头序楤木叶中三萜化学成分的研究

从头序楤木(Aralia dasyphyla Miq)叶中分离到6个三萜化合物,用化学方法和波谱(UV,IR,MS,¹HNMR,¹³CNMR,¹³CDEPT,HMQC,HMBC)分析,确定其中4种化合物的结构,分别为齐墩果酸(I),16β-羟基-18β-H-齐墩果酸(I),齐墩果酸-28-O-β-D-吡喃葡萄糖甙(II)和16β-羟基-18β-H-齐墩果酸-28-O-β-D-吡喃葡萄糖甙(IV)。用NOESY谱确定化合物I的立体构型。以上4个化合物均为首次从该植物中分离到,化合物IV为新化合物。     

升麻中的三萜类成分

从升麻(Cimiccifuga foetida L.)的根茎中分得五个环菠萝蜜烷型三萜化合物,经光谱解析(IR,MS,¹H及¹³CNMR),分别确定为25-脱水升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(I),升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(II),25-乙酰氧基升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(III),actein(IV)和27-deoxyactein(V),其中I为新化合物,命名为升麻甙E(cimisideE)。     

黄毛忽木皂甙A的分离和结构测定

黄毛木(Aralia decaisneana Hance)为五加科木属植物。从其根的甲醇提取物中分离得到一个皂甙化合物(I),根据光谱(IR,¹HNMR,¹³CNMR,MS,Longrange ¹H-¹HCOSY和¹H-¹³cHETCOR)解析和化学反应(酸水解,乙酰化和碱水解)证明,化合物1的结构确定为3-O-[β-D-吡喃木糖1→3)]-β-D-吡喃葡萄糖(1→2)-β-D-吡喃葡萄糖-28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙。该化合物是一个新的三萜皂甙,命名为黄毛木皂甙A(aradecoside A)。     

蛇毒中鞣花酸类及三萜类成分研究

自蛇毒(Duchesnea indica Fock)全草中分离出6个化合物,其中,2个为新化合物,分别命名为蛇莓甙A(duchesideA)和蛇莓甙B(duchesideB),经化学及光谱(UV,1R,¹HNMR,¹³CNMR,NOEDS和MS)分析确定,蛇莓甙A的结构为3'-O-甲基-鞣花酸-4-O-β-D-吡喃木糖甙(Ⅰ),蛇莓甙B的结构为3'-O-甲基-鞣花酸-4-O-α-L-呋喃阿拉伯糖甙(Ⅱ)。另外4个化合物为已知三萜类化合物:3β-羟基-乌苏烷-12-烯-28-羧酸(Ⅲ),2α,3β,19α-三羟基-乌苏烷-12-烯-28-羧酸(Ⅳ),2α,3β,19α-三羟基-乌苏烷-12-烯-28-羧酸-28-O-β-D-吡喃葡萄糖甙(Ⅴ),2α,3α,19α-三羟基-乌苏烷-12-烯-28-羧酸-28-O-β-D-吡喃葡萄糖甙(Ⅵ)。其中化合物Ⅳ,Ⅴ和Ⅵ为首次从该属植物中分离得到。     

何首乌乙酸乙酯不溶部分化学成分的研究

从四川何首乌(polygonu mnultiflorum Thunb)块根乙醇提取物的乙酸乙酯不溶部分分离得到五个单体,经理化常数测定,光谱(IR,UV,FAB-MS,¹HNMR,¹³CNMR,¹H-¹³CCOSY和NOE差谱)分析及衍生物制备,确定了两个化合物的结构为新化合物。化合物Ⅰ1,3-二羟基-6,7-二甲基酮-1-O-β-D-葡萄糖甙,命名为何首乌乙素,化合物Ⅱ为2,3,5,4′-四羟基-二苯乙烯-2,3-二-O-β-D葡萄糖甙,命名为何首乌丙素。其余三个结晶因量少有待进一步分离、鉴定。     

红参中新化合物——精氨酸衍生物的分离与结构鉴定

红参水提液经聚丙烯酰胺(Bio-gelP-2)柱层析,分离得到五个茚三酮反应阳性物质。其中一个为已知化合物精氨酸(I)。另一个为新化合物精氨酸双糖甙(I),根据红外、紫外、质谱、氢谱及碳谱等光谱解析,推定为1-(精氨酸-N^α基)-1-去氧-4-O-(α-D-吡喃葡萄糖基)-D-果糖。并用半合成法进一步确证其结构。化合物II,IV和V的结构正在研究中。     

虎眼万年青的化学成分

目的：研究栽培于长白山区的虎眼万年青Ornithogalum caudatum Ait全草的化学成分。 方法：用各种色谱技术进行分离和纯化,用ESIMS,IR,¹HNMR,¹³CNMR,DEPT,¹H-¹H COSY, ¹H-¹³C COSY, HMBC和NOESY等波谱数据分析鉴定结构。结果：从虎眼万年青全草中分离得到3个化合物,其中化合物I为新化合物,其结构鉴定为（25S, 23S, 24S）-螺甾-Δ⁵⁽⁶⁾-烯-1β, 3β,23,24-四醇-1-O-α-L-吡喃鼠李糖基-（1→2） ［β-D-吡喃木糖基-(1→3)］-α-L-吡喃阿拉伯糖苷(I),另外2个已知化合物为海柯皂苷元-3-O-{β- D-吡喃葡糖基（1→2）-［β-D-吡喃木糖基（1→3）］-β-D-吡喃葡糖基（1→4）-β-D-吡喃半乳糖苷}(II)和β-谷甾醇(III)。结论：化合物I为新化合物,命名为虎眼万年青苷A,化合物II和III是首次从该植物中分得的已知化合物。     

知母中呋甾皂甙的研究

自知母 Anemarrhena asphodeloides Bge.根茎的乙醇提取物中,经硅胶柱层析和制备型HPLC分得四种呋甾皂甙。用化学反应和波谱(IR,FAB-MS,EI-MS,¹HNMR,¹³CNMR,DEPT,一维多重接力CoSY,二维接力HOHAHA,¹H-¹H COSY,¹H-¹³C COSY和NOE差谱)解析,确定其结构为知母皂贰B(anemarsaponinB,I),(25S)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃哺葡萄糖甙(Ⅱ),(25S)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-3β,26-二醉-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅲ),(25S)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-3β,26-二醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(Ⅳ)。Ⅱ为一新的呋甾皂甙,命名为知母皂甙C;化合物Ⅳ为首次从知母中分离得到,命名为知母皂甙E。初步的药理实验显示,化合物1～Ⅳ均有一定的清除羟自由基的作用。     

中药升麻的化学成分

从中药兴安升麻[Cimicifuga dahurica(Turcz.)Maxim.]的干燥根茎中分得五个化合物,其中四个为三萜木糖甙:升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅰ),25-O-乙酰升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅱ),12-羟基升麻醇-3-O-β-D-吡喃木糖甙(23R,24S)(Ⅲ),升麻醇-3-O-β-D-吡喃木糖基(3→1)-β-D-吡喃木糖甙(23R,24S)(Ⅳ),另一个为异阿魏酸(Ⅴ)。Ⅲ和Ⅳ为新化合物,通过光谱(IR,MS,¹H及¹³C NMR)解析确定了它们的结构,分别命名为升麻甙A(cimiside A)和升麻甙B(cimiside B)。     

薤白甙J,K和L的结构

进一步用HPLC自小根蒜(Allium macrostemon Bunge)鳞茎中分得两种新的呋甾皂甙,薤白甙J(1)和薤白甙L(III),以及I的甲基化人工产物薤白甙K(II)。经过化学降解和光谱(¹H-NMR,¹³C-NMR和FAB-MS等)分析,确定其结构分别为:(25R)-26-O-β-D-吡喃葡萄糖基-22-羟基-5β-呋甾-2β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(I);(25R)-26-O-β-D-吡喃葡萄糖基-22-甲氧基-5β-呋甾-2β,3β,26-.三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(II)和(25R)-26-O-β-D-吡喃葡萄糖基-5β-呋甾-20(22)-烯-26β,3β,26-三醇-3-O-β-D-吡喃葡萄糖基(1→2)-β-D-吡喃半乳糖甙(III)。     

银杏叶中的黄酮醇苷类成分

目的　对银杏（Ginkgo biloba L.）叶的化学成分进行分离、鉴定。方法　采用各种色谱技术进行分离,用IR,UV,MS,¹HNMR,¹³CNMR和2DNMR光谱技术确定化合物的结构。结果　分得8个黄酮醇苷类成分：槲皮素-3-O-β-D-葡糖苷（1）,山奈酚-3-O-β-D-葡糖苷（2）,芦丁（3）,山奈酚-3-O-β-D-芸香糖苷（4）,异鼠李素-3-O-β-D-芸香糖苷（5）,槲皮素-3-O-β-D-葡萄糖基(1-2)-α-L-鼠李糖苷（6）,山奈酚-3-O-β-D-葡萄糖基(1-2)-α-L-鼠李糖苷（7）,异鼠李素-3-O-β-D-葡萄糖基(1-2)-α-L-鼠李糖苷（8）。结论　化合物8为新化合物。     

Lignan glycosides from the leaves of <Emphasis Type="Italic">Osmanthus heterophyllus</Emphasis>

Seven known lignan glycosides were isolated from the leaves of Osmanthus heterophyllus: (+)-syringaresinol 4-O-β-d-glucopyranoside, (+)-syringaresinol 4, 4′-O-di-β-d-glucopyranoside, (+)-medioresinol 4, 4′-O-di-β-d-glucopyranoside, (+)-medioresinol 4-O-β-d-glucopyranoside, (+)-pinoresinol 4, 4′-O-β-d-glucopyranoside, (+)-epipinoresinol 4-O-β-d-glucopyranoside and phillyrin. Their structures were determined on the basis of spectral data.     

New iridoid glycosides from the twigs and leaves of Callicarpa formosana var. formosana

Four new iridoid glycosides, 6-O-benzoylphlorigidoside B (1), 6-O-trans-cinnamoylphlorigidoside B (2), 6-O-trans-p-coumaroylshanzhiside methyl ester (3), and 4′-O-trans-p-coumaroylmussaenoside (4), were isolated from the EtOH extract of the twigs and leaves of Callicarpa formosana var. formosana. Their structures were elucidated by extensive spectroscopic analysis.     

Simultaneous quantitative analysis of 11 flavonoid derivatives with a single marker in persimmon leaf extraction and evaluation of their myocardium protection activity

An improved, reliable and comprehensive method for assessing the quality of the ethyl acetate extract from persimmon leaves (EAPL) and its commercial preparation, Naoxinqing (Brain and Heart Clear capsules), has been developed and validated. Based on HPLC–DAD-ESI-Q-TOF–MS analysis, myricetin-3-O-β-d-galactoside (1), myricetin-3-O-glucoside (2), quercetin-3-O-β-d-galactoside (3), quercetin-3-O-β-d-glucoside (4), quercetin-3-O-(2″-O-galloyl-β-d-galactoside) (5), quercetin-3-O-(2″-O-galloyl-β-d-glucoside) (6), kaempferol-3-O-β-d-galactoside (7), kaempferol-3-O-β-d-glucoside (8), kaempferol-3-O-(2″-O-galloyl-β-d-galactoside) (9), kaempferol-3-O-(2″-O-galloyl-β-d-glucoside) (10), quercetin (11) and kaempferol (12) were identified from 15 batch samples. A HPLC fingerprint analytical method was established. All compounds, with the exception of compound 2, were simultaneously quantified by the single standard to determine multi-components (SSDMC) method, using kaempferol-3-O-β-d-glucoside as the internal standard. The rate of analysis was found to be faster with the SSDMC method than with current acid hydrolysis method (Pharmacopoeia of the People's Republic of China 2015 edition) and the results were more intuitive and reliable. Three-dimensional principal component analysis revealed that there were similar characteristics in persimmon leaf from same district. Analysis of the myocardial cell protection activity of 11 monomeric compounds showed that compounds 12, 11 and 10 were the main active ingredients that produce pharmacologic functions in EAPL. Among these compounds, the bioactive constituent of myricetin-3-O-β-d-galactoside was determined for the first time in Diospyros khaki. Thus, we have established an effective assessment method that can be applied to the comprehensive quality evaluation of EAPL extract and Naoxinqing capsule.

     

Irritant and co-carcinogenic diterpene esters from the latex of Euphorbia cauducifolia L.

Ten (1–10) irritant and mild co-carcinogenic diterpene esters were isolated from the latex of Euphorbia cauducifolia L. using bioassay-guided countercurrent distribution and other chromatographic techniques. The isolated compounds were characterized on the basis of spectroscopic results and mass measurements. As an outcome, the ingenane-type esters were established with the following structures: 3-O-angeloyl-17-O-palmatoylingenol (1), 3-O-palmatoyl-5-O-angeloylingenol (2), 5-O-angeloyl-17-O-palmatoylingenol (3), 3-O-angeloyl-5-O-palmatoylingenol (4), 17-O-(2Z,4E,6Z)-2,4,6-tetradecatrienoyl-20-O-palmatoylingenol (5), 5-O-angeloyl-17-O-benzoylingenol (6), 5-O-angeloyl-17,20-diacetoxyingenol (7), 3-O-angeloyl-17-O-benzoyl-20-acetoxyingenol (8), 3-acetoxy-5-O-angeloyl-17-O-benzoylingenol (9), and 5-O-angeloyl-3,17,20-triacetoxyingenol (10). Their biological screening revealed that they are moderate irritants, and low to moderate tumor promoters compared to TPA, but hardly showed any solitary carcinogenic activity. The isolated esters represent new compounds and were not reported before from any source.     

合欢皂苷J20的结构鉴定

目的:研究合欢皮的化学成分及活性。方法:用现代色谱法分离合欢皮皂苷,用化学和现代波谱法,主要是二维核磁共振技术鉴定结构。结果及结论:分离并鉴定了一个新三萜皂苷,结构为3-O-[β-D-吡喃木糖基-(1→2)-α-L-吡喃阿拉伯糖基-(1→6)-β-D-吡喃葡糖基]-21-O-｛(6S)-2-反式-2-羟甲基-6-甲基-6-O-β-D-吡喃木糖基-2,7-辛二烯酰基｝金合欢酸28-O-β-D-吡喃葡糖基-(1→3)-[α-L-呋喃阿拉伯糖基-(1→4)]-α-L-吡喃鼠李糖基-(1→2)-β-D-吡喃葡糖基酯,命名为合欢皂苷J₂₀(JulibrosideJ₂₀)。     

Two new anthraquinone glycosides from the roots of Rheum palmatum

Two new anthraquinone glycosides, named 1-methyl-8-hydroxyl-9,10-anthraquinone-3-O-β-d-(6′-O-cinnamoyl)glucopyranoside (1) and rhein-8-O-β-d-[6′-O-(3″-methoxyl malonyl)]glucopyranoside (2), have been isolated from the roots of Rheum palmatum, together with seven known compounds, rhein-8-O-β-d-glucopyranoside (3), physcion-8-O-β-d-glucopyranoside (4), chrysophanol-8-O-β-d-glucopyranoside (5), aleo-emodin-8-O-β-d-glucopyranoside (6), emodin-8-O-β-d-glucopyranoside (7), aleo-emodin-ω-O-β-d-glucopyranoside (8), and emodin-1-O-β-d-glucopyranoside (9). Their structures were elucidated on the basis of chemical and spectral analysis.     

Three new lignans from the seeds of Saussurea involucrata

Three new lignans, arctigenin-4-O-(6″-O-acetyl-β-d-glucoside) (1), arctigenin-4-O-(2″-O-acetyl-β-d-glucoside) (2), and arctigenin-4-O-(3″-O-acetyl-β-d-glucoside) (3), together with two known lignans, were isolated from the seeds of Saussurea involucrata. Their structures were established by spectroscopic methods, mainly 1D and 2D NMR, and mass spectral analysis.     

New acylated flavonoid glycosides from flowers of Aerva javanica

Chromatographic purification of ethyl acetate soluble fraction of the methanolic extract of the flowers of Aerva javanica yielded three new acylated flavone glycosides: kaempferol-3-O-β-d-[4?-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-galactoside (1), kaempferol-3-O-β-d-[4?-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-(3″-E-p-coumaroyl)galactoside (2), and kaempferol-3-O-β-d-[4?-E-p-coumaroyl-α-l-rhamnosyl(1 → 6)]-(4″-E-p-coumaroyl)galactoside (3), along with p-coumaric acid (4), caffeic acid (5), gallic acid (6), eicosanyl-trans-p-coumarate (7), hexadecyl ferulate (8), and hexacosyl ferulate (9). The compounds 1–9 were characterized using 1D (¹H, ¹³C) and 2D NMR (HMQC, HMBC, and COSY) spectroscopy and mass spectrometry (EI-MS, HR-EI-MS, FAB-MS, and HR-FAB-MS) and in comparison with the reported data in the literature. Compound 1 showed weak inhibitory activity against enzymes, such as acetylcholinesterase, butyrylcholinesterase, and lipoxygenase with IC₅₀ values 205.1, 304.1, and 212.3 μM, respectively, whereas compounds 2 and 3 were only weakly active against the enzyme acetylcholinesterase.     

川续断中皂甙Ⅺ,Ⅻ和ⅩⅢ的结构研究

从川续断(Dipsacus asper Wall.)根的醇提物中得到三个微量新三萜皂甙(Ⅺ～ⅫⅠ),根据光谱分析和化学反应,其结构分别鉴定为3-O-[β-D-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-β-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-常春藤皂甙元(Ⅺ)、Ⅺ的28-O-β-D-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙( Ⅻ)和3-O-[β-D-吡喃木糖(1→4)-B-O-吡喃葡萄糖(1→4)][α-L-吡喃鼠李糖(1→3)]-B-D-吡喃葡萄糖(1→3)-α-L-吡喃鼠李糖(1→2)-α-L-吡喃阿拉伯糖-齐墩果酸-28-O-β-吡喃葡萄糖(1→6)-β-D-吡喃葡萄糖酯甙(ⅫⅠ)。