曼地亚红豆杉针叶中紫杉烷二萜类化学成分

目的 研究栽培于我国辽宁本溪的曼地亚红豆杉（Taxus media ‘Hicksii’）针叶中紫杉烷二萜类化学成分。方法 采用大孔树脂、硅胶柱色谱、ODS柱色谱、凝胶柱色谱及MDS柱色谱等方法进行分离纯化,通过NMR分析鉴定化学结构。结果 从曼地亚红豆杉针叶的乙醇提取物中得到6个已知化合物,分别鉴定为10-去乙酰基-10 β-羟基丁酸酯基紫杉醇A(1)、紫杉宁B(,2)、5 α-桂皮酰基红豆杉素(3)、紫杉宁A(4)、5 α-去桂皮酰基紫杉欧吉酚(5)、10-去乙酰基巴卡亭(6)。结论 化合物1、2、3、5为首次从曼地亚红豆杉中分离得到。     

美丽红豆杉心木中紫杉烷二萜的研究

从福建产的美丽红豆杉(Taxus mairei)心木中分离得四个紫杉烷二萜。其结构分别为1-去羟基巴苦亭Ⅵ(1-dehydroxy-baccatin Ⅵ,1),巴苦亭Ⅵ(baccatin Ⅵ,2),1-去羟基巴苦亭Ⅳ(1-dehydroxybaccatin Ⅳ,3)和红豆杉素J(taxinine J,4),其中1为新化合物,结构鉴定应用了高分辨¹HNMR,¹H-¹H COSY等方法。     

由短叶红豆杉的内寄生真菌生产紫杉醇和紫杉烷

从短叶红豆杉韧皮部分离到的内寄生真菌在半合成液体培养基中产生紫杉醇及其相关化合物，以质谱，色 谱以及对紫杉醇特异的单克隆抗体反应鉴定了紫杉醇，真菌培养物中的[1-^14C]乙酸和L-[U-^14C]苯丙氨酸为紫杉醇的前体。     

用东北红豆杉愈伤组织培养物生产具生物活性的紫杉烷[英]／Bai J…∥J Nat Prod

作者以改良的Gamborg’s B5固体介质为培养基对东北红豆杉Taxus cuspidata愈伤组织进行了培养，并对培养物中的紫杉烷类进行了分析。     

东北红豆杉愈伤组织中紫杉烷类化合物的分离与鉴定

目的明确东北红豆杉(Taxus cuspidata)愈伤组织中的化学成分,为开发可持续利用的红豆杉资源提供理论依据。方法采用硅胶柱色谱、制备型高效液相色谱等手段对愈伤组织的正己烷和乙酸乙酯提取物进行分离和纯化;根据化合物的理化性质和波谱数据并结合相关文献对化合物结构进行鉴定。结果从东北红豆杉愈伤组织中分离得到11个紫杉烷类化合物,分别鉴定为tax-uyunnanine C(1)、2α,5α,10β-triacetoxy-14β-propionyloxy-4(20),11-taxadiene(2)、2α,5α,10β-tri-acetoxy-14β-isobutyryloxy-4(20),11-taxadiene(3)、2α,5α,10β-triacetoxy-14β-(2′-methyl)butyrylo-xy-4(20),11-taxadiene(4)、云南红豆杉甲素(yunnanxane,5)、紫杉醇(paclitaxel,6)、taxol C(7)、baccatin VI(8)、1β-deoxybaccatin VI(9)、taxayuntin C(10)、baccatin I(11)。结论化合物9、11为首次从东北红豆杉愈伤组织中分离得到,化合物1-4、8-10尚未在东北红豆杉中发现。     

红豆杉属植物中的紫杉烷二萜

作者从大约100篇文献中收集了来自红豆杉属植物的紫杉烷二萜化合物205个,并按理论与应用化学国际联盟(IUPAC)规定的碳原子编排顺序,分别给出其化学名,并与美国化学文摘(CA)的编号和命名方法举例对照,以供参考。     

曼地亚红豆杉中一个新3,11-环紫杉烷型二萜(英文)

研究曼地亚红豆杉针叶的化学成分,应用硅胶、SephadexLH-20、MCI和反相HPLC等多种色谱手段进行分离和纯化,通过1D,2DNMR和MS方法确定化合物的结构。分离得到一个新化合物,命名为1β,2α,9α,10β-tetrahydroxy-5α-cinnamoyloxy-3,11-cyclotaxa-4(20)-en-13-one(1)。另外鉴定了6个已知紫杉烷型二萜类化合物,分别为2α,7β,9α,10β,13α-pentaacetoxytaxa-4(20),11-dien-5α-ol(2),2-deacetoxy-5-decinnamoyltaxinineJ(3),taxuspineF(4),taxuspinananeK(5),taxchinA(6),baccatinIV(7),其中化合物2,5,6,7为首次在曼地亚红豆杉中得到。     

东北红豆杉愈伤组织中紫杉烷类化合物的分离与鉴定(2)

目的进一步明确东北红豆杉(Taxus cuspidata)愈伤组织中的化学成分,为开发可持续利用的红豆杉资源提供物质基础。方法采用硅胶柱色谱、制备型高效液相色谱等手段对愈伤组织的甲醇提取物进行分离和纯化;根据化合物的理化性质和波谱数据并结合相关文献对化合物结构进行鉴定。结果从东北红豆杉愈伤组织甲醇提取物中分离得到7个紫杉烷型二萜类化合物,分别鉴定为taxusin(1)、2α-acetoxytaxusin(2)、14β-hydroxytaxusin(3)、2-deacetyltaxuyunnanine C(4)、10-deacetyltaxuyunnanine C(5)、7-表-紫杉醇(7-epi-taxol,6)、cephalomannine(7)。结论化合物1~5,7为首次从东北红豆杉愈伤组织中分离得到,化合物3~5尚未在东北红豆杉中发现。     

东北红豆杉中14种紫杉烷化合物对HLE细胞增殖的影响

东北红豆杉(Taxus cuspidata)为红豆杉科红豆杉属植物[1].本文通过观察从东北红豆杉中分离得到的14种紫杉烷化合物进行抑制人肝肿瘤细胞增殖活性的影响,为开发新的治疗肝癌药物提供实验室依据.     

Four new minor taxanes from cell cultures of Taxus chinensis

Four new minor taxanes (1–4) have been isolated from Ts-19 cell cultures of Taxus chinensis together with five known taxanes (5–9) by silica gel chromatography combined with semi-preparative HPLC chromatography. On the basis of the analyses of the chemical and spectroscopic (IR, MS, 1D, and 2D NMR) data, the structures of new compounds were elucidated as 5α-hydroxy-2α,10β-diacetoxy-14β-(3-hydroxy-2-methyl-butyryl)oxytaxa-4(20),11-diene (1), 2α,5α,10β-triacetoxy-14β-(2-hydroxy-propionyl)oxytaxa-4(20),11-diene (2), 2α,5α,10β-triacetoxy-14β-(2-hydroxy-3-methyl-butyryl)oxytaxa-4(20),11-diene (3), and 2α-benzoxy-4α,9α,10β,13α-tetraacetoxytax-11-ene (4), respectively. Compounds 1–5 were pharmacologically evaluated for their cytotoxicities against five human cancer cell lines (HCT-8, Bel-7402, BGC-823, A549, and A2780) and their reversing activity towards multi-drug resistance A549/taxol tumor cell line, and the results showed that all of the tested compounds exhibited very low cytotoxicities, while compound 4 possessed twice the reversing activity as that of verapamil at 10 μM.     

东北红豆杉及其伤愈组织粗提物中紫杉醇的HPLC-ESI-MS/MS分析研究

目的研究紫杉醇的二级质谱裂解规律，对东北红豆杉及其伤愈组织粗提物中的紫杉醇进行HPLC-ESI-MS/MS分离定性，为天然产物中该化合物的分离分析提供一种快速可靠的方法。方法对HPLC-ESI-MS/MS条件进行优化，研究紫杉醇电喷雾质谱的一级电离规律和二级质谱裂解规律，并结合液相色谱的保留时间判断东北红豆杉及其伤愈组织粗提物中紫杉醇色谱峰的归属。结果详细阐明了紫杉醇的二级质谱裂解规律，并利用HPLC-ESI-MS/MS法准确快速地分离定性了两种粗提物中紫杉醇。结论本方法灵敏度高，快速，选择性高，专属性好，能够作为天然产物及其产品中紫杉醇分离定性的一种快速可靠的技术手段。     

Strong antioxidant phenolics from Acacia nilotica: profiling by ESI-MS and qualitative-quantitative determination by LC-ESI-MS

Acacia nilotica (L.) Del. syn is a species rich in polyphenolic constituents, in which catechins are hypothesized to possess antioxidant properties and to play a role in the anti-inflammatory activity of several plants. Due to the complexity of catechin derivatives, the investigation of this class of natural compounds has been limited by difficulties in their separation. In this paper, rationalization of the phenolics occurring in the 80% EtOH extract of Acacia nilotica pods, on the basis of ESI-MS and ESI-MS/MS profiles, has been proposed. Additionally, an LC-ESI-MS qualitative study has been performed by using a C18 polar endcapped stationary phase. The fragmentation pattern obtained evidenced the presence in A. nilotica pods of galloylated catechin- and gallocatechin derivatives along with galloylated glucose derivatives. The structures were confirmed by NMR, after isolation of the pure compounds.In addition, the radical scavenging activities of extracts and pure compounds were investigated, by using the TEAC assay. Furthermore quantitative analyses were performed by LC-ESI-MS/MS, confirming the interest of this species as a rich source of very strong antioxidant principles.     

东北三省不同产区北五味子中有害重金属含量和禁用农药残留量分析研究

目的: 考察来自东北三省31个不同产区北五味子中有害重金属和禁用农药的分布和残留情况。方法: 应用微波消解技术处理北五味子样品,电感耦合等离子体质谱(inductively coupled plasma-mass spectrometry,ICP-MS)法对铅、镉、砷、汞、铜5种重金属元素进行含量测定。同时采用QuEChERS法提取农药,液相色谱-质谱联用(liquid chromatography-mass spectrometry,LC-MS/MS)法对31个产区各10批北五味子中30种禁用农药[《中国药典》(2020年版)四部通则2341农药残留量测定法中新增第五法药材及饮片(植物类)中禁用农药多残留测定法]进行检测。结果: 所检测的31个产区各10批北五味子样品中均未检出30种禁用农药;5种重金属元素含量范围为,铅0.03~0.40 mg·kg^-1;镉0.01~0.06 mg·kg^-1;砷0.04~0.20 mg·kg^-1;汞0.003~0.02 mg·kg^-1;铜3~6 mg·kg^-1。结论: 药材中5种有害重金属的含量均未超过《中国药典》(2020年版)中限定值的三分之一,不存在重金属超标现象;且所有检测药材中均未检出30种禁用农药。     

红豆杉细胞提取物对肿瘤细胞SMMC-7721和HEp-2的作用研究

目的　了解红豆杉细胞提取物对肿瘤细胞SMMC 772 1和HEp 2生长的影响及其抑制机制。 方法　运用MTT比色法测定细胞毒性和流式细胞仪分析细胞周期。结果　红豆杉细胞提取物对SMMC 772 1和HEp 2的IC50 分别为 0 1 61 4 gDCW·L- 1 和 0 2 75 6gDCW·L- 1 。细胞周期分析发现两肿瘤细胞G2 ～M期含量均有所增高。结论　红豆杉细胞提取物可以通过诱导SMMC 772 1和HEp 2发生凋亡而抑制肿瘤细胞的生长     

阿糖胞苷在大鼠体内转化为阿糖尿苷的药动学研究

目的 建立测定大鼠血浆中阿糖尿苷的LC-MS/MS方法,用于大鼠尾iv注射用盐酸阿糖胞苷后阿糖尿苷在体内的药动学研究。方法 采用LC-MS/MS法。ACQUITY UPLC BEH C₁₈色谱柱（50 mm×2.1 mm,1.7 μm）;流动相：水–乙腈,梯度洗脱;体积流量：0.2 mL/min;柱温：40 ℃;进样量：5 μL。离子源：ESI源;扫描方式：多反应监测（MRM）方式,扫描时间为0.1 s;毛细管电压：2.5 kV;锥孔电压：26 V;离子源温度：110 ℃;去溶剂气温度：350 ℃;去溶剂气流量：500 L/h;锥孔气流量：50 L/h。采用回归方程计算血浆中阿糖尿苷。SD大鼠尾iv注射用盐酸阿糖胞苷,制备血药质量浓度–时间曲线,计算药动学参数。结果 阿糖尿苷在1.0～1 000 ng/mL线性关系良好,日内、日间RSD值均小于15%,准确度在±15%,平均提取回收率在90%以上,基质效应在97.3%,稳定性良好。药动学参数：t_max是1.0 h,C_max是134.2 ng/mL,AUC_0-t是2 316.0 ng•h/mL,t_1/2是4.3 h。结论 该方法适合大鼠尾iv阿糖胞苷后阿糖尿苷在体内的药动学研究。     

LC-MS/MS法同时测定细胞孵化液中硫酸雌酮、染料木素及其主要代谢物的含量

目的建立同时测定硫酸雌酮与染料木素的细胞孵化液中硫酸雌酮、染料木素及它们主要代谢物含量的LC-MS/MS法,并用该法研究硫酸雌酮与染料木素在人乳腺细胞中的代谢相互作用。方法细胞孵化样品经处理后,采用Diamonsil C18柱分离,流动相为乙腈和5 mmol.L-1醋酸铵(pH7.8),梯度洗脱,以大豆苷元为内标。采用电喷雾电离(ESI)源,以多反应监测(MRM)方式进行检测,用于定量分析雌酮(estrone,E1)、雌二醇(estradiol,E2),硫酸雌酮(estrone-3-sulfate,E1S)、硫酸雌二醇(estradiol-3-sulfate,E2S)、β-D-葡萄糖醛酸雌酮(estrone-3-glucuronide,E1G)、β-D-葡萄糖醛酸雌二醇(estradiol-3-glucuronide,E2G)、染料木素(genistein,GEN)、染料木素-4'-硫酸结合物(genistein-4'-sulfate,G-4'-S)、染料木素-7-硫酸结合物(genistein-7-sulfate,G-7-S)、染料木素-4'-葡萄糖醛酸结合物(genistein-4'-glucuronide,G-4'-G)和染料木素-7-葡萄糖醛酸结合物(genistein-7-glucu-ronide,G-7-G)。结果该方法中E1、E1S、E2S、G-4'-S、G-7-G的线性为2.45～5 000.00 nmol.L-1,E2的线性为9.80～5 000.00 nmol.L-1,E1G的线性为0.25～500.00 nmol.L-1,E2G的线性为0.98～500.00 nmol.L-1,GEN的线性为19.50～10 000.00 nmol.L-1,G-7-S的线性为2.45～1250.00 nmol.L-1;日内和日间精密度均不大于6.7%,相对误差在±12.5%以内。在人乳腺细胞模型中,GEN促进E1S的代谢,而E1S抑制GEN代谢。结论该法适用于细胞孵化液中硫酸雌酮、染料木素及它们主要代谢物的同时测定,并成功应用于人乳腺细胞中硫酸雌酮与染料木素代谢相互作用的研究。     

Simultaneous Quantification of Six Major Flavonoids From Fructus sophorae by LC-ESI-MS/MS and Statistical Analysis

A new, sensitive and selective high-performance liquid chromatography–tandem mass spectrometric method has been developed for the determination of six major flavonoids including sophoricoside, genistin, genistein, rutin, quercetin, kaempferol in Fructus sophorae. Principal component analysis and hierarchical clustering analysis were used to classify and differentiate these samples. Chromatographic separation was performed on a C₁₈ column with linear gradient elution of methanol and 0.05% acetic acid (v/v) at a flow rate of 0.8 ml/min. The detection was accomplished in the negative mode using multiple-reaction monitoring. The total run time was 8.0 min. Full validation of the assay was carried out including linearity, precision, accuracy, recovery, limit of detection and limit of quantification. The validated method was successfully applied to the simultaneous determination of these active components in Fructus sophorae. The results demonstrated that the quantitative difference in content of six active compounds was useful for chemotaxonomy of many samples from different sources and the standardization and differentiation of many similar samples. Simultaneous quantification of bioactive components by high-performance liquid chromatography–tandem mass spectrometric method coupled with chemometric techniques would be a well-acceptable strategy to comprehensively control the quality of Fructus sophorae.     

Correlative analysis of metabolite profiling of Danggui Buxue Tang in rat biological fluids by rapid resolution LC-TOF/MS

In this work, the metabolite profiles of Danggui Buxue Tang (DBT) in rat bile and plasma were qualitatively described, and the possible metabolic pathways of DBT were subsequently proposed. Emphasis was put on correlative analysis of metabolite profiling in different biological fluids. After oral administration of DBT, bile and plasma samples were collected and pretreated by solid phase extraction. Rapid resolution liquid chromatography coupled to time-of-flight mass spectrometry (RRLC-TOFMS) was used for characterization of DBT-related compounds (parent compounds and metabolites) in biological matrices. A total of 142 metabolites were detected and tentatively identified from the drug-containing bile and plasma samples. Metabolite profiling shows that rat bile contained relatively more glutathione-derived conjugates, more saponins compounds and more diverse forms of metabolites than urine. The metabolite profile in plasma revealed that glucuronide conjugates of isoflavonoids, dimmers, acetylcysteine conjugates and parent form of phthalides, as well as saponin aglycones were the major circulating forms of DBT. Collectively, the metabolite profile analysis of DBT in different biological matrices provided a comprehensive understanding of the in vivo metabolic fates of constituents in DBT.     

Comprehensive chemical analysis of Venenum Bufonis by using liquid chromatography/electrospray ionization tandem mass spectrometry

A rapid, sensitive and versatile liquid chromatography/electrospray ionization tandem mass spectrometry (LC/ESI-MS/MS) method was developed for the comprehensive analyses of the chemical constituents contained in the Chinese medicine-Venenum Bufonis (VB, Chan’ Su in Chinese). LC analysis was carried out on an Agilent Eclipse plus C₁₈ RRHD column (2.1 × 150 mm, 1.8 μm) with a linear gradient solvent system of water (0.1% formic acid) and acetonitrile (0.1% formic acid) as mobile phase. Detection and quantification were performed by multiple reaction monitoring (MRM) transitions via electrospray ionization (ESI) source operating in the positive ionization mode. Through “Molecular Feature Extraction” (MFE), more than 900 features were detected from VB extracts. Among them, a total of 97 components were identified using the Agilent METLIN accurate mass matching database (DB) established according to those reported in the literatures. Further more, 30 high quality matches were obtained by comparisons of their accurate mass and retention times (AMRT) with those imported out in the developed personal database (METLIN DB with AMRT). The characteristic fragmentation pathways were proposed for the tentative characterization of four representative types of bufadienolides in the present work. The targeted MS/MS experiment of the 30 major compounds was performed for their quantification and semi-quantification. And 7 of them were quantified over the assaying concentration range of 5.0-500 pg/μL. The lowest limit of detection and quantification of them were 0.25-0.50 and 1.25-0.25 pg/μL, respectively. The recoveries varied from 83 to 106% depending on the chemical types and different extraction solvents. The remained 23 bufosteroids were simultaneously semi-quantified using three representative standard compounds as their standard references, respectively.