木麻黄及山槐树皮单宁组分的研究(凝缩类单宁组分研究之二)

从木麻黄(Casuarina equisetifolia)及山槐(Albizzia kalkora)树皮提取物中分离出来的水溶性单宁,通过各种降解反应及波谱方法研究,判定均为原花青定,且二者在化学组成上十分相似,它们的终端单位均由各占一半左右的(+)—儿茶素及(-)—表儿茶素组成,二者的比例为6:4。延伸单元亦均由(+)—儿茶素与(-)—表儿茶素组成,而以(-)—表儿茶素占绝大部分,二者的比例约为3:7。它们的分子中,2,3—反式与2,3—顺式单元的比例约为2:8。木麻黄和山槐树皮单宁的平均聚合度分别为12和14。     

薯莨及红根皮单宁组分的研究(凝缩类单宁组分研究之四)

从薯莨(Dioscorea cirrhosa)块茎及红根(Rosa spp.)根皮提取物中分离出来的单宁,通过各种降解反应及波谱方法研究,均判定为原花青定。其中的终端单元及延伸单元,都由(+)-儿茶素及(-)-表儿茶素组成,但(-)-表儿茶素单元在薯莨原花青定中占大部分,(+)-儿茶素单元在红根原花青定中占大部分。     

毛杨梅及油柑树皮单宁组分的研究(凝缩类单宁组分研究之二)

从毛杨梅(Myrica esculenta)及油柑(Phyllanthus emblica)树皮提取物分离出米的单宁,通过各种降解反应及波谱方法研究判定,毛杨梅单宁是局部带有3-o-棓酰基的原翠雀定。油柑单宁是由局部带有3-o-棓酰基的原翠雀定与原花青定组成的混合型原花色素。两种单宁分子的组成单元大部分具有2,3-顺式构型。     

木榄花萼缩合单宁制备花青定及抗氧化能力研究

利用MALDI-TOF MS分析了红树植物木榄花萼缩合单宁的结构单元组成类型、平均聚合度和平均分子质量.并以木榄花萼缩合单宁为原料,通过HCl-正丁醇法酸解反应制备了花青定粗产品,同时测定了花青定粗产品对二苯基苦基苯肼自由基(DPPH·)的清除能力及铁离子还原/抗氧化能力(FRAP).结果表明:木榄花萼缩合单宁结构单元组成类型主要为儿茶素或表儿茶素,平均聚合度为7.5,平均分子质量为2 081.60 u;花青定粗产品具有较强的清除自由基能力,DPPH·半数抑制浓度(IC50)为43.889 mg/L,并具有较高的FRAP((7.718± 0.109)mmol/g).     

落叶松树皮黄烷-3-醇及其聚合物研究

从落叶松[Larix gmelini (Rupr.)Rupr.]树皮中分离、鉴定了三种黄烷-3-醇,即(-)表阿夫儿茶素,( )儿茶素和(-)表儿茶素。以乙酰衍生物形式分离出四种二聚黄烷-3-醇(二聚原花青定)B1—B4,并通过与标样薄层共层析及其核磁共振氢谱进行了鉴定。对可溶于甲醇的多聚黄烷-3-醇(多聚原花青定)用甲苯-α-硫醚和醋酸进行了化学分解。根据分解产物确定, 落叶松树皮含有分别以( )儿茶素和(-)表儿茶素为终端单元之多聚黄烷-3-醇,其延伸单元亦由2,3反式和2,3-顺式3,5,7,3′,4′黄烷五醇所组成。用高效液相色谱定量测定了上述化学分解产物,并在此基础上得出该多聚黄烷-3-醇之平均聚合度为6-7,相应数均分子量为1700—2000。     

光催化提高黑荆树单宁与甲醛反应能力研究

为提高黑荆树单宁与甲醛反应能力,以纳米TiO 2为催化剂对黑荆树单宁进行紫外光催化降解。以降解物的甲醛结合量为指标,分析催化剂用量对黑荆树单宁降解产物甲醛反应能力的影响。采用基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)测定黑荆树单宁和具有最大甲醛结合量黑荆树单宁降解产物的分子量和聚合度。采用傅里叶转换红外光谱(FT-IR)对黑荆树单宁及具有最大甲醛结合量黑荆树单宁降解产物的官能团进行表征。结果表明,催化剂用量对降解物甲醛结合量的影响较大,当紫外光功率为400 W、溶液初始质量浓度为60 g/L、反应温度为(35±5)℃、纳米TiO 2添加量为4%(质量分数,以黑荆树单宁质量计)、降解时间为10 h时,降解物的甲醛结合量达到最大值(1.13 g/g),超过了苯酚和间苯二酚的甲醛结合量(0.89 g/g和0.94 g/g),有替代苯酚和间苯二酚与甲醛反应制备木材用胶黏剂的潜能。MALDI-TOF MS分析表明,黑荆树单宁的聚合度和分子量均有明显地下降趋势,降解物分子量分布集中于低分子量部分。FT-IR分析表明,单宁结构中连接棓酰基的醚键、棓儿茶素的苯环骨架、芳醚键、单元间C—C连接键均被破坏。以上结果表明,可通过紫外光催化降解调控黑荆树单宁的化学组成并降低其聚合度和分子量,获得的降解物具有良好的甲醛反应能力。     

杨梅不同部位单宁含量与结构研究

对杨梅的叶、枝和树皮的总酚含量与可溶缩合单宁含量进行了测定,并利用基质辅助激光解吸附飞行时间质谱(MALDI-TOFMS)详细研究了不同部位中缩合单宁的类型、聚合度及聚合物的分布情况。结果表明:树皮的总酚含量最高(43.56%),叶次之(34.69%),枝最低(18.53%);树叶的可溶缩合单宁含量最高(25.67%),皮次之(17.93%),枝最低(8.01%);3组分的缩合单宁都以(表)棓儿茶素-3-O-棓酸酯(EGCG/GCG)为基本结构单元的原翠雀定,且大部分聚合物的结构单元之间存在A型和B型两种连接方式,但其中叶和枝缩合单宁的聚合度要大于树皮。     

微生物降解葡萄皮单宁研究

为降低葡萄皮单宁的分子量和聚合度,选取青霉(Penicillium sp.)和米曲霉(Aspergillus oryzae)为微生物菌株对葡萄皮单宁进行生物降解。以儿茶素的生成量和转化率为指标,分析碳源、氮源、时间、温度、pH和诱导培养基中单宁质量浓度对降解效果的影响。结果表明:外加碳源和氮源有利于青霉和米曲霉菌株的生长;时间为葡萄皮单宁降解得到不同中间产物的关键参数;温度、pH和葡萄皮单宁的质量浓度对菌株活性和降解能力均有不同程度影响;青霉对葡萄皮单宁的降解效果好于米曲霉。青霉最佳降解条件:培养时间24 h,温度28℃,pH6.5,单宁质量浓度12.5 g/L,儿茶素最大生成质量浓度0.32 mg/mL,转化率52.3%;米曲霉最佳降解条件:培养时间36 h,温度28℃,pH 6.5,单宁质量浓度10.0 g/L,儿茶素最大生成质量浓度0.16 mg/mL,转化率32.2%。因此,可通过生物降解法调控葡萄皮单宁的化学组成,适当降低单宁的分子量和聚合度。     

黑荆树树皮单宁组分研究——Ⅲ.原花色素的分离鉴定及其~(13)C NMR特征(英文)

从我国江西四年生黑荆树(Acacia mearnsii)树皮单宁中分离鉴定了三个二聚原花色素:刺槐亭醇-(4α→8)-儿茶素、菲瑟亭醇-(4β→8)-儿茶素和刺槐亭醇-(4β→8)-儿茶素。其中刺槐亭醇-(4β→8)-儿茶素为首次从黑荆树树皮中以天然形式分离得到,为一新天然化合物。文中首次对黑剂树树皮二聚原花色素的~(13)CNMR进行了报道,并就其特征和确定二聚原花色素的相对和绝对构型进行了讨论。     

落叶松树皮单宁组份分离及结构鉴定

落叶松[Larix gmelini(Rupr·)Rupr]树皮丙酮浸提物的剩余水溶物,经制备型高效液相色谱分离得到了大分子的单一组份Ⅲ、Ⅳ、Ⅴ、Ⅵ,光谱分析表明为儿茶素类的聚合物,估计其聚合度大于8,根据红外、元素分析,色谱分析确定其聚合度大小顺序为8≤Ⅲ<Ⅳ<Ⅵ<Ⅴ。组份Ⅴ为C_4—Cs连结的Cs,C_4全反式构型的儿茶素多聚体。 剩余水溶物用间苯三酚降解后,得到4—取代(2,4,6-三羟基苯基)儿茶素,其立体构型为2R,3S,从而进一步证实剩余水溶物是儿茶素类[以(+)—儿茶素为主]的聚合体。     

Two A-type proanthocyanidins from Prunus armeniaca roots

Two A-type proanthocyanidins, ent-epiafzelechin-(4alpha-->8, 2alpha-->O-->7)-(-)-epicatechin and its isomer, ent-epiafzelechin-(4alpha-->8', 2alpha-->O-->7')-catechin, together with other known compounds, have been isolated from the roots of Prunus armeniaca. The concerted use of one- and two-dimensional NMR methods (1H-(1)H COSY, HMQC, HMBC and NOESY) allowed the identification of these compounds.     

Reactivity of green tea catechins with formaldehyde

In the reaction of green tea catechins with formaldehyde at room temperature (25°C), tea catechins were found to have reactivity. In particular, (-)-epicatechin gallate and (-)-epigallocatechin gallate, which have a galloyl moiety at the C-3 position, showed higher reactivity than (+)-catechin, (-)-epicatechin, or (-)-epigallocatechin. Reactivity of various kinds of simple phenolic compounds and flavonoids with formaldehyde was also examined. Among these compounds, only phloroglucinol showed reactivity to the same degree as that of nongalloylated catechins. These results suggest that factors for reactivity with formaldehyde at room temperature may be the presence of a phloroglucinolic A-ring structure and the absence of the electron-attractive group such as a carbonyl group in Cring. The comparison of the reactivity of 3-O-acylated catechins with that of 3-O-galloylated catechins indicated that only a galloyl group effectively enhanced reactivity with formaldehyde.     

Characterization of proanthocyanidins from grape seeds

Leucoselect (grape seed selected proanthocyanidins) was analyzed. HPLC thermospray mass spectrometry (TSP-MS) allowed the detection of monomeric flavan-3-ols and dimeric proanthocyanidins. Fractionation over Sephadex LH-20 resin and analysis of the isolated fractions by gel permeation chromatography (GPC) and electrospray mass spectrometry (ESI-MS) led to the complete characterization of the proanthocyanidin constituents of Leucoselect. The analysis revealed the presence of approximately 15% of (+)-catechin (1) and (-)-epicatechin (2), 80% of (-)-epicatechin 3-O-gallate (3), dimers, trimers, tetramers and their gallates and 5% of pentamers, hexamers, heptamers and their gallates.     

三球悬铃木树皮的酚类化学成分研究

研究了三球悬铃木树皮的酚类化学成分.采用SephadexLH-20柱色谱及薄层色谱等方法进行分离,从其70%丙酮提取物乙酸乙酯溶性部分中分到11种化合物,经波谱分析及理化性质化合物分别鉴定为:儿茶素、表儿茶素、没食子儿茶素、表没食子儿茶素、山奈酚、槲皮素、阿福豆苷、异槲皮苷、紫云英苷-6″-没食子酸酯、异槲皮苷-6″-没食子酸酯和酪醇.11种化合物均首次从该树种中分得.     

日本落叶松新鲜松针的化学成分及其抗氧化活性研究

研究了日本落叶松新鲜松针的化学成分及其抗氧化活性.采用Sephadex LH-20柱色谱及薄层色谱等方法进行分离,从其95%乙醇提取物乙酸乙酯溶性部分中分到7种化合物,经波谱分析及理化性质化合物分别鉴定为:儿茶素(1)、表儿茶素(2)、没食子儿茶素(3)、异鼠李素-3-O-葡萄糖苷(4)、紫云英苷(5)、2"-O-鼠李糖牡荆黄苷(6)和cedrusin (7).7种化合物均首次从该植物中分得.经DPPH试验,测定了核酸溶性部分、二氯甲烷溶性部分、乙酸乙酯溶性部分、水溶性部分、粗提物及分得化合物的抗氧化活性.其中乙酸乙酯溶性部分及化合物1～3具有很强的抗氧化活性.     

Development of an isocratic HPLC method for catechin quantification and its application to formulation studies

The aim of this study was to develop a simple, rapid and accurate isocratic HPLC analytical method to qualify and quantify five catechin derivatives, namely (+)-catechin (C), (-)-epigallocatechin (EGC), (-)-epicatechin gallate (ECG), (-)-epicatechin (EC) and (-)-epigallocatechin gallate (EGCG). To validate the analytical method, linearity, repeatability, intermediate precision, sensitivity, selectivity and recovery were investigated. The five catechin derivatives were completely separated by HPLC using a mobile phase containing 0.1% TFA in Milli-Q water (pH 2.0) mixed with methanol at the volume ratio of 75:25 at a flow rate of 0.8ml/min. The method was shown to be linear (r(2)>0.99), repeatable with instrumental precision<2.0 and intra-assay precision<2.5 (%CV, percent coefficient of variation), precise with intra-day variation<1 and inter-day variation<2.5 (%CV, percent coefficient of variation) and sensitive (LOD<1μg/mL and LOQ<3μg/mL) over the calibration range for all five derivatives. Derivatives could be fully recovered in the presence of niosomal formulation (recovery rates>91%). Selectivity of the method was proven by the forced degradation studies, which showed that under acidic, basic, oxidation temperature and photolysis stresses, the parent drug can be separated from the degradation products by means of this analytical method. The described method was successfully applied in the in vitro release studies of catechin-loaded niosomes to manifest its utility in formulation characterization. Obtained results indicated that the drug release from niosomal formulations was a biphasic process and a diffusion mechanism regulated the permeation of catechin niosomes.     

Proanthocyanidins and a phloroglucinol derivative from Rumex acetosa L.

From the ethyl acetate soluble fraction of an acetone–water extract of the aerial parts of Rumex acetosa L. (Polygonaceae), a variety of monomeric flavan-3-ols (catechin, epicatechin, epicatechin-3-O-gallate), A- and B-type procyanidins and propelargonidins (15 dimers, 7 trimers, 2 tetramers) were isolated with 5 so far unknown natural products. Dimers: procyanidin B1, B2, B3, B4, B5, B7, A2, epiafzelechin-(4β→8)-epicatechin, epiafzelechin-(4β→8)-epicatechin-3-O-gallate (new natural product), epiafzelechin-(4β→6)-epicatechin-3-O-gallate (new natural product), epiafzelechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate, B2-3′-O-gallate, B2-3,3′-di-O-gallate, B5-3′-O-gallate, and B5-3,3′-di-O-gallate. Trimers: procyanidin C1, epiafzelechin-(4β→8)-epicatechin-(4β→8)-epicatechin (new natural product), epicatechin-(4β→8)-epicatechin-(4β→8)-catechin, cinnamtannin B1, cinnamtannin B1-3-O-gallate (new natural product), tentatively epicatechin-(2β→7, 4β→8)-epiafzelechin-(4α→8)-epicatechin (new natural product), and epicatechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate-(4β→8)-epicatechin-3-O-gallate.Tetramers: procyanidin D1 and parameritannin A1. All compounds were elucidated by ESI-MS, CD spectra, 1D- and 2D-NMR experiments as free phenols or peracetylated derivatives and, in part, after partial acid-catalysed degradation with phloroglucinol.A more abundant proanthocyanidin polymer was also isolated, purified and its chemical composition studied by ¹³C NMR.In addition a so far unknown phloroglucinolglycoside (1-O-β-d-(2,4-dihydroxy-6-methoxyphenyl)-6-O-(4-hydroxy-3,5-dimethoxybenzoyl)-glucopyranoside) was isolated.     

Effects of long-term,elevated ultraviolet-B radiation on phytochemicals in the bark of silver birch (Betula pendula)

Long-term outdoor experiments were conducted to investigate the effects of elevated ultraviolet-B (UV-B, 280-320 nm) radiation on secondary metabolites (phenolics and terpenoids) and the main soluble sugars (sucrose, raffinose and glucose) in the bark of silver birch (Betula pendula Roth) saplings. Saplings were exposed to a constant 50% increase in erythemal UV irradiance (UV-B(CIE); based on the CIE (International Commission on Illumination) erythemal action spectrum) and a small increase in UV-A radiation (320-400 nm) for three growing seasons in an irradiation field in central Finland. Two control groups were used: saplings exposed to ambient radiation and saplings exposed to slightly increased UV-A radiation. Concentrations of sucrose, raffinose and glucose in bark were higher in UV-treated saplings than in saplings grown in ambient radiation, indicating that stem carbohydrate metabolism was changed by long-term elevated UV radiation. Saplings in the elevated UV-A + UV-B radiation treatment and the UV-A radiation control treatment had significantly increased concentrations of certain UV-absorbing phenolics, such as salidroside, 3,4'-dihydroxypropiophenone-3-glucoside, (+)-catechin and (-)-epicatechin compared with saplings in ambient radiation. In contrast, the radiation treatments had no effect on the non-UV-B-absorbing terpenoids, papyriferic acid and deacetylpapyriferic acid. We conclude that plant parts, in addition to leaves, accumulate specific phenolic UV-filters in response to UV radiation exposure.