柱切换液相色谱法快速定量检测参附注射液中乌头碱类生物碱和人参皂苷

利用柱切换液相色谱,建立了参附注射液中苯甲酰新乌头原碱、苯甲酰乌头原碱、苯甲酰次乌头原碱、新乌头碱、次乌头碱和乌头碱6种乌头碱类生物碱,以及Rg1、Re、Rf、Rb1、Rc、Ro、Rb2、Rb3、Rd 9种人参皂苷的分析方法。首先利用强阳离子交换的在线固相小柱选择性富集和净化样品中生物碱类成分,优化了色谱条件;并采用EC－C18柱作为人参皂苷的分析柱,通过优化实验条件,结合柱切换方式,去除了样品中辅料等大极性基质成分对色谱柱的污染,实现了生物碱分析和人参皂苷分析的自动切换。结果显示,样品中的生物碱和人参皂苷分离良好,线性相关系数（r2）均大于0.999,连续进样精密度的相对标准偏差（RSD） < 2.0%,重复性的RSD < 2.0%;其中6种生物碱的平均回收率为95.1%～98.6%,检出限为4.0～8.2 ng/mL;9种人参皂苷的平均回收率为91.7%～104%。所构建的基于柱切换液相色谱技术的在线固相萃取方法能够有效去除样品中的基质干扰,快速完成参附注射液中3种单酯型生物碱和9种人参皂苷的快速定量,同时也可对3种双酯型生物碱进行限量检测,可应用于药物的质量评价。     

液相色谱-电喷雾离子阱质谱对芥子碱的测定方法

探讨了采用液相色谱-电喷雾串联质谱法检测小鼠前列腺中芥子碱硫氰酸盐的方法。流动相为V(乙腈)∶V(0.5%乙酸)=20∶80,色谱柱为ZorbaxXDB-C18(150 mm×4.6 mmi.d.,5μm),流速为0.6 mL/min。芥子碱硫氰酸盐的准分子离子和二级碎片离子分别为m/z 304和m/z 251,方法的检出限为0.7μg/L,线性范围为2.7~80.5μg/L,r为0.9934,相对标准偏差为7.5%~12.9%,样品的回收率为81.2%~102.5%。     

二维液相色谱法在线检测哈茨木霉发酵液中2460A含量

建立了在线检测哈茨木霉发酵液中微量2460A的二维液相色谱方法。利用Ultimate 3000双三元液相色谱仪,采用阀切换二维色谱技术,组合3根色谱柱实现2460A的在线净化、富集和含量检测。净化柱采用资生堂MF C8柱(10 mm×4.6 mm,5.0μm),富集柱采用资生堂MGC18柱(20 mm×4.6 mm,5.0μm),以水-甲醇为流动相,梯度洗脱,流速2.0 m L/min;二维分析柱采用Thermo Hypersil GOLD C18柱(250 mm×4.6 mm,5.0μm),以水-甲醇为流动相,梯度洗脱,流速1.0 m L/min;进样量1.0 m L;柱温40℃;检测波长424 nm。方法验证结果显示,2460A的线性范围为0.0025~10.0 mg/L(r=0.9981,n=8),检出限为1.2μg/L;定量限为2.5μg/L;方法回收率为88.0%~104.4%。     

高效液相色谱法在长链烷基小檗碱衍生物定量分析中的应用

采用高效液相色谱法(HPLC)对8-十六烷基小檗碱的含量进行测定,色谱条件为Thermo Hypersil Gold C18柱(5μm,150 mm×4.6 mm),流动相:乙腈-20 mmol/L KH2PO4溶液(V/V=80:20,用H3PO4溶液调p H至4.0),柱温:30℃,流速:1.0 m L/min,进样量:50μL。方法检出限为4 ng/m L,线性范围20~3000 ng/m L,回归方程y=91.501x+578.98,相关系数R2=0.9993,回收率为78.3%~89.9%(n=6),日内和日间相对标准偏差分别为3.4%~5.1%和5.4%~7.4%(n=6)。方法可用于对添加8-十六烷基小檗碱的大鼠血浆的测试。     

人血清白蛋白生物色谱柱的性能研究及应用于铁棒锤中活性成分的筛选

以大孔硅胶为基质,采用羰基咪唑法合成了人血清白蛋白(HSA)生物色谱填料。详细评价了该填料对药物的分离性能,温度和pH对药物保留的影响。结果表明,该种生物色谱填料的分离性能优良,可以在短时间内基线分离4种药物分子。用HSA色谱柱对铁棒锤中有效成分进行了分离,通过LC-MS分析结果显示,该色谱柱可以分离出其中4种活性成分(脱乙酰去氧乌头碱、苯甲酰脱氧乌头碱、乌头原碱、16-O-去甲基乌头次碱)。     

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.     

离心超滤质谱筛选川乌中与人血清白蛋白相互作用的乌头类生物碱

采用离心超滤质谱技术从川乌总生物碱提取物中筛选与人血清白蛋白相互作用的乌头类生物碱成分,并用LC-MSn技术对筛选出的活性成分进行了分离鉴定.结果表明,从川乌总生物碱中筛选并鉴定出9种与人血清白蛋白存在相互作用的乌头类生物碱:苯甲酰新乌头原碱、苯甲酰乌头原碱、10-OH-中乌头碱、中乌头碱、10-OH-乌头碱、乌头碱、次乌头碱、脱氧乌头碱和3,13-脱氧乌头碱.     

高效液相色谱-蒸发光散射法测定甘油磷脂酰胆碱

建立了高效液相色谱-蒸发光散射法(HPLC-ELSD)测定甘油磷脂酰胆碱(L-α-GPC)的方法。得到最佳色谱条件:色谱柱为Tigerkin Diol柱(250×4.6mm,5μm),流动相为甲醇-水(体积比90∶10),氮气流量为1.50L/min,漂移管温度为65℃。用外标法对L-α-GPC和磷脂酰胆碱(PC)进行定量分析,线性范围分别为0.25~3.00g/L和0.50~5.00g/L,相关系数分别为0.9993和0.9987;平均回收率分别为95.87%和95.72%;相对标准偏差分别为1.75%和1.93%。该方法能够简便快速的将L-α-GPC与其他磷脂进行分离。     

超高效液相色谱-串联质谱法同时测定血液中5种乌头类生物碱北大核心CSCD

采用超高效液相色谱-串联质谱法同时测定血液中乌头碱、次乌头碱、新乌头碱、滇乌头碱和雪上一枝蒿甲素等5种乌头类生物碱的含量。在1mL血液样品中加入0.1mol·L^(-1)盐酸溶液4mL,振荡10min,以8 000r·min^(-1)转速离心30min,上清液经Waters Oasis MCX固相萃取柱净化。以ACQUITY UPLC^(R○)BEH C_(18)色谱柱为分离柱,以不同体积比的乙腈和水(用氨水调pH至10)的混合液为流动相进行梯度洗脱,质谱分析中采用电喷雾离子源(正离子扫描)和多反应监测模式。5种乌头类生物碱的质量浓度均在1.0~200μg·L^(-1)内与其对应的峰面积呈线性关系,方法的检出限(3S/N)为0.1~0.5μg·L^(-1)。以空白样品为基体进行加标回收试验,所得回收率为75.6%~115%,测定值的相对标准偏差(n=6)为1.3%~6.5%。     

液相色谱特征图谱用于草乌成分定量

测定不同产地草乌的液相色谱指纹图谱,构建草乌的特征图谱,对不同草乌样品进行相似性对比分析,考察不同产地草乌的生物碱总量含量差异.采用色谱柱为WelchromC18柱(250 mm×4.6 mm,5μL),流动相为甲醇–0.1％三乙胺(体积比为75:25),流量为1 mL/min,检测波长为235 nm,柱温为30℃,进样体积为20μL.对10个批次样品进行相似度分析和含量测定,确定草乌的特征图谱共有模式,标定10个特征峰,指认了新乌头碱、乌头碱、次乌头碱的特征峰.10批不同产地草乌的相似度均大于0.90,相似度较好.产地1的草乌总生物碱含量为3.4046 mg/g,在10个产地中含量最高.其它产地草乌总生物碱含量相近.     

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.     

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。     

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.

     

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.     

恶臭嗅辨实验室建设探讨

针对恶臭测试的环境影响问题,提出了解决的实例方案,并对方案的要点及优缺点进行讨论,此方案在实际操作中具有较好的效果。     

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^-。     

Summary of development of the theory of stability of colloids and thin films

In this review, the research of the author in the field of colloidal systems is summarized. The factors influencing colloidal stability are systematized and analyzed. Examples are presented to illustrate the practical utilization of the theory of stability of colloids and thin films.This review was prepared on the basis of the works of the author, which were awarded the State Premium for 1991 in the field of science and technology, chemistry section.Institute of Physical Chemistry, Russian Academy of Sciences, 117915 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1708–1717, August, 1992.     

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.     

解决能源问题的新途径--光解水制氢的研究

面对日益枯竭的能源危机,氢能是一种洁净、最有前景的替代能源。目前在各种制氢的方法中光催化分解水制氢的研究最多,光解水过程中催化剂最关键,本文对利用太阳能光解水的途径、提高光催化反应效率以及光催化剂的开发研究进行了综述。