麻黄-甘草药对配伍过程中的主要药效成分的分析

利用高效液相色谱串联质谱联用法(HPLC-MS/MS)和气相色谱质谱联用法(GC-MS)分析了麻黄与甘草药对配伍前后水煎液中主要药效成分的变化,并通过小鼠的耳廓肿胀试验考察了甘草、麻黄单煎液及药对共煎液的抗炎活性变化。分别通过HPLC法和GC-MS法对甘草与麻黄中主要化学成分,甘草酸、甘草苷、麻黄碱和甲基麻黄碱进行了定量分析,通过单煎液和药对共煎液的对比,发现麻黄与甘草配伍共煎液中麻黄碱（含伪麻黄碱）的含量增加了14.52%;甲基麻黄碱（含甲基伪麻黄碱）的含量增加了64.0%;甘草酸含量增加了13.50%;而甘草苷含量降低了19.38%。药效实验证明,甘草与麻黄配伍后抗炎作用较甘草麻黄单煎液明显增强。从而在主要成分的变化程度上揭示了甘草与麻黄配伍过程中的增效机理。     

电喷雾串联质谱分析附子炮制中的化学成分变化

利用电喷雾质谱方法(ESI-MS)分析了附子加辅料(甘草)炮制前后水煎液中二萜类生物碱在种类和含量方面的变化,通过加入内标化合物,建立了电喷雾质谱的半定量分析方法。此方法具有快速、准确、灵敏的特点,能够更加全面地反映中药配伍炮制过程中多种化学成分的含量变化,并能根据电喷雾串联质谱的分析结果鉴定配伍后产生的新的化学成分,在共煎液中的次乌头碱、中乌头碱和乌头碱的相对含量分别是单煎液中的5.67%、4.05%和4.88%。通过研究附子与甘草的单煎液、共煎液以及药渣中化学成分的变化,揭示了甘草作为辅料,在炮制过程中对附子减毒作用机理。     

离子对色谱法测定麻杏石甘汤中的麻黄碱和伪麻黄碱

麻杏石甘汤出自《伤寒论》,由麻黄、杏仁、甘草和石膏四味中药组成。麻黄主要含麻黄碱和伪麻黄碱,两者是麻杏石甘汤中的主要有效成分。对麻黄及其制剂中的麻黄碱和伪麻黄碱含量测定的方法主要有高效液相色谱法（HPLC）、高效毛细管电泳法和气相色谱-质谱联用法等。由于麻黄碱和伪麻黄碱结构相似,而且生物碱容易产生拖尾现象,采用反相高效液相色谱法一般难以使两者达到良好的分离。本文采用反相离子对HPLC使两者获得了良好的分离,并以此法对麻杏石甘汤中的麻黄碱和伪麻黄碱进行了测定。     

电喷雾质谱半定量方法研究制川乌配伍后的大鼠肠内菌生物转化

利用建立的代谢前后生物碱成分的电喷雾质谱半定量分析方法,通过分析各药对共煎液经大鼠肠内菌群代谢后主要生物碱的含量变化,对制川乌与浙贝母、法半夏、白蔹分别配伍后共煎液中双酯型、单酯型及脂型生物碱的肠内菌生物转化进行了深入研究,研究结果表明,配伍后中药浙贝母增加共煎液中双酯型生物碱含量,法半夏降低共煎液中双酯型生物碱含量,而白蔹对共煎液中双酯型生物碱含量影响不大;在代谢过程中,大鼠肠内菌群能够将复方中双酯型生物碱转化为脂型生物碱,从而达到中药配伍的减毒增效目的。本文通过化学方法和肠内菌代谢研究证明了制川乌配伍及代谢的机理。     

高效液相色谱法测定麻黄浸膏粉中麻黄类生物碱

采用高效液相色谱法分离了麻黄浸膏粉中去甲基麻黄碱、去甲基伪麻黄碱、麻黄碱、伪麻黄碱和甲基麻黄碱等 5种主要麻黄类生物碱。所用分离柱为HIQSILC18,流动相为含少量 (体积分数为 0 .2 % )甲醇的 0 .0 2mol L磷酸二氢钠溶液 (用HCl和三乙胺调至pH 3.2 )。 5种麻黄类生物碱在 2 5min内得到了有效分离、峰型对称且尖锐。     

川乌与半夏、瓜蒌、贝母、白蔹、白芨配伍禁忌的化学研究

运用高效液相色谱方法,定量分析了川乌单煎液及其与生半夏、法半夏、全瓜蒌、瓜蒌皮、瓜蒌籽、浙贝母、川贝母、白蔹、白芨共煎液的双酯型生物碱含量.并利用电喷雾质谱通过加入内标的半定量分析方法研究生川乌配伍前后生物碱成分和含量的变化.结果显示生川乌与生半夏、瓜蒌籽、全瓜蒌、瓜蒌皮、浙贝母、白芨的共煎液中双酯型生物碱含量高于生川乌单煎液而生川乌与法半夏、川贝母、白蔹的共煎液双酯型生物碱含量变化微弱或有所减少.电喷雾质谱半定量分析方法与高效液相色谱方法的分析结果一致,并且与上述药对的LD50值结果也基本一致.而毒性成分的变化趋势与共煎前后溶液的pH变化相关.     

液质联用技术研究人参与干姜或赤芍配伍前后人参皂苷及其抗氧化活性的变化

采用高效液相色谱与电喷雾质谱联用技术(HPLC-ESI-MS),对不同质量比的人参与干姜或赤芍配伍过程中人参皂苷的变化进行了研究,发现随加入的干姜量增加,共煎液中的人参皂苷含量依次降低;少量的赤芍可以使各皂苷的溶出量增加;同时测定了人参单煎液、人参与干姜、赤芍共煎液中正丁醇提取物和水提物的抗氧化活性。 以抗坏血酸(500 μmol/L)作对照,人参与干姜、赤芍配伍溶液的抗氧化活性比人参单煎液要好,同时人参与干姜、赤芍共煎液中正丁醇提取物的FRAP(铁离子还原/抗氧化能力测定)值分别为1562.29和2969.78 μmol/L,高于人参与2种药单煎液（1260.27和2502.07 μmol/L）之和。     

"甘草附子汤"和"术附汤"肠内生物转化的电喷雾质谱研究

以电喷雾质谱法作为研究方法,以内标化合物为切入点,对复方中双酯型、单酯型及脂型生物碱的生物转化进行了深入研究,建立了电喷雾质谱对代谢前后生物碱成分的半定量分析方法.分析了中药复方甘草附子汤和术附汤经大鼠肠内菌群代谢主要生物碱的含量变化,研究结果表明,配伍中药甘草和白术可以有效地降低共煎液中双酯型生物碱含量,在代谢过程中...     

超高效液相色谱-质谱结合主成分分析方法研究制川乌配伍前后的肠内菌代谢差异

利用超高效液相色谱-质谱联用( UPLC-MS)技术结合主成分分析方法研究制川乌单煎液、制川乌与白芍、制川乌与防己共煎液在大鼠肠内菌中的代谢差异。采用SIMCA-P软件,以肠内菌代谢后乌头类生物碱的相对含量为变量进行主成分( PCA)分析。在主成分得分图中,制川乌单煎液与制川乌-白芍、制川乌-防己共煎液均可以明显区分,说明制川乌单煎液与制川乌-白芍、制川乌-防己共煎液的肠内菌生物转化存在显著差异。通过主成分分析载荷图及独立样本t检验,从制川乌-白芍组得到7种差异显著的标志物,从制川乌-防己组得到6种标志物,其中制川乌-白芍组有4种标志物经肠内菌代谢后含量高于制川乌组,而制川乌-防己组有1种化合物含量高于制川乌组,两组中其它标志物含量低于制川乌组。这些标志物可能是制川乌配伍前后药效差异的物质基础。     

毛细管微乳液电动色谱和胶束电动色谱分离冰毒及其麻黄碱杂质的比较

通过毛细管微乳液电动色谱10 m in内同时分离了安非他明、甲基安非他明、4,5-亚甲基二氧基安非他明(MDA)和3-甲氧基-4,5-亚甲基二氧基安非他明(MDMA)4种苯丙胺类毒品及其麻黄碱、伪麻黄碱、甲基麻黄碱、甲基伪麻黄碱、去甲麻黄碱等麻黄生物碱杂质。比较了毛细管微乳液电动色谱和丁醇改进的胶束电动色谱模式对分离的影响,发现正丁醇是影响分离的最主要因素。本方法具有很好的重复性和稳定性,可实现对冰毒及其麻黄生物碱杂质的快速分析和鉴定,相对保留时间和相对峰面积的RSD分别小于1.3%和5.0%,可用于冰毒的实际来源推断。     

Isolation and identification of the anti-isohumulones and the anti-acetylhumulinic acids

The anti-isohumulones [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-hydroxy-4-(4-methylpent-3-enoyl)-cyclopentane-1,3-diones] and the anti-acetylhumulinic acids [5-(3-methylbutanoyl)-2-(3-methylbut-2-enyl)-4-ethanoyl-4-hydroxy-cyclopentane 1,3-diones] have been isolated from an isomerisation reaction mixture of humulone [2-(3-methylbutanoyl)-4,6-di(3-methylbut-2-enyl)-6-hydroxy-cyclohexane-l,3,5-trione] by counter-current distribution and identified by spectroscopic techniques. The formation mechanism is presented and the stereochemical consequences are discussed. The anti-isohumulones are the most bitter hop compounds presently known.     

The energy pump and the origin of the non-equilibrium flux of the dynamical systems and the networks

The global stability of dynamical systems and networks is still challenging to study. We developed a landscape and flux framework to explore the global stability. The potential landscape is directly linked to the steady state probability distribution of the non-equilibrium dynamical systems which can be used to study the global stability. The steady state probability flux together with the landscape gradient determines the dynamics of the system. The non-zero probability flux implies the breaking down of the detailed balance which is a quantitative signature of the systems being in non-equilibrium states. We investigated the dynamics of several systems from monostability to limit cycle and explored the microscopic origin of the probability flux. We discovered that the origin of the probability flux is due to the non-equilibrium conditions on the concentrations resulting energy input acting like non-equilibrium pump or battery to the system. Another interesting behavior we uncovered is that the probabilistic flux is closely related to the steady state deterministic chemical flux. For the monostable model of the kinetic cycle, the analytical expression of the probabilistic flux is directly related to the deterministic flux, and the later is directly generated by the chemical potential difference from the adenosine triphosphate (ATP) hydrolysis. For the limit cycle of the reversible Schnakenberg model, we also show that the probabilistic flux is correlated to the chemical driving force, as well as the deterministic effective flux. Furthermore, we study the phase coherence of the stochastic oscillation against the energy pump, and argue that larger non-equilibrium pump results faster flux and higher coherence. This leads to higher robustness of the biological oscillations. We also uncovered how fluctuations influence the coherence of the oscillations in two steps: (1) The mild fluctuations influence the coherence of the system mainly through the probability flux while maintaining the regular landscape topography. (2) The larger fluctuations lead to flat landscape and the complete loss of the stability of the whole system.     

On the transport and trajectories of the chernobyl debris across Canada and the arctic

A scenario is presented for the transport of the Chernobyl radioactive debris across Canada and the Arctic. It is based on the analysis of the¹⁰³Ru/¹³⁷Cs ratios in terms of the Chernobyl release pattern. The ratios which ranged from 0.2 to more than 4.0 were associated with four different phases of the Chernobyl emissions which lasted 10 days, from April 26 to May 6, 1986. Debris from the initial phase /ratios of 0.2 to 0.5/ and the last phase /ratios above 2.5/ would have entered Canada on a very broad front extending from northern Quebec to the North West Territories by way of Greenland and the Arctic; debris from the second phase /ratios of 0.5 to 2.0/ and the third phase /ratios of 2.0 to 2.5/ would have entered Canada from the west after travelling by way of northern Siberia and the Bering Sea.Paper presented at the IVth International Symposium of Radioecology of Cadarache, France, March 1988.     

Analysis and assessment of the occurrence, the fate and the behavior of nanomaterials in the environment

Nanomaterials have one dimension <100 nm and possess physico-chemical properties dictated by their unusually small size, large surface area, shape and chemical composition. New properties of nanomaterials have boosted their production and industrial applications in many fields (e.g., microelectronics, catalysis, fuel cells, materials science, textiles, biotechnology and medicine). In biomedical fields, nanomaterials are of the appropriate dimensions to interact with biological matter. However, they may also have negative effects on biological systems. Nanotechnology is a major, innovative, scientific and economic growth area, but the increasing production and use of nanomaterials have led to calls for more information regarding the potential impacts that their release may have on human health and the environment.This review addresses analytical approaches for characterization and quantification of nanomaterials in the environment and recent studies on their occurrence, fate and behavior.     

Decorating step-by-step and independently the surface and the core of dendrons

Dendrons possessing one activated vinyl group at the core and several chlorine atoms at the end of the branches are used as starting materials to study the possibility to react independently the surface functions and the core function. In particular, the most powerful sequence of reactions for decorating them by organometallic complexes as end groups and amine or alcohol at the core has been determined. In the first step, phenol phosphines are grafted as end groups of the dendrons, and they can be used for the complexation of metals. However, these phosphines must be kept free when amines are used to react with the vinyl core in the next step. Depending on the type of phosphine end groups and on the type of function of the core (amine or alcohol), the complexation of ruthenium ([RuCl₂(p-cymene)]₂) and rhodium ([RhCl(COD)]₂) derivatives by the phosphine end groups can occur without side reaction at the core.     

Age of the earth and the moon

We have examined the isotopic compositions of lead reported for 55 terrestrial and 65 lunar samples. The lead ages indicate that the 4.55 billion years generally accepted as the age of the solar system refers instead to the time of the breakup of the meteorite parent body.