油菜蜂花粉黄酮醇苷的体内外抗氧化研究

以油菜蜂花粉黄酮醇苷组分为原料,以还原力和DPPH 自由基清除率为指标研究黄酮醇苷在化学模拟体系中的抗氧化活性。结果表明,油菜蜂花粉黄酮醇苷的抗氧化活性不及其苷元成分。以CCl4 制备小鼠脂质过氧化损伤模型,通过体内自由基发生体系进一步研究花粉黄酮醇苷的抗氧化作用,并对可能的作用机制进行探讨。结果显示：油菜蜂花粉黄酮醇苷组分能够显著地降低脂质过氧化小鼠肝匀浆和血清中MDA 含量,提高小鼠SOD 活性和总抗氧化能力(T-AOC),对脂质过氧化损伤有很好的保护作用,原因可能是体内有关酶系可将黄酮醇苷水解使其游离出酚羟基而发挥作用。本研究进一步肯定了油菜蜂花粉黄酮醇苷对机体氧化损伤的保护作用。     

超微粉碎技术对油菜花粉中槲皮素和山奈素溶出率的影响

为了探讨超微粉碎技术对油菜花粉中有效成分(槲皮素和山奈素)溶出的影响,采用高效液相色谱法分析比较油菜花粉超微粉与普通粉(65～100 目)中槲皮素和山奈素的溶出差异。结果表明,油菜花粉超微粉中槲皮素和山奈素的溶出率比普通粉分别提高了45.16% 和27.86%,超微粉碎可显著提高油菜花粉有效成分的溶出率。     

油菜蜂花粉中黄酮类化合物的提取与鉴定

以湖北大宗油菜蜂花粉为材料,对其中微量特征成分黄酮类化合物进行鉴定。采用超声波辅助技术提取,运用二次回归正交旋转组合实验优化提取工艺,通过响应面分析和岭嵴寻优分析,确定黄酮类化合物的最佳提取条件;采用HPLC-DAD 以及HPLC-MS 对酸解后的提取液进行分析。结果表明：超声波辅助技术提取油菜蜂花粉中黄酮类化合物的最佳条件为体积分数76% 乙醇、料液比1:30、超声波时间33min,超声波温度为51℃。蜂花粉中总黄酮含量的理论得率为2.12%,实际得率为1.89%,实测得率达到理论预测值的89.15%。HPLC-DAD 以及HPLCMS分析结果证实油菜蜂花粉中可能含有9 种黄酮苷元。其中可以推定的黄酮类物质是槲皮素、山奈酚、异鼠李素和柚皮素。可为识别蜂花粉的植物来源,鉴别真伪提供研究方法和实验依据。     

Evaluation of pollen as a source of kaempferol in rosemary honey

The content of the flavonoid kaempferol in different experimental rosemary honey samples produced in Aragón (Spain) and in some commercial rosemary honey samples produced in different Spanish regions was evaluated by HPLC. The content ranged between 0·33 and 2·48 mg kg⁻¹ of honey. Nectar has been suggested recently as the origin of this flavonoid. Rosemary pollen contained kaempferol 3-diglucoside and 3-glucoside, and therefore could be an alternative source for the kaempferol found in rosemary honey. However, there was no correlation between the kaempferol present in honey and pollen content. This suggests that the contribution of pollen flavonoids to the pool of flavonoids found in honey is very small, and that the search for phenolic markers of the botanical origin of honey should be addressed to the identification of nectar flavonoids or other nectar constituents. © 1998 SCI.     

Aglycone and glycoside specificity of apple skin flavonoid glycosyltransferase

O-Glycosyltransferase(s) extracted from apple (Malus pumila Mill) fruit skin showed activity towards a range of flavonols and anthocyanins. However, no glycosylating activity was shown towards a dihyroflavonol (dihydroquercetin), a flavanone (eriodictyol) or a flavone (luteolin). The enzyme preparation glycosylated those flavonoids normally present in apple skins (quercetin and cyanidin) and in addition several other related compounds (delphinidin, fisetin, isorhamnetin, kaempferol, myricetin and pelargonidin). This enzyme(s) specifically transferred the glycosyl moiety from sugar nucleotide donors to the 3-position of the flavonoid nucleus. Only flavonoid 3-glycosides occur naturally in apple skin. Activity with different sugar donors was in the order galactose>glucose>xylose, which reflected the ratios of cyanidin and quercetin glycosides found in apple fruit skin. There were slight differences in the relative UFGT activity with quercetin and the three different sugar donors between ‘Granny Smith’ and ‘Splendour’, and this was reflected by similar differences in the ratios of endogenous quercetin glycosides. ©1997 SCI     

An HPLc technique for flavonoid analysis in honey

A new technique for the analysis of flavonoids in honey has been developed. This uses filtration of honey through Amberlite-XAD-2 and purification of the flavonoid fraction by Sephadex LH-20. The flavonoid fraction is then analysed by HPLC. This technique allowed the identification of 16 flavonoids in honey, namely quercetin, kaempferol, 8-methoxykaempferol, quercetin 3-methyl ether, isorhamnetin, kaempferol 3-methyl ether, quercetin 3,3-dimethyl ether, quercetin 3,7-dimethyl ether, galangin, luteolin, apigenin, genkwanin, chrysin, luteolin 7-methyl ether, pinocembrin and pinobanksin. The flavonoids present in ten samples of honey from La Alcarria have been HPLC analysed by this technique. The fact that the flavonoid patterns are very similar, suggests that samples from other areas should be examined in order to assess if this procedure could be useful as an adjunct in studies of the geographical origin of honey.     

Descriptive analysis of Rubus honey from the north‐west of Spain

A study of Rubus honey was conducted to determine their sugar composition, physicochemical properties, phenol and flavonoid contents, and sensorial and pollen characteristics. The principal pollen types present in the studied samples were Rubus, Castanea and Cytisus. Other pollen types such as Trifolium, some Erica sp., Eucalyptus or Echium were present in more than 50% of the pollen spectra. The sensorial characteristics of Rubus honey were amber‐to‐amber dark in colour, floral and/or vegetal olfactory perceptions with medium‐to‐low intensity and persistence, medium floral aftertaste and a fruity aroma. Physicochemical analysis showed that the honey had good quality and freshness. Phenol and flavonoid contents varied greatly and were related to the mineral content and colour of the honey. A stepwise regression analysis was performed using colour as the dependent variable, and flavonoid, electrical conductivity, and Rubus pollen as the independent variables.     

薄层层析-生物自显影法筛选油菜蜂花粉中活性成分

采用薄层层析- 生物自显影法筛选油菜蜂花粉中清除DPPH 自由基的活性成分和抑菌活性成分。结果显示：油菜蜂花粉中清除DPPH 自由基的黄酮类活性成分主要以苷的形式存在,酸解后生成了包括槲皮素和山奈酚在内的多种抗氧化成分;在Rf 值0.29 和0.86 处存在抑菌活性成分,不同显色方法确认,抑菌活性成分的种类可能包括酚类、鞣质、黄酮类或皂苷类。     

The polyphenolic profiles of common bean (Phaseolus vulgaris L.)

Based on the phenolic profiles obtained by high performance liquid chromatography-electrospray ionization mass spectrometry (HPLC-DAD-ESI/MS), 24 common bean samples, representing 17 varieties and 7 generic off-the-shelf items, belonging to ten US commercial market classes can be organized into six different groups. All of them contained the same hydroxycinnaminic acids, but the flavonoid components showed distinct differences. Black beans contained primarily the 3-O-glucosides of delphinidin, petunidin and malvidin, while pinto beans contained kaempferol and its 3-O-glycosides. Light red kidney bean contained traces of quercetin 3-O-glucoside and its malonates, but pink and dark red kidney beans contained the diglycosides of quercetin and kaempferol. Small red beans contained kaempferol 3-O-glucoside and pelargonidin 3-O-glucoside, while no flavonoids were detected in alubia, cranberry, great northern, and navy beans. This is the first report of the tentative identification of quercetin 3-O-pentosylhexoside and flavonoid glucoside malonates, and the first detailed detection of hydroxycinnamates, in common beans.     

十种蜂花粉醇提物中总多酚和总黄酮含量测定

为测定蜂花粉的功能性成分,用不同浓度乙醇对蒲公英、野菊花、桃花、山楂、野藿香、黄玫瑰、野玫瑰、黄柏、山花、五味子十种蜂花粉进行提取。结果表明:桃花花粉多酚提取适宜用水或低醇,野藿香花粉水提多酚提取量高于醇提物,山楂花粉和山花花粉适宜用70%乙醇提取多酚,其余六种蜂花粉选用70%～80%乙醇提取多酚效果比较好;山花花粉适宜用无水乙醇提取黄酮,野菊花花粉适宜用70%乙醇提取黄酮,其余八种蜂花粉选用80%乙醇提取黄酮效果较好。黄玫瑰花粉的总多酚和总黄酮含量均为最高,野藿香花粉中总多酚和总黄酮含量都最低。     

Flavonoid content of commercial capers (Capparis spinosa, C. sicula and C. orientalis) produced in mediterranean countries

 The flavonol content of commercial capers (pickled flower buds of Capparis spinosa L., C. sicula Veill. in Duham. and C. orientalis Veill. in Duham.) produced in different Mediterranean countries (Spain, Italy, Greece, Turkey and Morocco) has been analysed. The content of quercetin 3-rutinoside, kaempferol 3-rutinoside; and kaempferol 3-rhamnosyl-rutinoside as well as the aglycones (quercetin and kaempferol) were evaluated by HPLC coupled with a diode-array detector. The free aglycones were not detected in the original flower buds, indicating that they were produced during the brining process. In addition, brining extracted most of the kaempferol 3-rhamnosyl rutinoside present in the original buds, this being a minor constituent in pickled capers. The average content of flavonoid glycosides in commercial capers was 5.18 mg/g fresh weight. When this value is converted to the corresponding aglycones (quercetin and kaempferol), capers provide an average of 3.86 mg/g fresh weight. A serving of capers (10 g) will provide 65 mg of flavonoid glycosides or the equivalent 40 mg of quercetin as aglycone. Received: 3 March 2000     

电感耦合等离子体质谱法测定荷花花粉和油菜花粉中镉含量的不确定度评定

目的评定荷花花粉和油菜花粉样品中镉含量可能产生的不确定度,以提高测量结果的准确性。方法采用NexIon 350X型电感耦合等离子体质谱仪对2种蜂花粉中镉的含量进行测定,建立实验过程的数学模型,对主要影响测量不确定度的样品称量、标准溶液的配制、标准曲线的拟合、测量的重复性等因素进行分析,并对各不确定度分量、合成标准不确定度以及扩展不确定度进行计算。结果荷花花粉中镉含量测定结果不确定度为:U=(0.166±0.010) mg/kg, k=2;油菜花粉中镉含量测定结果不确定度为:U=(0.0599±0.0033) mg/kg, k=2。结论影响测定荷花花粉和油菜花粉中镉含量的不确定度的主要来源为标准溶液稀释和样品重复性试验。电感耦合等离子体质谱法测定荷花花粉和油菜花粉中镉含量是可靠的。     

油菜花粉和茶花花粉中重金属含量的分布特征研究

目的 考察2种蜂花粉产品中7种重金属(类金属)元素含量的分布特征。方法 采用微波消解-电感耦合等离子体质谱法对所采集的蜂花粉样品中铬、锰、砷、铜、镍、镉和铅等7种元素含量进行分析测定,通过统计分析考察2种蜂花粉中各元素含量是否有显著性差异。结果 2种蜂花粉均存在重金属污染问题,但重金属污染水平存在差异。锰、镍、铜等3种元素在所采集的油菜花粉样品和茶花花粉样品中的含量差异具有显著统计意义(P < 0.05);铬、砷、镉和铅等4种元素含量在该2种蜂花粉中差异不显著(P > 0.05)。结论 油菜花粉和茶花花粉中部分元素含量差异有统计意义,对于具有较高重金属污染风险的花粉种类应加强监管,将样品来源地环境无机污染物引起的重金属污染问题纳入到生产规范标准制修订的考量之中。     

Pyrrolizidine alkaloids: their occurrence in Spanish honey collected from purple viper’s bugloss (Echium spp.)

The incidence and concentration of pyrrolizidine alkaloids (PAs) from Echium spp. plant have been defined in 103 Spanish honey samples. Each sample was examined to determine total pollen content, the percentage of Echium spp. pollen, and simultaneous measurements of PAs and their N-oxides concentrations by the HPLC-ESI/MS method to identify the potential origin of PAs in honey. PAs were found in 94.2% of the raw honey samples analysed, in the range of 1–237 µg kg^?1 (average concentration = 48 µg kg^?1). The PA pattern was clearly dominated by echimidine, lycopsamine and their N-oxides, representing the 97.8% of total ∑PAs, and only echimidine and echimidine-N-oxide surpassed the 87% of total ∑PA content. Others PAs, seneciphylline and heliotrine-N-oxide, appear to be reported in a lower incidence and concentration (average of 3 and 1 µg kg^?1, respectively). The Pearson Chi-squared test (p ≤ 0.01) confirms the non-correspondence between pollen plants and PA content. This study was also realised to generate a dataset in order to evaluate the potential risk of Spanish honeys containing PA plants belonging to the genera Echium.     

Physico-chemical properties, composition and pollen spectrum of french lavender (Lavandula stoechas L.) honey produced in Spain

The palynological and physico-chemical properties of 26 samples of French lavender (Lavandula stoechas) honey commercially produced in Spain have been defined. Each sample was examined to determine the total pollen content, percentage ofL. stoechas pollen and pollen spectrum. On the basis of the honey pollen analysis, 14 samples were excluded as they were of different botanical origin (Echium spp.). In total 67 different pollen types were identified. The sugar spectrum showed low percentages of trisaccharides and sucrose. The enzymatic activity was lower than that found in other unifloral Spanish honeys. A minimum of 10%L. stoechas pollen and maximum of 30%Echium sp. pollen are the suggested requirements to characterize this honey.

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Zusammensetzung, physikalisch-chemische Eigenschaften und Pollenspektrum im spanischen Heidehonig (Lavandula stoechas L.)

Zusammenfassung Anhand von 26 Stichproben wurden die physikalisch-chemischen Eigenschaften und das Pollen-Spektrum des kommerziell vertriebenen spanischen Heidehonigs (Lavandula stoechas L.) bestimmt. Jede Stichprobe wurde auf den Gesamtgehalt an Pollen sowie den prozentualen Anteil an Pollen desL. stoechas und auf das Pollen-Spektrum untersucht. Aufgrund der Analyse des Melissen-Spektrums mußten 14 Stichproben ausgeschlossen werden, da sie unterschiedlichen botanischen Ursprungs waren (Echium spp.). Es wurden 67 verschiedene Pollenarten identifiziert. Das Zuckerspektrum wies einen geringen Anteil an Trisacchariden und Sucrose auf. Die enzymatische Aktivität dieser Honigarten war geringer bei anderen Blütenpflanzen. Als Mindestmenge an Pollen desL. stoechas werden 10% vorgeschlagen, und ein Pollenanteil von <30% beiEchium sp. ist für diesen Honig charakteristisch.

     

Performance of green and conventional techniques for the optimal extraction of bioactive compounds in bee pollen

The exploitation of phenolic compounds in different fields has motivated researchers to explore eco-friendly and efficient extraction techniques. This study aimed to comparatively reveal that green extraction techniques (microwave- and ultrasound-assisted) are alternative to conventional extraction (maceration and magnetic stirring) with positive impact on the phenolic content, antioxidant activity, and bioactive profile of bee pollen extracts. The highest total phenolic and flavonoid content was reached using the microwave-assisted technique (MAE) with equivalent values of 28 and 8 mg g⁻¹, with magnetic stirring and maceration showing a lower value. The composition profile of the extracts revealed the presence of twenty-six bioactive compounds, including thirteen phenolics and thirteen phenylamides. Although the extraction technique had little impact on the chemical diversity, the amount of bioactive compounds raised significantly with the use of the green extraction techniques, with gains between 40% and 60% for phenolics and up to 200% for phenylamides. The radical scavenging activity and the reducing power of the extracts confirmed that bee pollens are potent antioxidant source, with the most bioactive extracts corresponding to green extraction techniques. Consequently, all findings recommend the use of MAE as the technique most effective for the extraction of bioactive compounds from naturally encapsulated structures such as bee pollen.     

Inhibitory effects of Chrysanthemum species extracts on formation of advanced glycation end products

The corolla of Chrysanthemum species (C.morifolium R. and C.indicum L.) has long been used to treat eye and inflammatory disease. However, little is known about the antiglycation properties of Chrysanthemum species. Our study sought to characterise their activity against the formation of advanced glycation end products (AGEs) in glycation model reactions. In BSA/glucose (fructose) systems, both Chrysanthemum species strongly inhibited the formation of AGEs and N^ε-(carboxymethyl)lysine (CML). C.morifolium R., not C.indicum L., also acted to inhibit the formation of fluorescent AGEs, including pentosidine. This difference correlated with the values of polyphenol and flavonoid components. We characterised the active components in these plants by liquid chromatography-diode array detector-atmospheric pressure chemical ionisation/mass spectrometry, which showed that C. morifolium R. contains large amounts of chlorogenic acid, flavonoid glucoside varieties, and apigenin, while C.indicum L. contains large amounts of caffeic acid, luteolin, and kaempferol. Our findings raise hopes for the successful treatment of pathogenesis in conditions associated with diabetic complications and aging.     

Chemical fingerprinting identifies Echium vulgare,Eupatorium cannabinum and Senecio spp. as plant species mainly responsible for pyrrolizidine alkaloids in bee-collected pollen

Various studies have shown that bee-collected pollen sold as nutritional supplements may contain toxic pyrrolizidine alkaloids (PAs) and, thus, pose a potential health risk for consumers. The level of contamination may vary according to its geographical and botanical origin. Here, the PA content of pollen produced in Switzerland was studied and 32 commercially available bee-collected pollen supplements produced between 2010 and 2014 were analysed. In addition, at what time period bees collect PA-containing pollen was investigated. Hence, this study looked into the occurrence of PAs in pollen samples collected daily during two-to-three consecutive seasons. Furthermore, the PA spectrum in pollen was compared to the spectrum found in flower heads of PA-plants to unambiguously identify plants responsible for PA contamination of pollen. The PA concentration of commercial and daily collected pollen was determined by target analysis using an HPLC-MS/MS system, allowing the detection of 18 different PAs and PA N-oxides found in the genera Echium, Eupatorium and Senecio, while the comparison of the PA spectrum in pollen and flower heads was performed by LC-HR-MS, allowing the detection of all PA types in a sample, including saturated, non-carcinogenic PAs. Of the commercially available pollen, 31% contained PAs with a mean concentration of 319 ng/g, mainly Echium- and Eupatorium-type PAs, while the PA concentrations were below the limit of quantitation (LOQ) in 69% of the pollen samples. Bees collected pollen containing Echium-type PAs mainly in June and July, while they gathered pollen containing Eupatorium-type PAs from mid-July to August. Senecio-type PAs appeared from June to September. Comparison of the PA array in pollen and plants identified E. vulgare and E. cannabinum as the main plants responsible for PA contamination of Swiss bee-collected pollen, and to a lesser extent also identified plants belonging to the genus Senecio.     

苦荞麸皮黄酮提取物及有效成分的抑菌活性

研究苦荞麸皮总黄酮粗品及精品对病原菌的抑制作用,并初步分析其黄酮类成分,评价不同黄酮单体的抑菌活性。通过平板打孔法及二倍稀释法检测苦荞麸皮总黄酮粗品及精品及其4种黄酮单体的抗菌活性,使用高效液相色谱法定性定量检测苦荞麸皮总黄酮粗品及精品的黄酮成分。结果表明,苦荞麸皮黄酮精品对金黄色葡萄球菌、藤黄微球菌、肠球菌、大肠杆菌、志贺氏杆菌、沙门氏菌的抑制效果优于粗品。苦荞麸皮黄酮主要黄酮成分为芦丁、山奈酚-3-O-芸香糖苷、槲皮素和山奈酚,精品的总黄酮含量是粗品总黄酮含量的2.84倍。4种黄酮单体的抑菌能力具有一定的构效关系,其中槲皮素对所有供试菌均表现出较好的抑菌活性。     

Carbohydrate composition and physico chemical properties of artisanal honeys from Madrid (Spain): occurrence of Echium sp honey

Artisanal honey samples produced in Madrid province (central Spain) were characterised from their melissopalynological analysis, carbohydrate composition and physicochemical parameters. Melissopalynological analysis showed that Echium sp pollen appeared as the dominant palynomorph in most samples. It was also observed that many honey samples were natural blends from both nectar and honeydew botanical origins. Twenty‐five carbohydrates (glucose, fructose, 16 disaccharides and seven trisaccharides) were detected and quantified. Discriminant analysis was used to describe the variability of compositional data, which was probably associated with the different honey sources analysed (honeydew, Echium sp and other nectar plants), which in turn was related to the physiographical conditions (plain or mountain) occurring in Madrid province. Copyright © 2004 Society of Chemical Industry