乌头属植物二萜生物碱研究进展

乌头属植物中含有的特征成份二萜生物碱具有较强的毒性和广泛生物活性,多年以来一直是药物学家寻找新药和先导化合物的一个重要来源．也是植物化学分类学家研究的热点。本文从乌头属植物中二萜生物碱的来源,结构及其特点等方面,综述了1998-2008年从乌头属植物中分得的新的二萜生物碱的研究情况。     

黔产乌头的二萜生物碱类成分研究

目的:研究贵州地区产乌头中的二萜生物碱类成分,为进一步丰富乌头属植物的化学成分以及开发利用该药用植物提供参考。方法:取贵州产乌头块根,采用酸提碱沉法提取总生物碱浸膏,并采用硅胶柱层析对总生物碱浸膏进行分离纯化,获得二萜生物碱类成分。结合核磁共振和高分辨质谱分析技术对所获化合物进行结构鉴定。结果与结论:从贵州产乌头中分离鉴定出15个二萜类生物碱,分别为12-epi-15-O-acetyl-17-benzoyl-16-hydroxy-16,17-dihydronapelline(Ⅰ)、宋果灵(Ⅱ)、Songoramine(Ⅲ)、10-羟基乌头碱(Ⅳ)、次乌头碱(Ⅴ)、去氧乌头碱(Ⅵ)、乌头碱(Ⅶ)、新乌头碱(Ⅷ)、14-benzoyltalasamine(Ⅸ)、塔拉萨敏(Ⅹ)、尼奥宁(Ⅺ)、6-表查斯曼宁(Ⅻ)、异塔拉定(ⅩⅢ)、萨卡可尼亭(ⅩⅣ)和多根乌头碱(ⅩⅤ)。其中化合物Ⅸ、Ⅻ均为首次从乌头中分离得到。     

圆滑番荔枝的化学成分研究

目的从番荔枝科植物圆滑番荔枝(annona glabra linn)树皮中分离其化学成分并进行成分分析.方法采用柱层析和红外、核磁共振、质谱仪等进行结构分析.结果分离到6个化合物,其中5个为贝壳杉烷型二萜,1个为生物碱.根据理化性质和波谱特征鉴定其为萜Ⅰ、Ⅱ分别为ent-19-carbomethoxykauran-17-oic acid、19-hydroxy-16α-(-)-kauran-17-oic acid,生物碱Ⅰ、Ⅱ分别为liriodenine、oxoglaucine.结论其中萜Ⅰ ent-19-carbomethoxykauran-17-oic acid、萜Ⅱ19-hydroxy-16α-(一)-kauran-17-oic acid和生物碱Ⅱoxoglaucine为首次从该植物中分得.     

雷公藤多苷片的不良反应

雷公藤多苷片为卫矛科雷公藤属雷公根提取的有效成分制剂，雷公藤作为药物，最早收载于《神农本草经》，名莽草。含生物碱、二萜、三萜、苷类。如雷公藤晋碱、雷公藤甲素、雷酚萜、雷公藤内脂等多种成分。近年来，在临床使用发现有不少不良反应，检索献主要表现在：     

雷酚内酯的结构修正

雷公藤别名黄藤,系卫矛科植物雷公藤(Tripterygium wilfordii Hook.f.)。其根有舒筋活血,祛风湿,消肿止痛的功效,多用于类风湿关节炎的治疗。根皮中含有生物碱、甙、萜以及其它成分,其中多种二萜内酯成分有抗肿瘤活性和免疫     

藏药植物药内源性生物碱类毒性成分的代谢转化及减毒特征研究进展

某些藏药植物药中的活性成分同时也是毒性成分,需要在使用中确切了解其作用机制及代谢途径。毒性较大的藏药植物药,其内源性毒性成分主要为生物碱,如乌头类、甲基牛扁碱等二萜生物碱、莨菪烷类生物碱、马钱子碱、士的宁、罂粟碱和苦马豆素等。藏药植物药中具有代表性的内源性生物碱类毒性成分多存在于根、种子和果实中,多因其剧毒或高毒化学物本质,表现出神经毒性和心脏毒性。一般经去烷基、羟基化和水解等Ⅰ相代谢过程及与葡萄糖醛酸、磺酸结合等Ⅱ相代谢过程,产生多种高极性和毒性减弱的代谢产物,排出体外。多种生物碱的中毒剂量与治疗剂量相近,藏药典籍中常采用炒制、奶制、青稞酒制和诃子配伍等减毒后入药。本文针对包括乌头类二萜双酯、莨菪烷和马钱子碱等在内的5类12种生物碱,着重评述其代谢转化、减毒和安全性评价特点,以期为制定藏药植物药内源性毒性成分限量、临床用药和减毒治疗提供全面参考。     

三叶鼠尾草化学成分的研究

自从丹参酮Ⅱ-A磺酸钠一类化合物应用于冠心病临床以来,我们对同科属植物中二萜醌类的化学成分进行了研究,在寻找资源和新的二萜醌类活性物质过程中,除将甘西鼠尾草褐毛变种[Salvia przewalskli Maxim Var mandarinorum(Diels) Stib]俗名紫丹参推荐工厂,作为投产之原料外,又找到了含丹参酮Ⅱ-A高达0.6%的三叶鼠尾草。     

拟康定乌头中二萜生物碱成分的研究

目的 研究毛茛科乌头属拟康定乌头中的二萜生物碱成分.方法 采用硅胶柱色谱法进行分离,再根据HR-ESI-MS和NMR等多种方法鉴定化合物的结构.结果 从拟康定乌头95％乙醇提取物中分离并鉴定了 17个单体化合物,分别鉴定为 talatisamine、14-O-acetyltalatisamine、dolichotine...     

宣威乌头中生物碱成分的研究

目的 研究宣威乌头Aconitum nagarumvar lasiandrum中的生物碱成分.方法 采用酸提碱沉法提取总碱、硅胶层析法分离,用波谱法鉴定结构.结果和结论 从宣威乌头中分得10个单体化合物,应用光谱法鉴定了其结构为:光翠雀碱(denudatine)、宋果灵(songorine)、delnuttaline等3个C20-二萜生物碱和尼奥灵(neoline)、3-去氧乌头碱(3-deoxyaconitine)、8-methoxy-14-benzoylaconine、伏乌碱(flavaconitine)、异塔拉萨敏(isotalatizidine)、乌头碱(aconitine)和nevadensine等7个C19-二萜生物碱.     

聚伞翠雀生物碱成分的研究

目的研究聚伞翠雀根中生物碱成分。方法采用pH梯度洗脱及硅胶柱层析分离,应用光谱方法鉴定结构。结果从根中分得5个已知二萜生物碱:氨茴酰牛扁碱、牛扁碱、德尔塔生、DelsemineA和DelsemineB。结论5个化合物是首次从该植物中分离得到。     

Alkaloid profiling of herbal drugs using high resolution mass spectrometry

Herbal infusions are consumed worldwide thanks to their “natural” beneficial effects, also due to the presence of alkaloids, although these compounds can have poisonous effects. A method combining online solid‐phase purification with high resolution mass spectrometry was used to define the alkaloid profiles of 117 herbs and 7 commercial blends. Forty‐one alkaloids were quantified in reference to analytical standards, while the presence of a further 116 was confirmed based on accurate mass, retention time, and fragmentation profile. The targeted study showed that 52% of herbs and 42% of commercial blends contained at least one alkaloid. Pyrrolizidines were the most commonly present (26% of samples), with concentrations generally ranging from the quantification limit to roughly 100 μg kg^?1. Moreover, a homemade infusion was studied, finding on average 45% and 6% lower extraction for pyrrolizidine and steroidal alkaloids, respectively. Nevertheless, the migration of pyrrolizidines was confirmed. The study confirmed the frequent presence, natural or accidental, of alkaloids in commercial infusion herbs, highlighting the urgent need for routine and accurate controls.     

延胡索与川楝子配伍中总生物碱含量变化的研究

目的：测定延胡索及其与川楝子配伍中总生物碱的含量，研究中药配伍的合理性。方法：采用有机溶剂提取法对样品中生物碱进行提取，酸碱滴定法分别测定延胡索及延胡索与川楝子配伍水煎液中总生物碱的含量。结果：延胡索和延胡索与川楝子配伍中总生物碱含量分别为2．219mg／g和3．422mg／g，配伍后较延胡索单品中生物碱含量高1．203mg／g，经统计学处理，P〈0．01。结论：川楝子与延胡索配伍，对其生物碱的含量有显著的影响。     

附子配伍原则的电喷雾质谱研究

目的从化学角度探讨附子配伍的原则。方法利用电喷雾质谱分析和比较生附子及其复方中药煎煮液中二萜类生物碱的变化规律；测定附子及其他中药煎煮液的pH值并用电喷雾质谱考察酸性对药材中乌头碱水解的影响。结果生附子单煎煮及与甘草共煎后双酯型乌头生物碱大部分发生水解，生附子与半夏或五味子共煎生物碱水解受抑制，生附子和甘草单煎液的酸性远低于半夏或五味子单煎液，中乌头碱在酸性条件下不水解。结论酸性是影响乌头碱类双酯型生物碱水解的重要因素，强酸条件下水解受抑制，附子煎煮液毒性增加。     

Chemical constituents and analgesic activity of Aconitum kusnezoffii Reichb.

In the present study,we aimed to investigate the chemical constituents and analgesic activity of Aconitum kusnezoffii Reichb. The isolation and purification of components were achieved by a series of chromatography, including silica gel, Sephadex LH-20 and HPLC. By using spectroscopic analysis, their structures were identified. Using PDE-4A as analgesic target, moleculardocking was conducted between isolated compounds by using Schrodinger software. Neoline is a typical non-ester diterpene alkaloid. It was studied by using the mouse torsion body method and hot plate method. A total of 12 diterpene alkaloids were obtainedand identified as Mesaconitine(1), Bewutine (2), Bewudine (3), Songoramine (4), Songorine (5), Neoline (6), Talasamine (7), isotalatizidine (8), Hokbusine A (9), Mesaconine (10), 8-OEt-14-benzoylmesaconine (11), 8-Methoxy-14-benzoyl-beiwutinine (12).Compounds 9 and 12 were isolated from Aconitum kusnezoffii Reichb. for the first time. Twelve diterpenealkaloids could act on the analgesic target. Neoline is a typical non-ester diterpene alkaloid. It had significant analgesic effect. Diterpene alkaloids were the main components of Aconitum kusnezoffiiReichb., and they had good analgesic activity.     

Structural analyses of protoberberine alkaloids in medicine herbs by using ESI-FT-ICR-MS and HPLC-ESI-MS(n)

The Electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FT-ICR-MS) using sustained off-resonance irradiation (SORI)/collision-induced dissociation (CID) method at high mass resolution has been first applied to investigate the characteristic fragment ions of four protoberberine alkaloids in medicine herbs. The ESI-FT-ICR SORI-CID experiment results demonstrate that the unambiguous elemental composition of fragment ions can be obtained at high mass resolution, then the logical fragmentation pathways of the protoberberine alkaloids has been proposed. The characteristic fragment ions of CID and MS(n) of protoberberine alkaloids have been discussed, which are specific and useful for the identification of some protoberberine alkaloid compounds. Then, the extracts of four kinds of medicine herbs have been analyzed by HPLC-ESI-MS(n). According to these characteristic fragmentation pathways, the retention time (t(R)) of HPLC and mass spectra of product ion, the structures of six kinds of protoberberine alkaloids have been identified. And, in the present paper, the selected ion monitoring (SIM) method has been used to separate and identify the alkaloid isomers.     

千里光属(Senecio)13种植物的形态和组织学特征

千里光在很多中成药中应用,但因其含有肝毒性吡咯里西啶生物碱而引起国际上的关注。为保证临床用药的安全,本文对千里光属11种、2变种药用植物的形态组织学特征进行了鉴定研究,了解千里光属植物的显微鉴定特征,为该类生药的商品鉴定提供依据。在性状鉴定的基础上,对千里光属生药茎横切面、叶表皮形态进行了观察比较。千里光属药材在生药性状、茎横切面、叶表面垂周壁观形态特征具有不同程度的差异,可以明显鉴别13种生药,为千里光类生药的鉴定提供依据。     

~(60)Co-γ射线辐照贮藏对川贝母质量的影响

目的:研究~(60)Co-γ射线辐照贮藏对川贝母质量的影响。方法:对不同剂量~(60)Co-γ射线辐照处理过的川贝母的霉变、虫蛀情况进行观察,并对辐照和未辐照川贝母的总生物碱和水溶性核苷类成分进行含量比较。结果:经辐照后的川贝母的化学成分、感观形态无明显变化,能有效地防止霉变和虫蛀,明显延长药材的贮藏期;川贝母辐照前后总生物碱和水溶性核苷类成分无含量显著变化。结论:应用~(60)Co-γ射线辐照灭菌杀虫工艺可为富含淀粉及贵重中药材的贮藏提供有效方法。     

两种工艺对舒胃颗粒中黄连生物碱含量的影响

目的:比较黄连与其余药材混煎及分煎合并两种工艺对舒胃颗粒中黄连生物碱含量的影响。方法:以黄连生物碱提取量为考察指标,采用紫外分光光度法测定黄连生物碱含量,对两种水提取方法进行比较。结果:按黄连药材投量计,混煎、分煎合并和黄连单煎所得3个样品中生物碱含量以盐酸小檗碱计,分别为3.88%,6.47%,8.37%。结论:分煎合并工艺中黄连生物碱损失量明显少于混煎工艺。     

黄连中原小檗型生物碱的分离与鉴定

目的:研究黄连中的原小檗型生物碱成分。方法:采用溶剂提取、色谱分离等手段对样品进行分离、纯化,根据波谱数据进行化合物结构鉴定。结果:从黄连中分离出6个生物碱成分,分别鉴定为盐酸小檗碱、盐酸黄连碱、盐酸药根碱、盐酸非洲防己碱、盐酸表小檗碱、盐酸巴马汀。结论:该方法简单、可行,可为黄连药材及其制剂的质量标准提供对照品。本试验为首次采用直接分离纯化的方法从黄连中得到盐酸表小檗碱。     

A comparative study of commercial samples of ephedrae herba

A total of 22 commercial Ephedra herba samples which belonged to EPHEDRA SINICA, E. INTERMEDIA, E. EQUISETINA, and E. DISTACHYA, respectively, were collected from the Taiwan herbal market. The contents of the six ephedrine alkaloids - ephedrine (E), pseudoephedrine (PE), methylephedrine (ME), methyl-pseudoephedrine (MPE), norephedrine (NE), and nor-pseudoephedrine (NPE) - in these samples were determined by capillary electrophoresis and were found to differ greatly among the samples. Generally, E. SINICA was superior (1.594 +/- 0.467%) and E. INTERMEDIA was inferior (1.210 +/- 0.372%). Among the individual constituents, the sum of E and PE contents in each sample was about nine-tenths of the total alkaloids, and the ratios of E/PE, ME/MPE, and NE/NPE in the given species were definite and could be used to aid in identifying the origin of the herbs. The alkaloid contents were found to be higher in the internodes of the herbs and in those items with thin stems, more powdery and less fibrous characters. There were no indications for alkaloids in the roots of the plants.