花青素相关代谢物，其内膛和外围果实花青素代谢物数量和种类一致，无差异代谢物；而对照品种内膛和外围果实分别检测出27 种和30 种花青素代谢物，其中内外差异代谢物达9 种，分属矢车菊素、飞燕草素、芍药花色素和黄酮4 类物质。‘塔罗科’血橙优系和对照品种花青素主要成分均为矢车菊素-3-O-丙二酰葡萄糖苷和矢车菊素-3-O-葡萄糖苷，两者在优系内膛和外围果实中分别约占总花青素含量的42.3%、41.0%和40.6%、41.4%，在对照品种内膛和外围果实中分别约占39.5%、41.0%和36.8%、40.6%。相比对照，‘塔罗科’血橙优系果实中矢车菊素类物质绝对含量和总花青素占比均显著提高，其内膛和外围果实矢车菊素类花青素总量分别为48.68 μg/g（91.90%）和62.16 μg/g（92.28%），此外，飞燕草素、芍药花素以及黄酮3 类代谢物占各自花青素总量的百分比也相近，推测‘塔罗科’血橙优系果实花青素合成可能受温度的影响较小。研究发现‘塔罗科’血橙优系较对照品种花青素含量高且代谢物种类多，综合品质优良，可为血橙品种遗传改良及利用提供一定的理论依据。     

Phenolic Analyses of Haskap Berries (Lonicera caerulea L.): Spectrophotometry Versus High Performance Liquid Chromatography

Haskap berries (Lonicera caerulea L.) are known for their high phenolics, anthocyanins, and antioxidant potential. The data on the phenolic profile of these fruits are lacking. In this study, the phenolic profiles of three haskap varieties; tundra, berry blue, and indigo gem grown in Nova Scotia, Canada were investigated for the first time using spectrophotometery and high-performance liquid chromatography. Berries were analyzed for total phenolic content/total reducing capacity, total anthocyanin content, and antioxidant potential (2,2-diphenyl-1-picrylhydrazyl radical scavenging activity). The total reducing capacity, total anthocyanin content, and 2,2-diphenyl-1-picrylhydrazyl values were 6.17–8.42 mg gallic acid equivalents/gram fresh weight, 4.49–6.97 mg cyanidin-3-glucoside equivalents/gram fresh weight, and 78.70–89.55%, respectively. The extracts were analyzed by reversed-phase diode array detector–high-performance liquid chromatography through a gradient elution using Synergi 4 µm Max-RP C12 column and the chromatograms were acquired at 520, 360, and 320 nm for athocyanins, flavonoids, and free phenolic acids, respectively. The identified anthocyanins were cyanidin-3-glucoside (82.81–91.99% of the total anthocyanins), cyanidin 3,5-di-glucoside (2.31–4.27%), cyanidin-3-rutinoside (1.54–9.20%), peonidin-3-O-glucoside (0.75–3.44%), and pelargonidin-3-glucoside (0.77–2.98%). Other flavonoids (quercetin-3-β-D-glucoside and quercetin-3-rutinoside) and free phenolic acids (chlorogenic and neochlorogenic) were also quantified.     

Blackberry Juice and Wine: Processing and Storage Effects on Anthocyanin Composition, Color and Appearance

Blackberry wine was made from thawed fruit (Evergreen variety) by fermentation of pulp, depectinized juice, and high-temperature short-time (HTST)-treated and depectinized juice. The effects of fining and storage on pigment composition, color and appearance were investigated. Seven anthocyanin pigments (cyanidin-3-glucoside, cyanidin-3-rutinoside, a xylose-cyanidin derivative, two acylated cyanidin derivatives, cyanidin and a polymeric derivative) were detected in the juices and wines by HPLC. Cyanidin-3-glucoside was highly unstable during fermentation. Haze development and sediment formation occurred, and 85 to 100% of total anthocyanins degraded. Blackberry juice that had been HTST-pasteurized, depectinized and fined produced wine with the most stable color and best appearance after storage.     

Nutritional composition of commercial pickled garlic

The effect of pulp treatment on the qualitative and quantitative changes to polyphenol compounds, such as anthocyanins and flavanols, in musts and wines from blackcurrant and cherries was investigated. The following variants of pulp treatment were used: hot maceration, hot maceration and pulp pectinolysis with Rohapect MA Plus and Pectopol PM preparations, and also pulp pectinolysis with Rohapect and Pectopol preparations. The method of treatment affected the content of anthocyanins and flavan-3-ols in the musts. Different types of phenolic compounds reacted differently under must-making conditions. Wines made with different treatments presented statistical differences with the control wine and between them for the parameters studied.As a result of the analysis of cherry musts and wines by HPLC, the following flavan-3-ols were identified: catechin, epicatechin, dimer B₂ and trimer C₁. In the cherry wines studied, in the variants subjected to pectinolysis and fermentation in the pulp, epicatechin occurred in a smaller amount than catechin, while in the wines subjected to thermal treatment it was predominant. In the blackcurrant musts and wines the following flavanols were identified: gallocatechin, catechin, epigallocatechin, dimer B₂, epicatechin and trimer C₁. In the cherry musts and wines the following anthocyanin pigments have been identified: cyanidin 3-glucoside, cyanidin 3-rutinoside and cyanidin 3-glucosylrutinoside, the amount of which was the greatest. Anthocyanins identified in the blackcurrant musts and wines were delphinidine and cyanidine glycosides: delphinidin 3-glucoside, delphinidin 3-rutinoside, cyanidin 3-glucoside and cyanidin 3-rutinoside; their aglycones were also found.     

Evolution of juice anthocyanins during ripening of new selected pomegranate (Punica granatum) clones

 For five new clones of pomegranate, cultivated under homogeneous conditions, changes in juice anthocyanin contents during ripening were studied. Six anthocyanin pigments were found to be responsible for the red color of pomegranate juice. These were quantitatively and qualitatively analyzed by high-performance liquid chromatography and identified as delphinidin 3-glucoside and 3,5-diglucoside, cyanidin 3-glucoside and 3,5-diglucoside and pelargonidin 3-glucoside and 3,5-diglucoside. Generally, there was an increase in juice pigmentation during fruit ripening. In the early fruit-ripening stages, delphinidin 3,5-diglucoside was the main pigment, followed by cyanidin 3,5-diglucoside, while in the later stages, the monoglucoside derivatives cyanidin 3-glucoside and delphinidin 3-glucoside increased considerably. The pelargonidin derivatives were always present in small amounts. Received: 1 March 1999     

‘紫娟’茶花色苷的分离鉴定

依次以MCI gel CPH 20P(75~150μm)树脂和Sephadex~(TM) LH-20葡聚糖凝胶为层析柱填料,对‘紫娟’茶花色苷进行分离纯化,采用5%乙酸-甲醇溶液和5%乙酸溶液对花色苷提取液梯度洗脱,得到6种花色苷组分。采用薄层层析、高效液相色谱及高效液相色谱-电喷雾-串联质谱对‘紫娟’茶花色苷组成成分进行研究。结果表明:从‘紫娟’茶鲜叶中分离出的花色苷为飞燕草素-3-O-半乳糖苷、矢车菊素-3-O-半乳糖苷、飞燕草素-3-O-(6-(Z)对香豆酸)吡喃半乳糖苷、矢车菊素-3-O-(6-(Z)对香豆酸)吡喃半乳糖苷、飞燕草素-3-O-(6-(E)对香豆酸)吡喃半乳糖苷、矢车菊素-3-O-(6-(E)对香豆酸)吡喃半乳糖苷。     

基于液相色谱-质谱联用技术定性定量分析黑豆种皮中可溶型和结合型花青素

以超声波辅助有机溶剂提取法获得黑豆种皮可溶型花青素提取物,再进一步对不含可溶型花青素的黑豆种皮残渣使用酸水解和碱水解以及酸碱/碱酸轮提水解,获得黑豆种皮结合型花青素提取物。采用超高效液相色谱-电喷雾-四极杆飞行时间质谱联用仪分析鉴定各黑豆种皮提取物中所含有的共17 种花青素成分,包括11 种花青素糖苷类：飞燕草素-3-O-葡萄糖苷、飞燕草素-3-O-半乳糖苷、矮牵牛花素-3-O-葡萄糖苷、矮牵牛花素-3-O-半乳糖苷、天竺葵素-3-O-芸香糖苷、矢车菊素-3-O-葡萄糖苷、矢车菊素-3-O-半乳糖苷、天竺葵素-3-O-己糖苷、芍药花素-3-O-己糖苷、天竺葵素-3-O-(6”-丙二酰葡萄糖苷)和芹菜定-3-O-(6”-丙二酰葡萄糖苷);6 种花青素苷元：飞燕草素、矢车菊素、矮牵牛花素、天竺葵素、芹菜定和芍药花素。采用高效液相色谱-电喷雾-三重四极杆质谱联用仪精确定量各类黑豆种皮提取物中的花青素含量,结果表明,酸性结合型花青素提取物中结合型花青素的总含量最高。此外,在黑豆种皮的可溶型花青素提取物中,花青素主要以花青素糖苷类形式存在,苷元含量相对极少;而在结合型花青素提取物中,则主要以花青素苷元为主,糖苷类化合物相对少见。     

The distribution of anthocyanins in grape skin extracts of port wine cultivars as determined by high performance liquid chromatography

The distribution of anthocyanins in methanolic skin extracts of 16 grape cultivars used for port wine production and grown at five sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Results are confined to the seven most readily separated and identified anthocyanins and are expressed as percentages of their total (88–99% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated. Of these, Mv 3-glucoside was the major pigment (33–60%), being exceeded by Mv 3-p-coumarylglucoside (2–51%) in only two cultivars; Mv 3-acetylglucoside (1–15%) was consistently the lowest. Peonidin 3-glucoside (1–27%) was prominent in four cultivars, but delphinidin 3-glucoside (1–11%), petunidin 3-glucoside (2–11%) and cyanidin 3-glucoside (trace-6%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site, and a useful aid to identification of grape cultivars. The coloured pulp of some cultivars contained peonidin 3-glucoside as a major component, present in greater proportions than in the skin; the percentage of Mv 3-p-coumarylglucoside was lower in pulp than in skin. The identities of six of the seven anthocyanins were confirmed by fast atom bombardment mass spectrometry and the structures of the Mv derivatives were determined by nuclear magnetic resonance. The formation of formyl and acetyl anthocyanin artefacts is described.     

The distribution and content of anthocyanins in young port wines as determined by high performance liquid chromatography

The distribution and content of anthocyanins in young port wines made in three successive years (1981–1983) from up to sixteen grape cultivars grown at five different sites in the Douro Valley in Northern Portugal has been assessed by high performance liquid chromatography. Distributions are confined to the seven most readily separated and identified anthocyanins and expressed as percentages of their sum (78–97% of the total integrated area). Anthocyanins based on malvidin (Mv) predominated (57–94%). Of these Mv 3-glucoside was the major pigment (43-76%), followed usually by Mv 3-p-coumarylglucoside (1–38%) and then Mv 3-acetylglucoside (2–18%). Peonidin 3-glucoside (2–39%) was prominent in a few cultivars but delphinidin 3-glucoside (1–13%), petunidin 3-glucoside (2–12%) and cyanidin 3-glucoside (trac-4%) were of low proportions throughout. The ratio Mv 3-acetylglucoside/total Mv glucosides appeared characteristic of cultivar, independent of site and a useful aid to identification. The percentages of Mv 3-p-coumarylglucoside were usually lower in ports than in grape skin extracts of the same cultivars. The contents of total anthocyanins in the ports ranged from 143–1080 mg 1^?1 (expressed as malvidin 3-glucoside chloride) and varied according to site and season.     

湛江地区不同桑葚品种的品质比较

本研究对17份桑葚种质资源的花青素、糖组分、可溶性总糖、可滴定酸、维生素C、总黄酮及总酚等品质性状进行了测定分析,并采用主成分、聚类分析对其进行综合评价。结果表明,在17个桑葚品种中共检测到飞叶草素、矢车菊素、天竺葵素、矮牵牛素、芍药色素和锦葵色素6种花青苷组分,其中矢车菊素的含量最高,其次为飞叶草素。果糖和葡萄糖是桑葚主要的糖组分。通过主成分分析得出飞叶草素、矢车菊素、天竺葵素、矮牵牛素、锦葵色素、总黄酮和总酚的含量可作为其营养价值评价的重要指标;基于花青素含量等指标聚类分析可将本研究的17个桑葚品种分为3类。     

Chemical,rheological and sensory characteristics of sweet spreads made from by-products of soya bean and maize

Sweet maize cob (SMC) and black soya bean seed coat (BSC) were used to prepare a sweet spread. Chemical composition of the prepared spread and its rheological and sensory characteristics were investigated. The results were compared with those of commercial plum and raspberry jams and spreads. Spreads made from SMC and BSC had the highest content of proteins, total fibres, hemicellulose and cellulose. In relation to fruit jams, they are distinguished by the presence and content of p-coumaric, ferulic and 3,4-dihydroxybenzoic acids, as well as of flavonoids such as catechin and quercetin. SMC spread with 3.2% of BSC had the highest content of total anthocyanins (666.75 mg CGE kg⁻¹) (cyanidin 3-glucoside equivalent). Cyanidin-3-glucoside (Cy-3-Glu) was the most abundant anthocyanins in SMC/BSC containing spreads, while in raspberry jam, that was cyanidin-3-sophoroside (Cy-3-Sop). According to chemical, rheological and sensory properties, SMC/BSC containing spreads could be competitive with fruit jams and spreads.     

Hepatoprotective and antioxidant activity of anthocyanins in black rice bran on carbon tetrachloride-induced liver injury in mice

The benefits of anthocyanin-rich black rice bran extract (ARBE) on the liver of carbon tetrachloride (CCl₄)-intoxicated mice was investigated. Based on the in vivo experiment, the effect of cyanidin-3-glucoside (Cy-3-G) and peonidin-3-glucoside (Pn-3-G), the predominant anthocyanins in ARBE, on CCl₄ insulted hepatocytes L-02 was further evaluated. Mice treated with ARBE for 7 weeks by oral administration showed reduced aminotransferase activities in serum, accompanied by enhanced superoxide dismutase (SOD) and glutathione peroxidase (GSH-Px) activity, while tiobarbituric acid reactive substances (TBARS), and 8-hydroxy-2′-deoxyguanosine (8-OHdG) levels were significantly decreased compared to CCl₄-intoxicated model group. Histopathological observation showed ARBE administration alleviated the pathological changes in livers of CCl₄-intoxicated mice. Similarly, preincubation of L-02 cells with Cy-3-G or Pn-3-G significantly alleviated CCl₄-induced injury dose-dependently, exhibited higher cell viability, decreased aminotransferase activity and enhanced cellular antioxidant status. Furthermore, Cy-3-G showed much stronger hepatoprotective activity than Pn-3-G at the same concentration. HPLC analysis showed that Cy-3-G accounted for more than 88% of total anthocyanins in ARBE. These results indicate that ARBE is significantly beneficial to liver health, and that Cy-3-G is the predominant anthocyanin in ARBE exerting this effect. The antioxidant activity of anthocyanins is an important mechanism by which ARBE exerts hepatic health benefit.     

Analysis of Phenolic Compounds of Dabai (Canarium odontophyllum Miq.) Fruits by High-Performance Liquid Chromatography

Dabai (Canarium odontophyllum Miq.) fruit is a popular seasonal indigenous fruit of Sarawak, Malaysia that is always appreciated as an exotic fruit by the local community. The present study was designed to identify and quantify the phenolic compounds of dabai fruits from different divisions of Sarawak. Difference between the purple and red varieties of the fruits was also investigated. Analysis of phenolic compounds was performed by reversed phase high-performance liquid chromatography coupled with diode array detector. Three detection wavelengths (280, 254 and 329 nm) were used to monitor all phenolic compounds (except for anthocyanidins) since they display absorbance maxima at different wavelengths. Characteristic spectra of eluted peaks provide useful information in confirming the identities of peaks. Hydrolysis of phenolic compounds of dabai fruits was insufficient under the milder conditions (30 °C, 2 h) employed thus resulted in unidentified peaks. Two phenolic acids (ellagic and vanillic acids), five flavonoids (catechin, epicatechin, epicatechin gallate, epigallocatechin gallate, apigenin) and ethyl gallate were detected in the fruits. Furthermore, three anthocyanidins (cyanidin, pelargonidin and delphinidin) and four anthocyanins (malvidin-3,5-di-O-glucoside, cyanidin-3-O-glucoside, cyanidin-3-O-rutinoside and peonidin-3-O-glucoside) were detected. All these phenolic compounds were reported in dabai fruits for the first time. The fruit variety affected the anthocyanidins and anthocyanins profile (p < 0.01) but had little or no effect on the phenolic acids and flavonoids profile of the fruits. Within the same variety, diversity in environmental conditions had an impact on the quantitative differences of phenolic compounds (p < 0.05).     

Identification of anthocyanins and distribution of flavonoids in tamarillo fruit (Cyphomandra betaceae (Cav.) Sendt.)

The major tamarillo (Cyphomandra betaceae) anthocyanin pigments were isolated and identified as pelargonidin-3-rutinoside, pelargonidin-3-glucoside, cyanidin-3-rutinoside, cyanidin-3-glucoside, delphinidin-3-rutinoside and delphinidin-3-glucoside. The intense purple-coloured jelly surrounding the seeds contained the greatest concentration of anthocyanins, delphinidin-3-rutinoside being the major pigment. Flavones, flavonols and leucoanthocyanins were also present in this material. The yellow-coloured flesh contained flavones and low concentration of anthocyanins. The major anthocyanin of the skins is cyanidin-3-rutinoside; flavones and leucoanthocyanins are also present. It is suggested that the presence of leucoanthocyanins in pigment extracts induced degradation of anthocyanins during isolation and purification.     

‘蓓蕾’蓝靛果中花色苷组成鉴定及抗氧化能力比较分析

对蓝靛果中花色苷的组成进行鉴定,并对其抗氧化能力进行比较分析。实验以蓝靛果（‘蓓蕾’品种）为原料,采用有机溶剂60%乙醇（0.1%盐酸酸化）溶液,超声辅助提取90 min;利用D101大孔树脂对获得的粗提物进行纯化,之后冷冻干燥制得粉末物质。通过pH示差法和福林-酚法分别测定总花色苷含量和总多酚含量,分别为（353.35±0.79）、（474.01±2.12）mg/g;并用高效液相色谱-质谱联用法对花色苷组成进行鉴定,共发现11 种花色苷,其中矢车菊-3-葡萄糖苷为主要花色苷（90.679%）。此外,实验还通过总抗氧化能力测定和2,2’-联氨-二（3-乙基苯并噻唑-6-磺酸）二铵盐自由基、1,1-二苯基-2-三硝基苯肼自由基清除能力测定,比较分析蓝靛果花色苷提取物、矢车菊-3-葡萄糖苷、VC的抗氧化能力,结果表明,3 种物质的抗氧化能力排序为：矢车菊-3-葡萄糖苷＞花色苷提取物＞VC。     

红树莓果汁和桑椹果汁花色苷结构的鉴定及杀菌方式对果汁品质的影响

采用高效液相色谱-电喷雾质谱法和紫外-可见光谱法鉴定了红树莓及桑椹中主要花色苷及黄酮的组成,并 以红树莓果汁及桑椹果汁为原料,对比分析了经巴氏杀菌（pasteurization,PS）、煮沸杀菌（boiling sterilization, BS）、微波杀菌（microwave sterilization,MS）3 种杀菌方式处理前后其总花色苷、单个花色苷、总酚、主要黄 酮、H2O2的相对含量及其他理化性质（pH值、可溶性固形物含量、吸光度、褐变度、透光率）的变化。结果表 明：红树莓中的主要花色苷为矢车菊素-3-槐糖苷和矢车菊素-3-葡萄糖苷,桑椹中主要花色苷为矢车菊素-3-葡萄糖 苷和矢车菊素-3-芸香糖苷;与对照组相比,红树莓果汁和桑椹果汁总花色苷、单个花色苷及总酚的相对含量经3 种 杀菌方式处理后都有不同程度的降低,MS处理对其影响最小;3 种杀菌方式处理后的果汁中H2O2相对含量没有显 著性差别（P＞0.05）。MS处理可以较好地保持红树莓果汁和桑椹果汁的营养品质。     

Influence of Dekkera bruxellensis on the contents of anthocyanins,organic acids and volatile phenols of Dão red wine

The anthocyanin, organic acid and volatile phenol compositions of red wine obtained from Touriga Nacional grapes growing in the Dão region (Portugal) were determined by HPLC/DAD, HPLC/UV and GC/FID, respectively. By these means, nine anthocyanic compounds (malvidin-3,5-O-diglucoside, cyanidin-3-O-galactoside, cyanidin-3-O-glucoside, peonidin-3-O-glucoside, malvidin-3-O-glucoside, delphinidin, cyanidin, pelargonidin and malvidin), six organic acids (ketoglutaric, tartaric, malic, quinic, lactic and shikimic acids) and two volatile phenols (4-ethylguaiacol and 4-ethylphenol) were identified and quantified. Malvidin-3-O-glucoside, the pair lactic plus shikimic acids and 4-ethylguaiacol were the main anthocyanin, organic acids and volatile phenol, respectively. The effects of nine different Dekkera bruxellensis strains on these chemical parameters were also evaluated. The results obtained indicate that some strains of D. bruxellensis yeast are able to cause deterioration of red wine from the Dão region during its maturation by the production of volatile phenols, namely 4-ethylphenol.     

Mechanisms of anthocyanin degradation in grape must-like model solutions

Oxidative degradation of o-diphenolic (eg cyanidin-3-glucoside) and non-o-diphenolic (eg malvidin-3-glucoside) anthocyanins in the presence of caffeoyltartaric acid and grape polyphenoloxidase was studied in model solutions. Both anthocyanins reacted with the enzymically generated caffeoyltartaric acid o-quinone. Kinetic studies indicated that cyanidin-3-glucoside was degraded mostly by coupled oxidation whereas malvidin-3-glucoside formed adducts with caffeoyltartaric acid quinone. In solutions containing equimolar amounts of the anthocyanins, both reactions took place but coupled oxidation of cyanidin-3-glucoside occurred at a faster rate, partly protecting malvidin-3-glucoside. The occurrence of coupled oxidation resulted in sparing of caffeoyltartaric acid. Several oxidation products, including red pigments, were detected by HPLC. The UV-Vis spectra of the coloured condensation products suggested that they contained both caffeoyltartaric acid and anthocyanin moieties. All these pigments were gradually degraded to colourless compounds either by enzymatic oxidation or by further reaction with quinones.