加热方法对紫甘蓝花色苷组分及其清除自由基活性的影响

目的:研究蒸汽加热和微波加热处理对紫甘蓝花色苷及其清除自由基活性的影响。方法:采用HPLC-MS法分析花色苷组分,ORAC法评价其清除自由基活性。结果:紫甘蓝花色苷主要有7种组分:矢车菊素-3-槐糖苷-5-葡萄糖苷(组分Ⅰ)、矢车菊素-3-槐糖苷(组分Ⅱ)、芥子酰矢车菊素-3-槐糖苷-5-葡萄糖苷(组分Ⅲ)、芥子酰矢车菊素-3-槐糖苷(组分Ⅳ)、p-香豆酰阿魏酰芥子酰芍药素-3-槐糖苷-5-葡萄糖苷(组分Ⅴ)、芥子酰矢车菊素-3-槐糖苷-5-葡萄糖苷(组分Ⅵ)、二芥子酰矢车菊素-3-槐糖苷-5-葡萄糖苷(组分Ⅶ),其中,组分Ⅰ、Ⅲ、Ⅵ、Ⅶ含量较高。蒸汽加热和微波加热对紫甘蓝花色苷组分种类均无明显影响,而对其相对含量有所影响,微波加热较蒸汽加热对两种花色苷组分Ⅵ和Ⅶ影响显著。蒸汽加热,花色苷组分Ⅵ和Ⅶ分别增加4.46%和10.25%;微波加热,花色苷组分Ⅵ和Ⅶ分别增加10.90%和28.60%。加热后花色苷组分Ⅰ和Ⅲ相对含量有所减少,蒸汽加热两者分别减少2.15%和13.32%,微波加热分别减少6.07%和35.10%。两种加热处理对花色苷组分Ⅱ和Ⅳ相对含量无明显影响。ORAC评价结果表明,微波加热和蒸汽加热对花色苷清除自由基活性有一定的影响,对照组、微波组和蒸汽组的ORAC值分别为0.329±0.030,0.326±0.027,0.293±0.021μmol Trolox/m L。结论:蒸汽加热和微波加热影响紫甘蓝花色苷各组分的相对含量及其清除自由基活性。     

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。     

HPLC-ESI-MS/MS鉴定几种提取物的主要花色苷成分

随着人们对食品中合成添加物中潜在的健康意识的提高,水果和蔬菜中天然提取物在食品工业中的应用受到了广泛关注。本文通过高效液相色谱-电喷雾离子化串联质谱联用技术(HPLC-ESI-MS/MS)对几种提取物中的主要花色苷成分进行了成分鉴定。通过对比相关文献结果,推测出葡萄皮花色苷的主要成分为:飞燕草-3-半乳糖苷、矢车菊-3-葡萄糖苷、矮牵牛-3-葡萄糖苷、芍药素-3-葡萄糖苷、锦葵素-3-葡萄糖苷、飞燕草素-3-葡萄糖苷;黑米花色苷的主要成分为:矢车菊素-3-葡萄糖苷、矮牵牛素-3-葡萄糖苷、飞燕草素-3-葡萄糖苷;紫甘薯花色苷中主要检测出了:芍药素-3-咖啡酰-对羟基苯甲酰槐糖苷-5-葡萄糖苷、芍药素-3-咖啡酰-阿魏酰槐糖苷-5-葡萄糖苷。通过研究不同提取物中的花色苷成分,为其在食品中的应用提供理论数据。     

野生桑葚中花色苷成分分析

运用固相萃取纯化技术与高效液相色谱/二极管阵列检测器/电喷雾质谱联用技术,采用ZorbaxSB-C18色谱柱(250mm×4.6mm,5μm),甲醇-5%甲酸水溶液为流动相,流速为1.0mL/min,检测波长为520nm,以矢车菊素3-葡萄糖苷为对照,外标法测定了野生桑葚花色苷含量,并通过紫外扫描光谱和电喷雾质谱正离子碎片信息确定了花色苷的成分组成。结果表明:野生桑葚总花色苷含量为154.27mg/100g,含有的三种花色苷成分分别为矢车菊素3-葡萄糖苷、矢车菊素3-芸香糖苷和天竺葵素3-葡萄糖苷,其相对含量为67.52%、31.29%和1.06%。     

中压快速分离系统大量制备高纯度桑葚和树莓花色苷的工艺研究

为快速获得大量不同结构花色苷,本文以富含花色苷的桑葚和树莓为原料,通过大孔吸附树脂AB-8对两种花色苷粗提物初步分离后,利用中压快速分离系统分离得到高纯度的桑葚及树莓花色苷。制备条件为:以flash C₁₈(80 g,20~35 μm,100 A)为制备柱,两支串联,采用A相2%甲酸水,B相甲醇,流速30 mL/min,梯度洗脱程序:0~2 min,20% B;2~22 min,20%~30% B;22~32 min,30%~40% B,进样量300 mg,实现了3种不同结构花色苷的分离及纯化,桑葚中的矢车菊素-3-葡萄糖苷和矢车菊素-3-芸香糖苷产品纯度分别达到了95%和41%;树莓中的矢车菊素-3-槐糖苷和矢车菊素-3-葡萄糖苷产品纯度分别达到了60%和75%。其中桑葚中的矢车菊素-3-葡萄糖苷在32 min梯度程序内一次性可获得30 mg,且纯度为95%,可达到标准品的要求。     

紫薯花色苷分离纯化及主要成分的研究

以紫薯花色苷为研究对象,研究了5种大孔树脂和洗脱条件对紫薯花色苷的纯化的影响,并且利用液相色谱与质谱联用技术分离鉴定了紫薯花色苷的主要成分。结果表明,采用AB-8型大孔树脂纯化,原料液p H值为3,洗脱剂乙醇体积分数为60%时,能较好实现花色苷纯化;根据质谱分子离子峰和碎片峰等以及光谱信息鉴定为矢车菊素葡萄糖苷、原花青素、芍药素3-槐糖苷-5-葡萄苷、矢车菊素-3-(6'-咖啡酰槐糖苷)-5-葡糖苷、鞣花单宁、芍药素3-(阿魏酰-羟基苯甲酰槐糖苷)-5-葡萄苷等物质。     

超声辅助果胶酶法提取红树莓花色苷及其成分测定

本研究利用超声辅助果胶酶法来提取制备红树莓花色苷,通过单因素实验,研究花色苷提取工艺中果胶酶浓度、料液比、酶解pH、酶解温度、超声时间和超声功率对提取液中花色苷含量的影响,结合响应面实验对提取工艺进行了优化,对比超声辅助果胶酶法和单一提取法所得的花色苷含量,并利用超高效液相色谱仪串联四级杆/飞行时间质谱(UPLC-Q/TOF)对树莓花色苷进行结构鉴定。结果表明:红树莓花色苷最佳提取条件为:果胶酶浓度5 mg/g、料液比1:15(g/mL)、酶解pH3、酶解温度50℃、酶解时间60 min、超声时间20 min和超声功率450 W,此时所得花色苷含量为127.51 mg/100 g。超声辅助酶法所得到花色苷含量较酶法提高了24.58 mg/100 g,较超声法提高40.40 mg/100 g,较单一提取法,超声辅助酶法具有更好的提取效果。经过超高效液相色谱三重四级杆飞行质谱分离中主要花色苷为:芍药素-3-葡萄糖苷、矢车菊素-3-葡萄糖苷、矢车菊素-3-阿拉伯糖苷和矢车菊素-3-芸香糖苷。     

不同花色苷代表性成分的分离鉴定及体外抗氧化活性

本实验以紫甘薯、黑枸杞、黑加仑和桑葚花色苷提取物为原料,制备其单体花色苷组分并研究其体外抗氧化性质。选取每种花色苷中含量较高,分子量居中,具有代表性的单体化合物作为目标组分,采用高速逆流色谱制备分离四种来源的花色苷。选用甲基叔丁基醚-正丁醇-乙腈-水-三氟乙酸作为溶剂体系,流速设定为5 mL/min,转速为850 r/min,分离得到高纯度花色苷单体化合物。采用分光光度法、HPLC-MS法分析测定花色苷含量及主要组成,用DPPH自由基、羟自由基清除能力和总还原力的测定分析其体外抗氧化活性。结果表明,四种来源的花色苷中代表性的成分依次为芍药素-3-咖啡酰-阿魏酰槐糖苷-5-葡萄糖苷、矮牵牛素-3-O-对香豆酰芸香糖苷-5-O-葡萄糖苷、矢车菊-3-芸香糖苷和矢车菊-3-O-葡萄糖苷,它们均具有良好的体外抗氧化活性。     

HPLC-ESI-MS分析紫色小白菜中花色苷组成分析

采用HPLC-ESI-MS方法测定并分析"新紫冠"紫色小白菜中花色苷的组分及其含量。结果表明,"新紫冠"紫色小白菜中含有矢车菊及飞燕草两类花色苷,以矢车菊-3,5-双葡萄糖苷标准品测得总花色苷含量为51.36μg/g·fw,其中矢车菊类花色苷含50.71μg/g·fw,占总含量的98.73%,飞燕草类花色苷含0.65μg/g·fw,仅占1.27%。矢车菊类花色苷全部以酰基化的形式存在,共检测出10种矢车菊类花色苷及相应的9种同分异构体,其中矢车菊-3-阿魏酰-槐糖苷-5-丙二酰-葡萄糖苷是含量最多的花色苷成分,达16.36μg/g·fw,占总含量的31.85%。     

结球红菊苣(Cichoricum intybus var.foliosum Hegi.)花色苷初步研究

采用pH示差法测定结球红菊苣中花色苷的含量,并采用高效液相色谱-光电二极管阵列检测器-离子阱/飞行时间质谱(HPLC-DAD-IT/TOFMS)技术对结球红菊苣花色苷溶液进行了检测和鉴定。结球红菊苣花色苷溶液是从结球红菊苣中用0.1%盐酸-甲醇溶液提取,并经C18固相萃取小柱纯化制备而成。结果表明,结球红菊苣中花色苷含量为37.3±12.25mg/100gFW,主要由四种矢车菊花色素的糖苷衍生物组成,分别是矢车菊-3-O-葡萄糖苷、矢车菊-3-丙二酰半乳糖苷、矢车菊-3-丙二酰葡萄糖苷、矢车菊-3-琥珀酰葡萄糖苷,其中矢车菊-3-丙二酰葡萄糖苷含量最高,占结球红菊苣叶子中花色苷总量的82.01%。     

Anthocyanin Determination in Black Raspberry (Rubus occidentalis) and Biological Specimens Using Liquid Chromatography-Electrospray Ionization Tandem Mass Spectrometry

ABSTRACT: The capabilities of mass spectrometry for microscale determination of anthocyanins were investigated using high-performance liquid chromatography electrospray ionization mass spectrometry (LC-ESI/ MS) and tandem mass spectrometry (MS-MS). Four anthocyanins [cyanidin 3-glucoside, cyanidin 3-sambubioside, cyanidin 3–(2^G−xylosylrutinoside) and cyanidin 3-rutinoside] were characterized in black raspberry samples by LC-ESI/MS-MS using both positive and negative ion analyses. Quantification of anthocyanins was conducted using ESI/MS-MS with selected reaction monitoring (SRM). Linear responses of several anthocyanins were determined during MS-MS analyses. Detection limits as low as 1 femtomol for most anthocyanins were obtained during ESI/MS-MS. Compared with other quantitative procedures such as high-performance liquid chromatography (HPLC) and ultraviolet/visible spectrophotometry, the current method provides an improved sensitive, specific technique for direct determination of intact anthocyanins. The developed methodology was successfully applied to analysis of trace levels of anthocyanins in human plasma and epithelial cells.     

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.     

鲜切紫甘蓝中花青苷和硫代葡萄糖苷在贮藏过程中的变化

采用高效液相色谱和液相色谱-质谱联用技术,对紫甘蓝（Brassica oleracea L. ssp. capitata f. rubra）中花青苷、硫代葡萄糖苷（简称硫苷）成分和含量进行鉴定和分析,并对低温（8±1）℃条件下经鲜切处理的紫甘蓝中花青苷和硫苷在货架期内（7 d）的变化情况进行研究。结果表明：紫甘蓝中存在11 种不同矢车菊花青苷,矢车菊-3-阿魏酰-槐糖苷-5-葡萄糖苷作为紫甘蓝中最主要的花青苷,在贮藏过程中的损失量占总花青苷损失量的55.51%,其占总量比例也在贮藏7 d后由35.12%下降至30.60%;紫甘蓝中存在10 种硫苷（由6 种脂肪族硫苷、3 种吲哚族硫苷和1 种芳香族硫苷组成）,以4-戊烯基硫苷和3-丁烯基硫苷为主,贮藏7 d后,二者损失率均为7%左右,损失量相加却达总花青苷损失量的50.07%,而所占比例相加也由71.68%上升到74.33%。     

Characterization of a new anthocyanin in black raspberries (Rubus occidentalis) by liquid chromatography electrospray ionization tandem mass spectrometry

Anthocyanin composition of black raspberry (Rubus occidentalis) was studied using high-performance liquid chromatography coupled to photodiode array (PDA) detection and electrospray ionization mass spectrometry (LC-ESI/MS) and tandem mass spectrometry (MS/MS). Pelargonidin 3-rutinoside was isolated and identified in black raspberries using HPLC, UV–Vis spectroscopy, MS, and NMR spectroscopy. No pelargonidin derivative had been previously found in Rubus occidentalis. In addition, the presence and identities of four previously reported anthocyanins (cyanidin 3-glucoside, cyanidin 3-sambubioside, cyanidin 3-rutinoside and cyanidin 3-xylosylrutinoside) were confirmed by HPLC/MS and MS/MS analyses.     

Comparative analyses of copigmentation of cyanidin 3-glucoside and cyanidin 3-sophoroside from red raspberry fruits

Cyanidin 3-glucoside (Cy 3-glu) and cyanidin 3-sophoroside (Cy 3-soph) from red raspberry extracts were selected as pigments, and five phenolic acids as copigments. The influences of pH, temperature, structure of anthocyanins and copigments, and molar ratio of anthocyanins to copigments on the copigmentation effect were analyzed with a UV–Visible spectrophotometer. The reaction was thermodynamically defined in terms of ΔH⁰, ΔG⁰ and ΔS⁰ values.     

Anthocyanin changes in the Korean purple-fleshed sweet potato,Shinzami, as affected by steaming and baking

As hydrophilic pigments, anthocyanins reduce the incidence of cancer and cardiovascular diseases. In this study, the anthocyanin content and composition following steaming and baking of the roots of the Korean purple-fleshed sweet potato variety “Shinzami” were evaluated using liquid chromatography with diode array detection and electrospray ionisation/mass spectrometry (LC-DAD-ESI/MS). Anthocyanins of Shinzami were composed of mono- or di-acylated forms of p-hydroxybenzoic acid, caffeic acid and ferulic acid with the basic structure of cyanidin 3-sophoroside-5-glucoside or peonidin 3-sophoroside-5-glucoside. A total of 15 individual anthocyanins were isolated and confirmed, one of which was presumed to be a newly identified compound, peonidin 3-feruloyl-p-hydroxybenzoyl sophoroside-5-glucoside. Additionally, the amounts of di-acylated cyanidin 3-caffeoyl-p-hydroxybenzoyl sophoroside-5-glucoside and peonidin 3-caffeoyl-p-hydroxybenzoyl sophoroside-5-glucoside were the highest (137.0 and 565.9 mg/100 g DW, respectively) among cyanidin and peonidin compounds. After steaming, the total anthocyanin content was reduced by nearly a half, while roasting only slightly reduced the total anthocyanin content.     

Differentiation of raspberry varieties according to anthocyanin composition

 Four Spanish raspberry (Rubus idaeus L.) cultivars, Autumn Bliss, Heritage, Rubi, and Ceva, were studied in order to determine, qualitatively and quantitatively, both anthocyanins and vitamin C composition, owing to their significance as dietary compounds with antioxidant activity and also to the relation with color quality. Raspberry anthocyanin composition, determined by HPLC and GC-MS, was characteristic to each cultivar. The higher anthocyanin content expressed as cyanidin-3-glucoside was found in the late cultivars, Rubi (96.08 mg/100 g f.w.) and Ceva (122.88 mg/100 g f.w.). Three cultivars showed cyanidin-3-sophoroside (63.86–21.91 mg/100 g f.w.) and cyanidin-3-glucoside (25.12–14.00 mg/100 g f.w.) as the major pigments, while Autumn Bliss had a similar relative amount of cyanidin derivatives, cyanidin-3-rutinoside being the pigment in major concentration (10.53 mg/100 g f.w.). The vitamin C contents were determined by HPLC. The Rubi cultivar showed the highest amount of vitamin C (31.14 mg/100 g f.w.). The organic acids were determined by HPLC as fruit constituents related to color quality. Citric acid was the main non-volatile organic acid (90%) in all raspberry cultivars and the Rubi cultivar showed the highest total non-volatile organic acids content (2003 mg/100 g f.w.). Hunter color CIE values were also determined, showing that Rubi was the reddest raspberry cultivar. Received: 28 May 1998     

Analysis and metabolite profiling of glucosinolates,anthocyanins and free amino acids in inbred lines of green and red cabbage (Brassica oleracea L.)

We profiled and quantified glucosinolates (GSLs), anthocyanins and free amino acids in thirty-seven inbred lines green and red cabbage. Analysis of these distinct cabbages revealed the presence of 8 GSLs, 13 anthocyanins and 12 free amino acids. GSL contents were varied among the different lines of cabbage. The maximum levels of glucoraphanin (14.91 μmol/g DW) and glucobrassicin (12.37) were found in FX 1-28 and FX 1-32 lines, respectively. Total GSLs in red cabbage lines were 50% higher than those of green cabbage. Anthocyanin contents in red cabbage were ranged from 4.11 to 6.81 mg/g DW in FX 2-3 and FX 1-34 lines, respectively. Among the 13 anthocyanins, both cyanidin 3-(feruloyl) (sinapoyl)diglucoside-5-glucoside and cyanidin 3-(sinapoyl) (sinapoyl)diglucoside-5-glucoside levels were the highest amounts. The amounts of total free amino acids were ranged from 523.5 to 1308 mg/100 g fresh weight (FW) in green cabbage and 484.8 to 1271 in red cabbage, respectively. In red cabbage lines, 9.4% of the total free amino acids accounted essential amino acids such as valine, threonine, isoleucine, leucine and lysine. Thus, the amounts of GSLs, anthocyanins, and amino acids varied widely, and the variations in these compounds between the lines of cabbage were significant.