蜂胶中多酚类成分分析及其抗氧化活性

为研究不同地区蜂胶提取物中组分含量的差异及抗氧化活性的大小,采用75%乙醇溶液对9 个蜂胶样品进行提取,以高效液相色谱法（high performance liquid chromatography,HPLC）对不同提取物中多酚类成分进行定性和定量分析。并利用氧化自由基吸收能力（oxygen radical absorbance capacity,ORAC）法和用流式细胞仪Hep G2细胞模型评估了9 个蜂胶样品的体外和细胞水平抗氧化能力。结果表明：蜂胶样品中含有包括黄酮、酚酸及酯类物质在内的大量多酚类成分,其中含量较高的黄酮类成分有短叶松素-3-乙酸酯、松属素、柯因、短叶松素、高良姜素,含量较高的酚酸及酯类成分有咖啡酸苯乙酯、p-香豆酸、咖啡酸、异阿魏酸。ORAC法结果显示所有蜂胶样品都具有很好的体外抗氧化能力;在细胞水平上,所有样品也都表现出一定的抗氧化能力。9 个总黄酮和总酚酸含量高的蜂胶具有较强的抗氧化能力。     

蜂胶功能成分及生物活性研究进展

蜂胶是一种胶状天然产物,是工蜂腺体分泌物、植物嫩芽和树干分泌物的混合物.蜂胶的主要功能成分为黄酮类化合物、酚酸类化合物和萜烯类化合物等.研究表明蜂胶中的黄酮类化合物包括槲皮素、高良姜素和山奈酚等;酚酸类化合物包括咖啡酸、阿魏酸、p-香豆酸等;萜烯类化合物包括单萜、二萜、三萜等.地域、植物来源、气候、季节和蜂种等因素都会...     

荞麦蜜酚酸含量的高效液相色谱测定及其抗氧化作用的研究

以中国产荞麦蜜为原料,采用高效液相色谱-电化学检测法(HPLC-ECD)测定其中的原儿茶酸、没食子酸、咖啡酸、丁香酸、p-香豆酸、绿原酸、阿魏酸和鞣花酸等8种酚酸的含量。结果表明,中国荞麦蜜中含有原儿茶酸、没食子酸、咖啡酸、p-香豆酸、阿魏酸等五种酚酸,其含量分别为没食子酸为461μg/100g蜂蜜,p-香豆酸为150μg/100g蜂蜜,咖啡酸为79μg/100g蜂蜜,原儿茶酸为30μg/100g蜂蜜,阿魏酸为39μg/100g蜂蜜。本文还对荞麦蜜酚酸提取物的抗氧化作用进行了研究,结果显示荞麦蜜酚酸提取物对超氧阴离子自由基、羟基自由基、DPPH自由基和脂质过氧化均有抑制作用。     

松花粉提取物抗氧化活性及其酚类化合物的研究

为研究松花粉抗氧化活性,采用HPLC-ECD方法测定了松花粉的水提取物和乙醇(乙醇体积分数为80%)提取物中的酚类化合物的含量。同时评价了其对羟基自由基介导的2-脱氧核糖裂解的保护作用。结果表明:2种提取物中均含有原儿茶酸、咖啡酸、p-香豆酸、阿魏酸和高良姜素,乙醇提取物中含有芦丁、槲皮素和山奈酚。松花粉乙醇提取物中的总酚含量显著高于水提物(P<0.05),但水提取物的还原能力和络合能力显著高于乙醇提取物(P<0.05)。2种提取物对非定位羟基自由基介导的2-脱氧核糖裂解的保护作用均显著高于定位羟基自由基(P<0.05),表明松花粉提取物对羟基自由基介导的2-脱氧核糖裂解的保护作用主要通过清除羟基自由基来实现的,这可能与松花粉提取物中含有大量的酚类化合物有关。     

模型反应中不同酚酸物质抑制PhIP形成效果分析

2-氨基-1-甲基-6-苯基-咪唑[4,5-b]吡啶(2-amino-1-methyl-6-phenyl-imidazole[4,5-b]pyridine,PhIP)是食品加工和烹饪中含量较高且有致癌风险的杂环胺类化合物。该文在以苯丙氨酸和肌酐为前体物质的模型体系中,考察阿魏酸、咖啡酸、对香豆酸3种单体酚酸以及混合酚酸对PhIP形成的抑制效果,并进一步探讨酚酸类物质在模型体系中对PhIP形成的抑制效果是否存在相互协同作用。结果表明,在单体酚酸模型中,当酚酸浓度为10^-10mg/mL或10^-9mg/mL时,从整体效果比较3种单体酚酸对PhIP形成的抑制效果,由强到弱分别为咖啡酸、对香豆酸、阿魏酸,而当酚酸浓度为10^-8mg/mL时,阿魏酸对PhIP形成的抑制效果强于对香豆酸;在混合酚酸模型中,阿魏酸+对香豆酸的组合对PhIP形成抑制效果最强,抑制率为56.37%,咖啡酸+对香豆酸的组合对PhIP形成抑制效果最弱,抑制率为13.33%。推测其反应机理可能是酚酸类物质与前体物质发生反应生成新的化合物,消耗掉前体物质的量,从而抑...     

比光谱-导数分光光度法同时测定对-香豆酸和阿魏酸

根据对-香豆酸和阿魏酸的紫外吸收特点,确立得到两种酚酸稳定的紫外吸收图谱的条件,建立比光谱-导数分光光度法,同时测定对-香豆酸和阿魏酸的含量。在溶剂为乙醇或水或乙醇与水的混合溶液时,调节溶液pH2.0,得到两种酚酸稳定的紫外吸收光谱图,最大吸收峰分别为对-香豆酸308nm、阿魏酸320nm。运用比光谱-导数分光光度法测定对-香豆酸和阿魏酸的二元混合物,回收率在93.40%～103.34%之间,结果良好。对蔗渣碱解提取的酚酸样品进行检测,阿魏酸检测受影响较大,而对-香豆酸检测结果较理想。本法对波谱严重重叠的两种酚酸能进行有效测定,     

HPLC法测定苹果浓缩汁中的多酚类物质

利用高效液相色谱法(HPLC)分析了儿茶素、绿原酸、咖啡酸、表儿茶素、香豆酸、阿魏酸等六种酚类物质在鲁加1号和鲁加5号苹果浓缩汁中的的含量.色谱条件:色谱柱为EdipseXDB-C18色谱柱(150mm×4.6mm id,5μm),以甲醇-1%乙酸水溶液作为流动相进行梯度洗脱.柱温30℃,流速为1.0ml/min,检测波长为280nm.在此色谱条件下,各组分均得到很好的分离.经测定鲁加1号苹果浓缩汁中含有儿茶素、绿原酸、咖啡酸、表儿茶素、香豆酸、阿魏酸等六种酚类物质;鲁加5号苹果浓缩汁中含有较少的绿原酸、咖啡酸、表儿茶素、香豆酸、阿魏酸等五种酚类物质.     

亚麻籽中木脂素及其水解产物的分离、鉴定和抗氧化活性

采用快速柱层析和制备薄层色谱相结合的新方法,从亚麻籽中分离木脂素开环异落叶松脂酚二糖苷和对香豆酸苷甲酯。同时发现,亚麻籽开环异落叶松脂酚二糖苷在酸水解时除生成开环异落叶松脂酚和无水开环异落叶松脂酚,还部分转化为开环异落叶松脂酚单糖苷。从亚麻籽的酸水解产物中分离出6 个化合物,分别鉴定为：开环异落叶松脂酚单糖苷、开环异落叶松脂酚、无水开环异落叶松脂酚、对香豆酸甲酯、阿魏酸甲酯和5-羟甲基糠醛;其中对香豆酸苷甲酯、对香豆酸甲酯和阿魏酸甲酯为首次从亚麻籽水解产物中分离获得,分别由对香豆酸苷、对香豆酸和阿魏酸在水解时与甲醇发生酯交换形成。体外抗氧化测试结果表明,开环异落叶松脂酚二糖苷、开环异落叶松脂酚单糖苷和开环异落叶松脂酚对1,1-二苯基-2-三硝基苯肼（1,1-diphenyl-2-picrylhydrazyl,DPPH）自由基、羟自由基（·OH）和超氧阴离子自由基（O2－·）均具有清除作用,且呈明显的量效关系。     

肉桂酸及其衍生物抗氧化活性研究

目的:研究肉桂酸及其衍生物等8种中草药有效成分对超氧阴离子自由基的清除和抑制脂质过氧化的作用和规律,以期为食品和药物等抗氧化剂的筛选和应用提供理论依据。方法:O2·测定采用改良的硝基四氮唑蓝-(NBT)还原法,微粒体脂质过氧化产物丙二醛(MDA)测定采用TBA分光光度法。结果:咖啡酸、氯原酸、连翘酯甙和阿魏酸对O2·具有较强的清除能力,对-羟基香豆酸、邻-羟基香豆酸和间-羟基香豆酸对O-2·的清除-能力较弱,肉桂酸则没有,清除O2·的能力强弱顺序为:咖啡酸>氯原酸>连翘酯甙>阿魏酸>对羟基香豆酸>邻-羟基香豆酸>间羟基香豆酸;对肝脏微粒体脂质过氧化产物MDA的形成具有抑制作用,作用的强弱关系与清除O2·能力基本一致。结论:除肉桂酸外,7种肉桂酸衍生物均具有抗氧化作用,而肉桂酸没有,进一步表明各-药物的抗氧化能力与其结构有明显的关系。结构—活性显示:-CHCHCOOH基团不是肉桂酸衍生物抗氧化的活性基团,而酚羟基是其抗氧化的必需基团;在肉桂酸-CHCHCOOH基团的对位含有酚羟基的化合物比在邻位或间位含有酚羟基化合物清除O2·活性强;在肉桂酸衍生物酚羟基的邻位有含孤对电子的杂原子取代基(-OH,-OCH3)时,-其清除O·的能力进一步提高。-2     

高效液相色谱-质谱法测定紫色马铃薯花色苷组成

对我国两种紫色马铃薯中花色苷进行鉴定。紫色马铃薯样品经过乙醇提取、固相萃取和HPLC/DAD/MS分析等步骤,最终确定红色马铃薯(2472)中含有天竺葵-3-芸香糖苷-5-葡萄糖苷、天竺葵-3-芸香糖苷、天竺葵-3-咖啡酰-芸香糖苷-5-葡萄糖苷、矢车菊-3-p-香豆酰-芸香糖苷-5-葡萄糖苷和天竺葵3-p-香豆酰-芸香糖苷-5-葡萄糖苷,其中天竺葵3-p-香豆酰-芸香糖苷-5-葡萄糖苷为主要成分。紫色马铃薯(紫香玉)中含有牵牛花-3-芸香糖苷-5-葡萄糖苷、牵牛花-3-p-香豆酰-芸香糖苷-5-葡萄糖苷、牵牛花-3-咖啡酰-芸香糖苷-5-葡萄糖苷、牵牛花-3-阿魏酰-芸香糖苷-5-葡萄糖苷和锦葵-3-p-香豆酰-芸香糖苷-5-葡萄糖苷,其中牵牛花-3-p-香豆酰-芸香糖苷-5-葡萄糖苷为主要成分。值得注意的是,矢车菊-3-p-香豆酰-芸香糖苷-5-葡萄糖苷在马铃薯中为首次检出。     

Development of High‐Performance Liquid Chromatographic for Quality and Authenticity Control of Chinese Propolis

A RP‐high‐performance liquid chromatography (HPLC) method was developed for quality control of Chinese propolis by simultaneous analysis of 12 flavonoids and 8 phenolic acids. The results showed that vanillic acid, rutin, myricetin, and luteolin were not detected in all of the analyzed propolis and poplar tree gum samples. The caffeic acid, ferulic acid and p‐coumaric acid were not detected in poplar tree gum but were detected in propolis, which suggest that they are practical indexes of distinguishing propolis from poplar tree gum. The flavonoid profiles of poplar tree gum were found to be similar to those of propolis, which are dominated by pinobanksin, pinocembrin, 3‐O‐acetylpinobanksin, chrysin, and galangin. Therefore, the proposed method could be applied to exclude poplar tree gum from propolis with cafferic acid, ferulic acid, and p‐coumaric acid as qualitative markers, and distinguish poplar source resin from other illegal substances, and evaluate the quality grading of poplar‐type propolis with pinobanksin, pinocembrin, 3‐O‐acetylpinobanksin, chrysin, and galangin as qualitative and quantitative markers.     

高效液相色谱法分析北方部分地区蜂胶醇提物成分

研究北方部分地区的蜂胶提取物中组分含量的差异并对成分分析。采用乙醇水溶液对中国北方11个省市的蜂胶进行提取,以NaNO2-Al(NO3)3比色法和Folin-Ciocalteu试剂比色法分别测定蜂胶不同提取物的总黄酮和总酚酸含量;并且借助标准品以高效液相色谱法对不同提取物中的酚类化合物进行初步定性和定量,进而模拟蜂胶的区域性。结果表明：不同地区的蜂胶含有的总黄酮和总酚酸不同,其中咖啡酸、坎非醇、松属素、柯因、高良姜素、苯甲酰肉桂酯以河南蜂胶含量最高;芹菜素、异鼠李素以辽宁蜂胶含量最多;山东蜂胶含有最多的鼠李素。     

Development and validation of HPLC method for determination of salicin in poplar buds: Application for screening of counterfeit propolis

The main plant origins of propolis are the populus species and their hybrids, both located in China. Poplar tree gum, the extract of populus buds, has been widely used as counterfeit propolis, but no efficient method was known for detecting the counterfeit. Salicin is a characteristic marker of the genus populus, which may be hydrolysed by β-glucosidase during propolis collection and processing. A simple, sensitive and specific reversed-phase high-performance liquid chromatography (RP-HPLC) method was developed and validated for the rapid assay of salicin, which was aimed at distinguishing poplar tree gum from propolis. Isocratic elution at a flow rate of 1.0 mL/min was employed on a Sepax HP-C18 column (150 × 4.6 mm, 5 μm) and the column temperature was 30 °C. The mobile phase consisted of acetonitrile and 0.5% aqueous phosphoric acid (5:95, v/v). The UV detection wavelength was 213 nm. Following this method, salicin was detected in populus buds and leaves and 11 poplar tree gum samples, but not in any of the 40 propolis samples, which indicates that salicin was hydrolysed in propolis collection and processing but was stable in the production process of poplar tree gum. The proposed method could be an effective technique for routine analysis of salicin and monitoring the quality of propolis as possible counterfeit poplar tree gum.     

蜂胶掺假鉴别技术研究进展

蜂胶具有广泛的生物活性,如抗氧化、防辐射、防龋齿、消炎抑菌及调节免疫等,是较为珍贵的蜜蜂产品。蜂胶依据胶源植物的不同可分为杨树型蜂胶、巴西绿蜂胶、红蜂胶等7大类。我国的蜂胶类型主要为杨树型蜂胶,其化学成分与杨树芽提取物相似,蜂胶资源紧缺和高利润导致杨树胶掺假冒充蜂胶现象日益严重。蜂胶掺假鉴别一直是蜂产品等天然产物的研究热点,本文综述近15年国内外研究者关于蜂胶掺假鉴别技术的研究进展,其中主要包括气相色谱法、液相色谱法、红外光谱法、核磁共振技术、薄层色谱法和特征物质鉴别等,其中液相-质谱技术应用最为广泛,鉴别结果较优。同时本文对多种蜂胶鉴别技术进行比较和总结,为蜂胶品质的鉴定和蜂胶的掺假鉴别提供资料参考和依据。     

Antioxidant activity of propolis of various geographic origins

Propolis is a resinous substance collected by honeybees from various plant sources. The antioxidant activities of propolis of various geographic origins, i.e., Argentina, Australia, Brazil, Bulgaria, Chile, China (Hebei, Hubei, and Zhejiang), Hungary, New Zealand, South Africa, Thailand, Ukraine, Uruguay, United States, and Uzbekistan were compared. Ethanol extracts of propolis (EEP) were prepared and evaluated for antioxidant activities of EEP samples by the β-carotene bleaching and 1,1-diphenyl-2-picrylhydrazyl (DPPH) free radical scavenging assay systems. Major constituents were identified in EEP by HPLC analysis with photo-diode array (PDA) and mass spectrometric (MS) detection, and quantitatively analyzed. EEP from Argentina, Australia, China, Hungary and New Zealand had relatively strong antioxidant activities, and were also correlated with the total polyphenol and flavonoid contents. Propolis with strong antioxidant activity contained antioxidative compounds such as kaempferol and phenethyl caffeate.     

对比福林酚法和高效液相色谱法测定酒神菊属蜂胶和国产蜂胶中酚酸类化合物含量

目的 比较福林酚法和高效液相色谱法测定酒神菊属蜂胶和国产蜂胶中的酚酸含量的差异。 方法 采用福林酚法(Folin-酚法)测总酚酸, 以没食子酸为对照品, 765 nm下检测样品的吸光值; 采用高效液相色谱法(high performance liquid chromatography, HPLC)测总酚酸, 以绿原酸、咖啡酸、异绿原酸A、异绿原酸C、咖啡酸苯乙酯、阿替匹林C为对照品, 优化HPLC洗脱条件, 利用标准品的进样量和色谱峰面积进行线性拟合, 线性回归方程以计算各个单体的含量。结果 Folin-酚法下, 酒神菊属蜂胶总酚酸含量为5.71%~14.68%, 平均为11.34% (n=14), 国产蜂胶总酚酸含量为5.87%~28.99%, 平均值为16.98% (n=12); HPLC法下, 酒神菊属蜂胶总酚酸含量为2.13%~9.20%, 均值为5.71% (n=14), 国产蜂胶总酚酸含量为1.69%~9.13%, 均值为5.05% (n=12)。结论 2种蜂胶都含有比较高含量的酚酸类成分, 不同测定方法下酚酸类成分含量存在明显差异, 选择合适的方法用于检测蜂胶中的酚酸类成分含量显得尤为重要。     

不同植物源蜂胶挥发性成分差异分析

采用顶空固相微萃取-气质联用技术分析4种不同植物来源的蜂胶挥发性成分,并结合主成分分析法对其进行分析。结果表明,不同植物源的蜂胶挥发性成分存在差异,主要表现在共有组分的含量和特有组分两个方面。其中的共有组分有3-甲基-3-丁烯-1-醇、异戊二烯、4-戊烯-1-乙酸酯、梨醇酯、4-异丙基甲苯、柠檬烯、桉叶油醇、3-蒈烯、壬醛、α-古巴烯、α-依兰油烯、去氢白菖烯、β-马榄烯、β-桉叶醇和α-桉叶醇,它们在各样品中的含量相差较大。特有组分,如：样品a,α-松油烯、α-柏木烯;样品c,α-姜黄烯、α-愈创木烯;样品d,石竹烯、γ-依兰油烯、苯甲酸苄酯。实验结果有利于提取蜂胶的特征信息,进行指纹图谱及区分模型的研究。     

蜂胶及杨树胶关键气味活性成分研究

采用固相微萃取的方法提取蜂胶及杨树胶中的挥发性成分,以气相-质谱-嗅闻仪联用对蜂胶中的挥发性成分进行分离鉴定。结果测得48种气味活性成分,包括酯、醛、醇、酮和酸。蜂胶中体现花香、果香的成分较多,从而赋予其更为清香、柔和的总体气味特征。     

Food preservative based on propolis: Bacteriostatic activity of propolis polyphenols and flavonoids upon Escherichia coli

Propolis was tested as food preserver, due its recognized bactericidal and bacteriostatic properties. Furthermore, most propolis components are natural constituents of food and recognized as safe substances. Fifteen propolis from Santa Fe, Argentine in 20% w/w ethanolic extracts, were tested upon Escherichia coli ATCC 25922 by agar diffusion and plate culture methods. Considering propolis physicochemical characteristics and inhibitory effects, tested samples were classified in three groups. A minimum inhibitory concentration mean value of 14.3 ± 6 mg soluble compounds/ml of the most active propolis was capable of inhibiting 10⁵ cfu/ml cellular concentration. Such extract had 32.31% total soluble compounds (2.1% coumaric + siringic acids, 5.16% quercetin, 0.47 apigenine, 8.15 galangine, 7.2 caffeic acid + crisine and 9.23% no-identified phenolics compounds). By relating the zone of growth inhibition with extracts concentration, a linear response was obtained. On the propolis samples tested, a single value of the minimum inhibitory concentration could not be established. Those values were strongly dependent on propolis composition and botanical origin. The propolis extracts tested, may successfully inhibit the E. coli development in vitro, and consequently may be useful as natural food preserver.     

Antioxidants in oats: Mono-esters of caffeic and ferulic acids

Two-dimensional thin-layer chromatography has shown the presence of 24 phenolic antioxidants in oats, and the present paper deals with the identification of five of these. Two of them have been isolated by column chromatography and characterised. One consists of the homologues, n-hexacosyl caffeate and n-octacosyl caffeate (proportions, 3:1, approximately) and the other, 26-O-caffeoyl-26-hydroxy-hexa-cosanoic acid with 28-O-caffeoyl-28-hydroxyoctacosanoic acid (proportions, 3:1, approximately). Evidence is presented for the probable structures of the remaining three antioxidants, based on two-way thin-layer chromatographic comparison with the synthetic ferulates: n-hexacosyl ferulate, 26-O-feruloyl-26-hydroxyhexacosanoic acid and hexacosane-1,26-diol monoferulate. The preparation of these ferulates is described, and in addition, that of two caffeates, n-hexacosyl and n-dodecyl. The antioxidant activities of the above compounds were measured.