人参与藜芦配伍化学成分变化的HPLC-ESI-MS与ESI-MS研究

采用电喷雾质谱(ESI-MS)和高效液相色谱与电喷雾质谱联用技术(HPLC-ESI-MS), 对人参与藜芦配伍过程中人参皂苷和藜芦生物碱的变化规律进行了系统研究. 在人参与藜芦配伍的共煎液中鉴定出八种人参皂苷, 其中有六种人参皂苷含量有所降低, Rf和Rb₂的含量基本不变; 此外还鉴定出八种藜芦生物碱, 其中有六种生物碱的含量随人参加入而明显增高. 人参与藜芦配伍, 煎煮液中人参皂苷的含量下降, 藜芦总碱的含量上升. 人参的加入有利于藜芦生物碱的溶出. 因藜芦总碱的毒性较强, 所以人参“反”藜芦具有一定道理.     

乌头与贝母配伍化学成分变化的UPLC/Q-TOFMS研究

利用UPLC/Q-TOFMS对中药十八反药对——乌头贝母配伍的合煎液与合并液进行检测,经过MassLynx 4.1分析其化学成分存在差异,发现合煎后次乌头碱水解受到部分抑制,而其他主要的双酯型二萜生物碱溶出较少且水解较彻底,乌头与川贝配伍合煎的毒性相对较小,因而可能通过合理炮制减毒后应用于临床治疗.     

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.     

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。     

基于UPLC/Q-TOF-MS分析附子半夏配伍相反的物质基础

利用超高效液相色谱-飞行时间质谱联用技术(UPLC/Q-TOF-MS)分析附子半夏药对配伍相反的物质基础,从化学成分层次阐释其配伍相反机制.基于UPLC/Q-TOF-MS建立附子半夏药对配伍后生物碱类成分的化学指纹图谱,通过主成分分析法和正交偏最小二乘判别法分析药对配伍在合煎过程中的生物碱类成分的含量变化,找出差异变化显著的化学成分.结果表明正离子模式时附子半夏药对合煎液中次乌头碱,中乌头碱,乌头碱,去氧乌头碱,10-OH-中乌头碱,10-OH-乌头碱等的含量明显增高,而中乌头原碱,去乙酸中乌头原碱,去乙酸次乌头原碱,苯甲酰乌头原碱,苯甲酰次乌头原碱,10-OH-苯甲酰中乌头原碱等含量降低.附子半夏药对配伍应用时双酯型二萜生物碱的含量明显增高,而单酯型二萜生物碱的含量明显降低,这可能是附子半夏药对配伍相反作用的物质基础.     

人参和五灵脂配伍的无机元素含量测定

采用电感耦合等离子体发射光谱法(ICP-AES)测定了人参和五灵脂配伍的无机元素含量。结果表明，人参和五灵脂及其合煎液中的铝含量均低于人参单煎液，人参和五灵配伍可减少有害元素铝的溶出；配伍合煎液中钙、硒、钼、钴、镁、铜、锰等有益元素的含量均高于人参单煎液。     

人参与附子、黄连配伍的HPLC-ESI-MS研究及抗氧化活性测定

采用高效液相色谱与电喷雾质谱联用技术(HPLC-ESI-MS)对不同比例的人参与附子或黄连的水煎液、药渣和沉淀进行研究, 共鉴定了8种人参皂苷, 发现加入附子或黄连后, 溶液中人参皂苷含量明显减少, 进一步研究证明附子或黄连中的某些成分阻止了皂苷的溶出; 同时以抗坏血酸作对照, 应用铁离子还原/抗氧化能力测定法(FRAP)测定了人参单煎液及人参与附子、黄连共煎液中正丁醇提取物和水提取物的抗氧化活性. 结果证明, 共煎液中正丁醇提取物的抗氧化活性高于人参单煎液, 同时也高于人参与附子或黄连单煎混合液的抗氧化活性, 但水提取物抗氧化活性的变化规律有所不同, 这可能与煎煮过程中物质之间的相互作用有关.     

复方丹参配伍比例对丹参化学成分溶出的影响

采用高效液相色谱峰比值法比较了由丹参和三七组成的复方丹参中丹参与三七的比例(以质量比计)从10∶0变化到1∶10的过程中丹参化学成分的变化。结果表明：所有合煎样品中丹参的主要成分含量均比单味药丹参中丹参主要成分的含量高,并且经典方(m(丹参)∶m(三七)＝5∶3)中丹参主要成分的含量最高。因此,丹参与三七以一定的比例(5∶3)配伍并且采用合煎的方法能够增加丹参成分的溶出率, 由此看来中医药中讲究的配伍规律是有其内在的科学道理的。     

液相色谱指纹图谱在当归、黄芪及其复方有效成分分析中的应用

将液相色谱指纹图谱与正辛醇-水分配体系模拟中药在人体内的吸收情况相结合分析中药活性成分,分析比较了当归、黄芪单煎液及合煎液在不同靶位酸度下化学成分种类、含量的变化情况,探讨了配伍及酸度变化对中药中各成分的形态分布及在人体中吸收情况的影响.发现不同靶位环境的酸度及不同配伍对中药中的有效物质组分、含量及各组分的吸收都有很大的影响.     

液质联用测定人参与五灵脂、莱菔子配伍的人参皂苷

采用液质联用(HPLC-ESI-MSn)技术,对不同比例的人参、五灵脂和人参、莱菔子的水煎液、沉淀和药渣进行研究,共鉴定了10种人参皂苷,并对这10种人参皂苷配伍前后的变化进行了系统的研究。实验结果表明,在共煎液中,除Ro外,其它皂苷的含量都有所下降。五灵脂或莱菔子的加入对人参皂苷的影响不同,莱菔子影响人参皂苷的溶出,而与五灵脂配伍,部分人参皂苷生成沉淀。     

非那雄胺合成工艺改进

非那雄胺能抑制5α-还原酶的活性,明显降低二氢睾酮水平,是一种治疗良性前列腺增生的有效药品。该合成工艺以甾烯酮酸为原料,将其与氯化亚砜反应,无须分离即与叔丁胺反应得17β-酰胺化合物,再氧化开环,环合,氢化,脱氢合成了非那雄胺。经元素分析、IR、1HNMR、13CNMR、MS分析表征了其结构。该法无须使用昂贵的2,2-二吡啶二硫化物和剧毒药品苯亚硒酸酐,且以乙酸铵代替氨气,降低了对设备的要求和腐蚀,更适用于工业生产。     

Dichroism of absorption and polarization of phosphorescence of molecules of the closed form of nitrobenzospirothiopyran

The spectral-polarization characteristics of absorption and phosphorescence of molecules of the initial form of nitro-substituted indolinospirobenzothiopyran were studied in oriented polyethylene films and in solutions with different polarity. An oscillator model of the electron transitions responsible for the formation of absorption and luminescence spectra was suggested. It was established that the principal differences in the spectral and photophysical properties of the compound studied and its oxygen-containing analog are associated with the fact that the electronegativity of the S atom is lower than that of the O atom. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1143–1146, June, 1997.     

Synthesis of phenolic components of Grains of Paradise

Two vanilloids, (5E)-8-(4-hydroxy-3-methoxyphenyl)oct-5-en-4-one (1) and 4-[3-hydroxydecyl]-2-methoxyphenol (2), isolated from the dried seeds of Grains of Paradise (Aframomum melegueta), were synthesized; the latter compound was made as the S-enantiomer and the material derived from the seeds was found to be a 1:1.7 mixture of the R and S isomers. The synthetic route used should allow the preparation of analogs having extended alkyl chains and consequently different lipophilicity, and 3, a homolog of 2, was also prepared.     

Study of hydration of two cements of different strengths

Main hydration products of two cement pastes, i.e. CSH-gel, portlandite (P) (and specific surface S) were studied by static heating, and by SEM, TEM and XRD, as a function of cement strength (C-33 and C-43) hydration time (th) and subsequent hydration in water vapour.Total change in mass on hydration and air drying, M_o, increased with strength of cement paste and with hydration time. Content of water escaping at 110 to 220°C, defined as water bound with low energy, mainly interlayer and hydrate water, was independent on cement strength but its content increased with (th). Content of chemically bound (zeolitic) water in CSH-gel, escaping at 220-400°C, was slightly dependent on strength and increased with (th). It was possibly derived from the dehydroxylation of CSH-gel and AFm phase. Portlandite water, escaping at 400-500°C, was independent on cement strength and was higher on longer hydration. Large P crystals were formed in the weaker cement paste C-33. Smaller crystals were formed in C-43 but they increased with (th). Carbonate formated on contact with air (calcite, vaterite and aragonite), decomposed in cement at 600-700^oC. It was high in pastes C-33(1 month) and C-43(1 month), i.e. 5.7 and 3.3%, respectively; it was less than 1% after 6 hydration months (low sensitivity to carbonation) in agreement with the XRD study showing carbonates in the air dry paste (1month), and its absence on prolonged hydration (6 months) and on acetone treatment. Water vapour treatment of (6 months) pastes or wetting-drying increased this sensitivity.Nanosized P-crystals, detected by TEM, could contribute to the cement strength; carbonate was observed on the rims of gel clusters.This revised version was published online in November 2005 with corrections to the Cover Date.     

Acid hydrolysis of carboxymethylcellulose of low degree of substitution

Cotton cellulose was swollen in a sodium hydroxide solution and carboxymethylated by a two-bath method for different periods of time for each process. The kinetics of acid hydrolysis and the crystallinity of the swollen and carboxymethylated samples were measured. The proportion of broken bonds, rate constants for hydrolysis, and permeability of cellulose to hydrolyzing agents were calculated. The susceptibility of glycosidic linkages to acid hydrolysis was improved by carboxymethylation more than by swelling in alkali. The increased accessibility of carboxymethylcellulose to acid was regarded as a consequence of increased intra-and intercrystalline swelling and of the glycosidic bonds' weakness caused by the electron-attracting carboxymethyl group on the C-6 position.     

氯氧化镁生成热的研究

用氧化镁氯化镁水溶液制备了8水合氯氧化镁[nMg(OH)2·MgCl2·8H2O], 并测定了其在盐酸中的溶解热, 实验结果表明, 氯氧化镁溶解热与n值呈线性关系, 根据溶解热求出5Mg(OH)2·MgCl2·8H2O和3Mg(OH)2·MgCl2·8H2O的生成热分别为-7727.1和5888.1kJ·mol^1^-。     

Estimation of Kinetic Parameters of Thermal Oxidation of Ilmenite

The aim of the presented work was the investigation of thermal oxidation of ilmenite in static air atmosphere. The investigations were carried out by use of a derivatograph (MOM, Hungary). The changes of crystallographic structure of investigated samples were identified by X-ray diffractometry on Philips PW-1710 diffractometer. In temperature above 500°C appears structure of hematite Fe₂O₃. On the basis of the thermogravimetric measurements, the contracting area and contracting volume models were found as the best fitting experimental data. This revised version was published online in August 2006 with corrections to the Cover Date.     

Mechanism of action of base-catalyzed oxygenation of phenol derivatives

Cyclopropyl derivative of 2,6-di-tert-butylphenol is synthesized as a probe to investigate the mechanism of base-catalyzed autooxidation of phenol derivatives. Our study indicates that one electron reduction of molecular oxygen from phenolate gives phenoxyl radical 3, a key intermediate of autooxidation. The coupling of phenoxyl radical and superoxide radical gives peroxylate anion 4 and produces the final epoxy alcohol adduct 6.     

Determination of heats of detonation and influence of components of composite explosives on heats of detonation of high explosives

The heats of detonation of 20 simple high explosives and explosive mixtures were determined by means of an adiabatic detonation calorimeter designed by the authors. The results indicated that the performance of the instrument was reliable and the experimental data were very accurate. For explosive mixtures, there was a linear accumulative relationship between the heats of detonation of the explosive mixture and its components. Accordingly, the heats of detonation of explosive mixtures could be calculated directly from the heats of detonation of simple explosives and the characteristic heats of other components. The experiments showed that the gold or brass shell of the cylindrical charge could be substituted by a thick-walled porcelain shell, which had the advantage of cheapness.