A New Flavan-3-ol Glucoside from Daphniphyllum oldhami

A new flavan-3-ol glucoside, (-)-afzelechin-7-O-β-D-glucopyranoside (1), has been isolated from the stem of Daphniphyllum oldhami. The structure of the new compound was elucidated on the basis of detailed spectroscopie analysis and comparison with related compounds.

Oldhamioside, A New Phenolic Glucoside from Daphniphyllum oldhamii

Further phytochemical investigation of the ethyl acetate extract of the stem of Daphniphyllum oldhamii afforded a new phenolic glucoside, named oldhamioside 1, together with eleven known compounds, koaburaside 2, betulin, 28-hydroxyl-3-lupenone, pineresinol, syringaresinol, 4-O-methyl- cedrusin, narigenin, eriodictyol, apigenin, loureirin C, and asperuloside. The structures of new and known compounds were characterized by detailed spectroscopic analysis and comparison of their spectral data with reported values.

Two New Triterpene Esters from Daphniphyllum oldhami

Two new triterpene esters, 2-O-caffeoylalphitolic acid (1) and methyl 2-O-caffeoyl- alphitolate (2), together with two known triterpenes were isolated from the shrub Daphniphyllum oldhami. The structures of new compounds were elucidated on the basis of detailed spectroscopic analysis and compared with related compound.

Daphmacrodins A and B, alkaloids from Daphniphyllum macropodum

Two new daphnicyclidin-type Daphniphyllum alkaloids,daphmacrodins A and B(1 and 2)were isolated from the leaves and stems of Daphniphyllum macropodum.Their structures were elucidated by extensive spectroscopic techniques,including 2D NMR spectroscopy and mass spectrometry.The relative configuration of 1 was further confirmed by a single-crystal X-ray diffraction analysis.Their cytotoxic activities against five human cancer cell lines,pesticidal activities against brine shrimp(Artemia salina),and antibacterial activities against five standard bacterial and fungal strains were evaluated.The structure of 1 was successfully transformed to 2 by a chemical method.

New Secodaphnane-Type Alkaloids with Cytotoxic Activities from Daphniphyllum angustifolium Hutch

One new Daphniphyllum alkaloid,daphnioldhanol A(1),together with three known ones,were isolated from the stem part of Daphniphyllum angustifolium Hutch.Their structures were elucidated by spectroscopic methods and comparing with the literature data.Compound 2 is a new natural product,but known by synthesis as a racemate.Compound 1 exhibited week cytotoxic activity against Hela cell line with IC50 of 31.9μM.

Dcalycinumines A-E,Alkaloids with Cytotoxic Activities of Nasopharyngeal Carcinoma Cells from Daphniphyllum calycinum

Fivenovel Daphniphyllum alkaloids,named dcalycinumines A-E(1-4,6),andeight previously described Daphniphyllum alkaloids(5,7-13)were isolated from Daphniphyllum calycinum.Compound 1 is the first Daphniphyllum alkaloid possessing a highly rearranged 6/6/6/7/5/6 hexacyclic architecture with a unique 3-methyl-1-azabicyclo[4,4,0]decane ring system.Compound 2 represents a rare diamino Daphniphyllum alkaloid with an unprecedented 6/5/5/6/6/5 carbon skeleton featuring a unique 1-aza-6-azaspiro[4,5]decane unit,whereas 3 also represents a rare diamino Daphniphyllum alkaloid as a possible precursor of 2.Compound 4 is the second example of c-22-nor yuzurimine-type alkaloids.Their structures and absolute configurations were elucidated by HRESIMS,NMR spectroscopic analyses,EcD calculations,and single-crystal X-ray diffraction.Moreover,compound 1 showed remarkable antitumor activities,which could inhibit the proliferation,migration and invasion of nasopharyngeal carcinoma cells,and promoted nasopharyngeal carcinoma cells apoptosis.

Total synthesis of a putative yuzurimine-type Daphniphyllum alkaloid C_(14)–epi-deoxycalyciphylline H

One of the largest subfamilies within the famous Daphniphyllum alkaloid family is made up of the yuzurimine-type(or macrodaphniphyllamine-type) alkaloids. Their complex aza-polycyclic caged structures, several contiguous stereogenic centers, and vicinal all-carbon quaternary centers make these alkaloids formidable challenge for synthetic chemists. Recently, synthesis of these alkaloids has received extensive attention from our community. Herein, we wish to report the total synthesis of C_(14)–epideoxycalyciphylline H, a putative member of yuzurimine-type alkaloid subfamily. Key transformations employed in our approach include an intramolecular Prins reaction and a Pd-catalyzed enyne cycloisomerization. In addition, synthesis of a daphnezomine L-type alkaloid, paxdaphnidine A, was also studied.

传统中药交让木Daphniphyllum macropodum生物碱成分的分离鉴别

目的:对采自中国广西的传统中药交让木Daphniphyllum macropodum的生物碱成分进行研究,从中寻找有生物活性的次生代谢产物。方法:用硅胶柱色谱和凝胶柱色谱对交让木D.macropodum氯仿提取物进行分离纯化;根据其理化性质,结合现代波谱技术(MS,NMR等)并与文献报道的数据相比较,对得到的化合物进行结构鉴定。结果:分离得到了4个具有不同骨架的虎皮南生物碱,其结构分别鉴定为:longistylumphylline A(1),deoxycalyciphylline B(2),daphnicyclidin B(3),daphnicyclidin H(4)。结论:4个化合物均系首次从该种植物中分离得到;daphnicyclidin H(4)的发现,进一步证明了它与之前报导的macropodumines A～C在生源上的密切联系。

Asymmetric synthesis of ABC tricyclic systems in Daphniphyllum alkaloid

Efficient synthetic routs for the direct and rapid construction of[5-6-6]ABC tricyclic systems of daphmanidin A-type and calyciphylline A-type alkaloids have been successfully developed.For the daphmanidin A-type,the synthesis of[5-6-6]tricyclic framework utilize a HCl-mediated intramolecular Aldol reaction to construct the bicyclo[2.2.2]octane core and a thermal condensation to afford the ABC ring system.In addition,for the calyciphylline A-type,an improved synthesis of ABC[5-6-6]tricyclic system was developed,featuring an introduction of methyl ester group at C2 before the Pd-catalyzed intramolecular oxidative alkylation to construct the desired bowl-shape tricyclic core with stereochemical control.

交让木内生真菌的分离和抑菌活性的研究

[目的]分离交让木中的内生真菌,并研究其抗菌活性。[方法]先采用尖端菌丝挑取法分离纯化交让木的内生真菌,然后依据《微生物分类学》和形态观察初步鉴定其内生真菌,最后用牛津杯法对内生真菌发酵液进行抑菌试验。[结果]从交让木的茎和叶组织部位分离得到8株内生真菌,初步鉴定为半知亚菌门得丝核菌属1种,头孢霉属2种,木霉属1种,青霉属2种,及接合菌纲的毛霉属1种,根霉属1种。其中JR0203菌株代谢产物有较强的抑菌活性。[结论]交让木内生真菌有一定的抑菌活性,值得进一步研究。

浙江天目山交让木种群空间点格局分析

基于浙江天目山国家级自然保护区常绿落叶阔叶混交林1 hm2样地调查数据,采用空间代替时间和点格局分析法,探究了交让木种群的结构特征、不同生长阶段的空间分布格局及其相互关系.结果表明：（1）交让木种群的径级结构大体呈倒J型,属增长型种群.（2）排除生境异质性影响,交让木幼苗、幼树、中树以及整个种群在1~3 m尺度上呈现微弱的均匀分布格局,其他尺度上呈现随机分布格局.（3）交让木中树与幼树之间基本呈微弱的负相关或无关联性;幼树与幼苗在小尺度区域内呈负相关,随空间尺度增大负相关性减弱至无关联性;中树与幼苗之间呈相对明显的负相关,JazenConnell假说可能是这种格局形成的主要原因.

牛耳枫提取物对甜菜夜蛾酚氧化酶的抑制作用

【目的】筛选对甜菜夜蛾(Spodoptera exigua(Hübner))酚氧化酶具有高抑制活性的化合物,寻找新型害虫控制剂的线索。【方法】以牛耳枫(Daphniphyllum calycinum Benth.)提取物Deoxycalyciphylline B和Methyl homosecodaphniphyllate为抑制剂,采用酶标仪微量法研究了其对甜菜夜蛾酚氧化酶的抑制活性及抑制类型。【结果】Deoxycalyciphylline B和Methyl homosecodaphniphyllate对甜菜夜蛾酚氧化酶的抑制中浓度(IC50)分别为2.439mmol·L-1和0.879mmol·L-1,2种化合物均为典型的可逆竞争型抑制剂,抑制常数(Ki)分别为2.051mmol·L-1和1.269mmol·L-1。【结论】2种生物碱对甜菜夜蛾酚氧化酶具有较好的抑制活性,可以以这2种化合物或其类似物为模板指导酶抑制剂的分子设计,是寻找新型害虫控制剂的重要途径。

黎药牛耳枫化学成分研究

目的:研究黎药牛耳枫枝叶的化学成分。方法:采用多种柱色谱方法进行化学成分分离,利用波谱技术对化合物进行结构鉴定。结果:从黎药牛耳枫中分离得到8个化合物,并鉴定了它们的结构,其分别为:羽扇豆酮(1),β-谷甾醇(2),胡萝卜苷(3),deoxycalyciphylline B(4),daphiodhanins D(5),calyciphylline B(6),槲皮素(7),芦丁(8)。结论:化合物1为首次从交让木属植物中分离得到,化合物3、7、8为首次从该植物中分离得到。

牛耳枫生物碱2-hydroxyyunnandaphnine D体外抗肿瘤活性及作用机制

为了研究牛耳枫生物碱2-hydroxyyunnandaphnine D体外抗肿瘤活性及作用机制,用MTT法检测6.25～100 mg/L 2-hydroxyyunnandaphnine D分别作用于人肝癌细胞(HepG-2)、人乳腺癌细胞(MCF-7)及人宫颈癌细胞(HeLa)后不同时间点的细胞存活并计算细胞增殖抑制率和IC50;FDA/PI双染色荧光显微镜观察细胞死亡情况;分光光度法检测Caspase-3酶活性变化;MTT法检测凋亡抑制剂Z-VAD-FMK对2-hydroxyyunnandaphnine D抑瘤活性的影响.结果显示:2-hydroxyyunnandaphnine D对3种瘤株均有明显的抑制作用,且具有明显的时效量效关系,其48h的IC50值分别为(1.30±0.09),(7.32±0.10)和(8.41±0.11)mg/L.FDA/PI双染色荧光显微镜观察显示2-hydroxyyunnandaphnine D组中死亡细胞数较正常对照组细胞死亡数量增加,且随着剂量的加大细胞死亡数量增加.MTT法显示凋亡抑制剂Z-VAD-FMK不能阻断2个浓度的2-hydroxyyunnandaphnine D对HepG-2细胞的增殖抑制作用.Caspase-3酶活性测定显示l0,30mg/L 2-hydroxyyunnandaphnine D作用后肿瘤细胞的Caspase-3酶活力单位与正常对照组比较无统计学意义.结果表明:牛耳枫生物碱2-hydroxyyunnandaphnine D在体外具有明显的抑制肿瘤细胞增殖的作用,其作用机制并非通过激活Caspase-3途径.

牛耳枫生物碱F21对HepG-2细胞的抑制作用及机制

目的探讨牛耳枫生物碱F21对HepG-2增殖的影响及抗肿瘤作用机制。方法 F21 6.25～100 mg.L-1作用24,48和72 h,MTT法检测细胞抑制率并计算IC50。F21 10～100 mg.L-1作用48 h,瑞姬氏染色光学显微镜下观察细胞形态,琼脂糖凝胶电泳观察DNA的梯形条带,流式细胞仪检测细胞凋亡。F2110,30 mg.L-1+Z-VAD-FMK(胱天蛋白酶抑制剂)20μmol·L-1作用48 h,MTT法检测抑制率。结果 F21可明显抑制HepG-2细胞增殖,其于24,48和72 h的IC50值分别为5.3±0.1,1.3±0.1和(0.13±0.1)mg.L-1,且具有量效(F=232.39,P<0.05)和时效(F=65.59,P<0.05)关系。F21 10～30 mg.L-1可使HepG-2细胞体积增大、胞质内细胞核周围出现大量空泡、细胞膜完整、细胞核破碎甚至细胞形态消失。琼脂糖凝胶电泳未观察到典型的凋亡细胞DNA梯形条带。流式细胞术分析显示,与正常对照组比较,F21 10,30和100 mg.L-1处理HepG-2细胞48 h后,晚期凋亡率分别(17.34±0.01)%,(25.45±0.01)%和(43.67±0.03)%(P<0.05)。Z-VAD-FMK可明显抑制星形孢菌素诱导的细胞死亡。F21 10和30 mg.L-1组的增殖抑制率分别为(18.42±0.09)%和(42.77±0.01)%,而F21 10,30 mg.L-1+Z-VAD-FMK组的增殖抑制率分别为(16.46±0.01)%和(44.01±0.01)%,与相应的F21组相比无统计学差异。结论 F21在体外对HepG-2细胞具有显著的抑制作用,其作用机制并非通过激活胱天蛋白酶途径而诱导肿瘤细胞的凋亡。

牛耳枫的高效液相色谱指纹图谱研究

目的:采用HPLC法对广西荔浦地区的牛耳枫药材进行指纹图谱研究。方法:利用Agilent HP 1260,测定同一地区的12批牛耳枫药材。Waters XBridge^(TM)C_(18)色谱柱(250 mm×4.6 mm,5μm),乙腈(A)-0.1%磷酸溶液(B)为流动相进行梯度洗脱,流速1.0 mL/min,柱温35℃,检测波长254 nm。结果:建立了广西荔浦地区的牛耳枫药材的HPLC指纹图谱,标定了11个共有峰,指认了2个峰,各指纹图谱的相似度均达到0.85以上;利用系统聚类分析,将同一地区的牛耳枫分为3类;利用主成分分析,确定3个主成分,累计贡献率为81.980%;以两个主成分作二维散点图,将不同批次的牛耳枫分为3大类。结论:运用这3种统计分析方法均能够较好的对指纹图谱进行识别,为牛耳枫的鉴别、质量控制等提供了新的科学依据。

枫蓼肠胃康口服液HPLC指纹图谱研究

建立了一种整体定性鉴别和指标成分定量的HPLC指纹图谱方法,对由牛耳枫和辣蓼两味药材组成的枫蓼肠胃康口服液原料及成品进行了指纹图谱研究,并测定了指标成分芦丁、金丝桃苷和异鼠李素的含量。采用Waters ODS C18色谱柱(250 mm×4.6 mm I.D.5μm),用含甲醇和甲酸溶液作为流动相,进行梯度洗脱,并对原料和成品的相应色谱峰进行归属鉴别。结果显示芦丁、金丝桃苷和异鼠李素得到了满意的线性范围,相关系数均大于0.999。按照SFDA的要求,对原料和成品的色谱指纹图谱采用相关系数法和夹角余弦法两种数学方法计算它们的相似度,两种计算方法相似度均不小于0.852。表明建立的枫蓼肠胃康口服液的定性定量方法显著优于传统的质量控制方法。

交让木果实的化学成分研究

目的研究交让木果实的化学成分。方法采用硅胶,RP-18,Sephadex LH-20柱层析对交让木果实的乙醇提取物进行分离纯化,根据化学方法和波谱数据(ESIMS,1D-NMR,2D-NMR)对分离所得化合物进行结构鉴定。结果共分得了5个化合物分别为Paxdaphnine B(Ⅰ),Paxdaphnine A(Ⅱ),Daphgracine(Ⅲ),Daphgraciline(Ⅳ),Yuzurine(Ⅴ)。结论化合物Ⅰ-Ⅴ均为虎皮楠生物碱,并且化合物Ⅰ,Ⅱ为首次从该种植物中分得。

交让木属植物中生物碱类化合物的研究进展

生物碱广泛存在于自然界,是科学家们研究最早的一类有生物活性的天然有机化合物。随着植化分离和结构鉴定手段的提高,越来越多的生物碱类化合物被从交让木属植物中分离鉴定出来,近年来已鉴定80余种化合物。为了更好地开发和利用本属植物,作者在查阅国内外文献的基础上就这一领域的研究进展进行了综述。

牛耳枫中生物碱的研究(英文)

应用各种色谱方法从牛耳枫的茎叶乙醇浸提物中分离得到了8个生物碱,利用波谱(ESI-MS,1HNMR,13C NMR)技术及理化性质分别鉴定为Methyl homosecodaphniphyllate(1),Daphnezomine M(2),Caldaphni-dine E(3),Calyciphylline F(4),Calyciphylline B(5),Deoxycalyciphylline B(6),Daphnicyclidin H(7)和Macropodumine C(8)。