乌头类生物碱组分在CYP450中的代谢指纹图谱及对CYP450活性的影响

利用超高效液相色谱-串联质谱(UPLC-MS/MS)的多反应监测(MRM)技术, 结合多探针底物方法, 对单酯型及双酯型乌头类生物碱组分对细胞色素P450(CYP450)亚型的活性影响进行了研究; 同时利用超高效液相色谱-四极杆-飞行时间串联质谱(UPLC-Q-TOF-MS/MS)对单酯型和双酯型乌头类生物碱组分在CYP450中的代谢指纹图谱进行了研究. 活性影响研究结果表明, 单酯型生物碱组分对CYP2C及2D的抑制能力较强, 其IC₅₀值分别为7.44和6.74 μmol/L; 双酯型生物碱组分对CYP1A2, 3A, 2C和2D均有较弱的抑制作用, 其IC₅₀值分别为39.48, 70.44, 17.36和86.04 μmol/L. 代谢指纹图谱显示, 双酯型生物碱组分在大鼠肝微粒体中有6个特异性产物可以作为该反应的特征峰.     

草乌中二萜类生物碱的电喷雾串联质谱研究

利用电喷雾质谱技术对传统中药草乌中的二萜类生物碱进行直接分析鉴定.通过实验数据并对比文献发现,草乌中含有单酯型、双酯型、三酯型和脂类等共4种类型生物碱,其中三酯型和脂类生物碱在草乌中为首次发现.由于这些生物碱的结构相似,在电喷雾串联质谱中碎裂方式相同,因此根据电喷雾串联质谱结果确定了这些生物碱的结构.     

复方中药四逆汤中乌头碱类二萜生物碱的电喷雾串联质谱研究

利用电喷雾串联质谱方法不经柱分离而直接分析复方中药四逆汤中二萜生物碱的组成,乌头碱类二萜生物碱在质谱条件下形成质子化分子,一种生物碱对应一个分子离子峰.检测到了苯甲酰单酯型、双酯型和脂类生物碱等18种二萜生物碱,其中苯甲酰中乌头原碱等单酯型生物碱是四逆汤中的主要生物碱成分.     

吗啡烷型生物碱类药物的化学发光分析法研究

雷氏盐（ＮＨ４Ｃｒ（ＮＨ３）２（ＳＣＮ）４）．Ｈ２Ｏ）是生物碱类物质的沉淀剂，经研究发现，雷氏盐可以催化鲁米诺与过氧化氢的化学发光反应，而吗啡烷型生物碱能沉淀雷氏盐，可导致鲁米诺－过氧化氢－雷氏盐体系化学发光强度的降低，根据这一发现，本文建立了吗啡烷型生物碱类药物（吗啡，青藤碱，可待因）的流动注射化学发光分析方法，方法有较低的检出限，较宽的线性范围和较好精密度用于一些药物的测定，结果较为满意。     

近红外光谱法快速测定附子中6个生物碱的含量

应用近红外光谱(NIRS)技术结合偏最小二乘(PLS)和最小二乘支持向量机(LS-SVM)建立了附子中多指标成分的快速无损检测方法。选取38批样品建立了同时测定附子样品中6种成分含量的高效液相色谱(HPLC)方法;通过采集附子样品的NIRS图,分别采用PLS和LS-SVM建立了各个成分HPLC测定值与NIRS图的定量校正模型。所建立的苯甲酰新乌头原碱、苯甲酰乌头原碱、苯甲酰次乌头原碱、新乌头碱、次乌头碱、乌头碱、单酯型生物碱总量和双酯型生物碱总量LS-SVM模型的相对预测偏差(RPD)分别为3.3、3.2、4.1、7.7、8.8、7.6、4.0和8.6;验证集相关系数(rpre)分别为0.9486、0.9475、0.9668、0.9909、0.9946、0.9969、0.9669和0.9927,且LS-SVM模型优于PLS模型,说明NIRS模型验证集与HPLC测定值具有良好的非线性关系,模型预测效果良好。采用NIRS技术结合LS-SVM模型可以快速对附子中的上述6个生物碱含量以及单酯型生物碱总量和双酯型生物碱总量进行检测,方法操作简便,对控制附子中的生物碱含量具有一定的指导作用。     

液相色谱-质谱法研究附子生物碱的煎煮减毒机理

建立了基于液相色谱-质谱分析的附子中生物碱指纹分析方法,并将其应用于附子煎煮减毒的机理研究。基于质谱特征鉴定了生物碱标准品在加热回流过程中产生的6种降解产物,确定了双酯型生物碱的煎煮条件降解规律。在此基础上研究了附子饮片煎煮不同时间条件下生物碱的指纹变化,结果表明,长时间煎煮可明显降低双酯型生物碱和生物脂碱的浓度,为附子的安全用药提供了科学依据。     

生附片化学成分的HPLC/ESI-MSn研究

采用高效液相色谱与电喷雾质谱联用技术, 对生附片的化学成分进行了系统的研究. 并辅以提取离子色谱方法, 发现微量的化学成分. 通过保留时间, 质荷比及多级串联质谱数据, 共鉴定了48个成分, 其中双酯型生物碱8个, 单酯型生物碱7个, 脂型生物碱29个. 其中双酯型生物碱是生附片中的主要成分, 而单酯型和脂型生物碱的含量和种类较少.     

生附片化学成分的HPLC/ESI-MSn研究

采用高效液相色谱与电喷雾质谱联用技术, 对生附片的化学成分进行了系统的研究. 并辅以提取离子色谱方法, 发现微量的化学成分. 通过保留时间, 质荷比及多级串联质谱数据, 共鉴定了48个成分, 其中双酯型生物碱8个, 单酯型生物碱7个, 脂型生物碱29个. 其中双酯型生物碱是生附片中的主要成分, 而单酯型和脂型生物碱的含量和种类较少.     

金鸡纳生物碱-丙烯酸甲酯共聚物及其水解型聚合物的合成

不对称氢化反应;聚合物;金鸡纳生物碱-丙烯酸甲酯共聚物及其水解型聚合物的合成     

由黄连混合生物碱制备巴马汀

黄连混合生物碱经脱亚甲二氧基或甲氧基、加氢、甲基化及氧化反应完成生物碱转化制得巴马汀,总收率12％,其结构经1H NMR,IR和MS确证.     

Alkaloids from stems of Ervatamia yunnanensis

Six indole alkaloids were isolated from the stems of Ervatamia yunnanensis. Among them, yunnanensine (I) is new. The other five are known alkaloids, namely: 19,20-E-vallesamine (II), 19s-heyneanine (HI), ibogaine (IV), ibogamine (V), coronaridine (VI). The structural elucidation of the alkaloids was based on spectral means.     

Louis Pasteur,Chemist: An Account of His Studies of Cinchona Alkaloids

Pasteur carried out pioneering work on cinchona alkaloids and their derivatives and his studies led to important discoveries. He examined crystals of cinchona alkaloids for his correlation of crystal hemihedrism with molecular chirality, studies that led Pasteur to the discovery of physicochemical differences between diastereoisomeric salts of tartaric acids with optically active cinchona bases, an important insight into fundamentals of molecular chirality. These physicochemical differences also led to Pasteur’s invention of the vital method of racemate resolution through diastereoisomeric derivatives. Pasteur clarified the confusion around the cinchona alkaloids by elucidating their identities and relations. He discovered the conversion of the major cinchona alkaloids to quinicine and cinchonicine, a finding subsequently of considerable importance in studies of the structure and synthesis of the major cinchona alkaloids. The reaction producing quinicine and cinchonicine led Pasteur to the discovery of the racemization of tartaric acid and the finding of meso‐tartaric acid, fundamental breakthroughs in the development of stereochemistry.     

Pyrrolizidine-Derived Alkaloids: Highly Toxic Components in the Seeds of Crotalaria cleomifolia Used in Popular Beverages in Madagascar

Seeds of Crotalaria cleomifolia (Fabaceae) are consumed in Madagascar in preparation of popular beverages. The investigation of extracts from the seeds of this species revealed the presence of high amounts of alkaloids from which two pyrrolizidine-derived alkaloids were isolated. One of them was fully characterized by spectroscopic and spectrometric methods, which was found to be usaramine. Owing to the high toxicity of these alkaloids, issuing a strong warning among populations consuming the seeds of Crotalaria cleomifolia must be considered.     

吲哚类生物碱的合成研究进展

吲哚类生物碱是具有吲哚分子骨架的一类化合物,具有多种良好的生理活性。文章综述了近年来新发现吲哚类生物碱的合成研究进展,介绍了(-)-Arboricine,(±)-cis-Trikentrin A,(-)-Corynantheidol等化合物的合成方法。     

二维高效液相色谱技术用于分析中药制剂中麻黄类生物碱

构建了一个离线的二维高效液相色谱系统,以解决成分复杂的中药样品的分离和痕量组分的定量问题。该系统在原有的单泵、单检测器高效液相色谱仪的基础上作了相应的改进而构成,样品先在第一维的Zor-bax SB-C18色谱柱中进行分离之后,利用一个六通切换阀将目标组分切换并收集,浓缩后再注入第二维的Ai-chrom Bond-AQ C18色谱柱中进行分离。利用上述方法对3种麻黄类生物碱进行了二维分离和分析,实验结果表明,样品的分离明显改善,并且这个系统可用于中药的直接进样分析。     

Amaryllidaceae Alkaloids from Lycoris radiata

A phytochemical investigation on bulbs of Lycoris radiata resulted in the isolation of three new Amaryllidaceae alkaloids, named 5,6‐dehydrodihydrolycorine ( 1 ), 6β‐acetoxycrinamine ( 2 ), and (+)‐8‐O‐acetylhomolycorine α‐N‐oxide ( 3 ), together with eleven known alkaloids, 4 – 14 . The structures of the new alkaloids were established by means of spectroscopic methods, and the known compounds were identified by comparison of their data with those in the literature. Compound 2 showed cytotoxicity against HL‐60, A‐549, and MCF‐7 cells, with IC₅₀ values of 8.1, 24.3, and 15.0 μM , respectively.     

Two New Nitrone Alkaloids from Huperzia serrata

Two new nitrone alkaloids were isolated from the whole plant of Huperzia serrata (Thunb .) Trev . They are both phlegmarine‐type lycopodium alkaloids with a nitrone moiety. Their structures were elucidated on the basis of spectral evidences, and their configurations were established on the basis of optical rotation, CD, and NOESY‐NMR data.     

Two New Indole Alkaloids from Emmenopterys henryi

Two new indole alkaloids, 5‐oxodolichantoside ( 1 ) and deglycocadambine ( 2 ), were isolated from the twigs and leaves of Emmenopterys henryi, together with four known indole alkaloids and five known iridoids. The structures of the new compounds were elucidated on the basis of extensive spectroscopic analyses, including 1D‐ and 2D‐NMR experiments, and confirmed by single‐crystal X‐ray diffraction studies. This is the first report on the isolation of indole alkaloids from this species. The indole alkaloids were evaluated for their cytotoxic activities against five human cancer lines.     

Ring Enlargement of Alkaloids

Previouspublications'fromourlaboratoryhadreportedtheringenlargementreactionofquatemaryarnrnoniumsaltSofN-methyl-tetTahydroisoquinolinefollowedbyreductivedecyanationwiththenetresuItoftheinserti0nofanextraCH2group,assh0wninSckemeI.ThemethodologyfailedwithsomenatUrallyoccurringalkaloidssuchascephalotaxineandatropine'.Onereasonisthatsomeofthequaternaryammoniumsaltsaredifficulttoprepare,theotheroneisthatsome0fthequaternaryafnmoniumsaItsunderwentHofinarineliminationorSofnmeletrearrangement'.But…