复方五仁醇胶囊中5种成分的含量测定及其含量变化的相关性分析

目的：筛选复方五仁醇胶囊合适的质量控制指标。方法：高效液相色谱法测定10批制剂中五味子醇甲、五味子醇乙、五味子酯甲、五味子甲素和五味子乙素5种木脂素类成分的含量，对各成分的含量变化进行相关性分析，筛选含量较高且又能在一定程度上反映其他成分含量的指标成分。结果：10批制剂中5种木脂素类成分的含量存在较大差异，但各成分的含量变化之间具有很好的群体相关性，五味子醇乙、五味子酯甲、五味子甲素含量与五味子醇甲含量的相关系数分别为0．9708，0．9144，0．9849，与五味子乙素含量的相关系数分别为0．9815，0．9797，0．8932。结论：制剂中五味子醇甲、五味子乙素的含量在一定程度上能间接反映其他3种成分的含量，可以作为该制剂质量控制指标。     

不同炮制方法对五味子中木脂素类成分含量的影响

目的：探讨不同炮制方法对五味子木脂素类成分含量的影响。方法：采用HPLC法,分别测定用6种不同炮制方法炮制后的五味子中五味子甲素、五味子乙素和五味子醇甲等木脂素类成分的含量。结果：用清炒、醋蒸、酒蒸、酒浸、蜜炒和蜜蒸6种炮制方法炮制所得的五味子中,总木脂素的质量分数分别为0.7724％、0.8401％、0.8633％、0.7832％、0.7697％和0.7902％,均高于生品（总木脂素的质量分数为0.7619％）;蒸法处理的样品中五味子甲素、五味子乙素和五味子醇甲的含量均比非蒸法的含量高,以酒蒸法炮制的样品中总木脂素含量最高。结论：五味子经炮制后,木脂素类成分的含量均有不同程度的提高,酒蒸法应是五味子的最佳炮制方法。     

HPLC测定五味子种子及果皮中的6种木脂素类成分

目的 采用HPLC测定五味子种子及果皮中6种木脂素类成分的含量.方法 采用Lichrosphere C18色谱柱(250 mm× 4.6 mm,5μm),流动相为乙腈-水,梯度洗脱,流速1 mL· min-1,柱温30℃,检测波长217 nm.结果 五味子种子中五味子醇甲、五味子醇乙、五味子酯甲、五味子甲素、五味子乙素和五味子丙素的平均含量分别占总含量的90.66％、86.37％、94.78％、90.15％、92.99％和89.92％.结论 五味子中木脂素类成分主要存在于种子中.     

超高效液相色谱法同时测定南、北五味子中的7种木脂素含量

目的：建立UPLC测定五味子中7种木脂素的方法,并测定不同地区的南、北五味子中木脂素成分含量。方法：色谱柱ZORBAX Eclipse Plus C₁₈ column （1.8 μm,100 mm×2.1 mm）;流动相乙腈-水,梯度洗脱;流速0.3 mL·min^-1;柱温40℃;检测波长220 nm;进样体积1 μL。结果：各成分即五味子醇甲、五味子醇乙、五味子酯甲、五味子酯乙、五味子甲素、五味子乙素、五味子丙素之间基本达到基线分离,且线性关系良好,线性范围分别为0.984~246.000,0.636~159.000,0.552~138.000,0.472~1.180,0.952~2.380,1.120~2.810,0.436~1.090 μg·mL^-1（r>0.999 6）。平均加样回收率在98.29%~102.5%之间,RSD在1.4%~1.9%之间。结论：所建立的测定方法快速、稳定、可靠,适用于不同产地南、北五味子中木脂素含量的测定。     

五味子配方颗粒中木脂素成分分析

目的:建立测定五味子配方颗粒中主要木脂素类成分(五味子醇甲、五味子酯甲、五味子甲素、五味子乙素)含量的方法,分析不同厂家的五味子配方颗粒中木脂素成分的差异。方法:采用RP-HPLC法,并结合二极管阵列检测器(PDA)进行光谱分析。色谱柱:Hypersil ODS C18柱(4.6 mm×250 mm,10μm),流动相:A为乙腈,B为水,梯度洗脱,流速1.0 mL/min,柱温25℃,检测波长254 nm。结果:不同厂家五味子配方颗粒中五味子醇甲含量为0~1.292 3 mg/包、五味子酯甲含量为0~0.560 8 mg/包、五味子甲素含量为0~0.168 8 mg/包、五味子乙素均未检测出。结论:不同厂家产品五味子醇甲、五味子酯甲、五味子甲素含量差异显著。     

北五味子提取物碱性水解主要木脂素增量及其优化

采用80％体积分数的乙醇回流提取方法对北五味子活性成分五味子醇甲、五味子酯甲、五味子甲素和五味子乙素进行提取,采用单因素实验考察水解催化剂的影响,确定以氢氧化钠作为催化剂;应用响应面分析对北五味子乙醇提取物碱水解工艺进行了优化,确定用1 mol/L的氢氧化钠15 mL回流水解2h.然后考察了三氯甲烷、1,2-二氯乙烷、乙酸乙酯和石油醚几种溶剂的萃取效果,确定以1,2-二氯乙烷作为70％浸膏溶液的萃取溶剂.北五味子木脂素的有效成分五味子醇甲、五味子酯甲、五味子甲素和五味子乙素含量分别由原来的150.42、44.02、248.30和514.29mg/kg增加到455.96、58.21、397.69和772.09 mg/kg;经验证后总木脂素的回收率可达到165.91％.     

不同产地五味子药材中木脂素类成分比较

目的通过测定不同产地五味子药材中五味子醇甲、五味子乙素、总木脂素的含量,评价不同产地五味子药材的质量。方法利用高效液相色谱法同时测定五味子药材中五味子醇甲及五味子乙素的含量。采用梯度洗脱法,流动相为甲醇 水,色谱柱为Lichrospher5 C18（4.6 mm× 250 mm,5 μm）;检测波长为250 nm;柱温为30 ℃;流速为1 mL·min 1。利用分光光度法测定五味子药材中总木脂素的含量, 以五味子乙素为对照品,于570 nm波长处测定吸光度。结果所测的五味子药材中五味子醇甲的含量均高于0.50%,五味子乙素的含量均高于0.25%。所测的五味子药材中总木脂素的含量均高于3.70%。结论五味子醇甲及总木脂素含量以黑龙江产五味子药材中含量最高, 五味子乙素含量以辽宁产五味子药材中含量最高。     

多指标优选五味子种子中木脂素类成分提取工艺

目的优选五味子中木脂素类成分提取工艺。方法以五味子醇甲、五味子醇乙、五味子酯甲、五味子甲素、五味子乙素、五味子丙素及总木脂素提取量为指标,采用正交试验考察回流次数、回流时间、乙醇浓度、乙醇用量对该指标的影响。结果优选的工艺为5倍量95%乙醇,回流提取3次,每次60 min。结论优选的提取工艺稳定可行,可用于为五味子种子中木脂素类成分的提取。     

不同炮制方法对五味子中木脂素类成分含量的影响分析

目的观察探究不同炮制方法对五味子中木脂素类成分含量的影响。方法对采用不同方法炮制的五味子采用高效液相色谱法对其中木脂素类成分含量及溶出率进行测定,炮制方法有生五味子、醋蒸、酒蒸、蜜蒸、酒浸、清炒、蜜炒,木脂素类成分包括醇甲、醇乙、甲素、乙素。结果酒蒸和酒浸五味子中五味子醇甲、醇乙、甲素、乙素等木脂素类成分含量和溶出率均最高,其次为生五味子,且炒法五味子供试品中木脂素类成分含量及溶出率均较低。结论在五味子炮制中可考虑采用酒蒸和酒浸法以增强药效。     

一测多评法测定五味子中4种木脂素类成分的含量

建立五味子中4个木脂素类化合物一测多评方法学考察模式,验证该方法在五味子质量控制中应用的可行性和技术适应性。采用HPLC以五味子醇甲为内参物,建立五味子酯甲、五味子甲素和五味子乙素与五味子醇甲的相对校正因子,并进行含量计算,实现一测多评。同时采用外标法测定13批五味子药材中4个成分的含量,比较计算值与实测值的差异,验证一测多评法的准确性。结果表明,建立的校正因子重现性良好,采用校正因子计算的含量值与外标法实测值之间无显著差异。表明在缺少对照品的情况下,以外标法测定五味子醇甲含量,利用相对校正因子实现对五味子酯甲、五味子甲素和五味子乙素的测定准确可行,此方法可以用于五味子中木脂素类成分的定量评价研究。     

Trichloroethylene. I. Carcinogenicity of trichloroethylene.

Trichloroethylene (TCE) as an industrial pollutant may damage human health and can be considered as carcinogen. TCE has been detected in the environment and in various human organs, e.g., liver, kidney and brain etc. There are histological alterations such as depletion of glycogen and hydropic degeneration in the liver, however, other signs of TCE effects can be found in various organs as well. TCE and its metabolites, e.g., trichlorethanol, trichloro-acetic acid and epoxides were recently identified as strong mutagens in Ames mutagenicity test inducing frameshift and base-substitution mutations. TCE induced predominantly hepatocellular carcinoma after long term administration in mice. In these animals, kidneys and liver were supposed to be primary target organs with low epoxy-hydrolase activity. A high level of mitotic gene conversion (or gene rearrangement) was indicated by the metabolism of TCE after repeated administration. Purified TCE by was a weak mutagen in the presence of S9 microsomal fraction of rats and as a consequence, the carcinogenic activity was low in the kidney of rats. However, a dose related increase of Leydig cell tumors was found in male rats.     

Trichloroethylene. II. Mechanism of carcinogenicity of trichloroethylene.

The cancer inducing effect of trichloroethylene (TCE) was studied by various methods. DNA complexing activity and apoptosis inhibition were found to be the key elements of the carcinogenicity of TCE and its metabolites. The ability of TCE to interact with DNA was low, but its incorporation into the RNA and DNA of the brain, testis, pancreas, kidney, liver, lung and spleen, cannot be excluded. Exposure to TCE and its metabolites provides a selective growth advantage to spontaneously occurring mutations in some K- and H-ras oncogenes (as non specific results of secondary DNA or RNA damage). The amount of DNA-TCE adducts was higher in mouse hepatocytes than in rat hepatocytes. These differences may explain the species difference in carcinogenicity of TCE, which was dose dependent (due to metabolism) in mice but independent in rats. The blood level kinetics of TCE confirmed the faster metabolic rate in mice, including peroxisome proliferation and induction in hepatocytes. Dichloroacetic- and trichloroacetic acid were found to be hepatic carcinogens in mice, and the specificity depends on peroxisome proliferation induction. Possibly, TCE and related compounds down regulated apoptosis in mouse liver, and the reduced ability to remove initiated cells by apoptosis could be responsible for liver cancer induction by TCE.     

Studies in antifertility agents. 11. Secosteroids. 5. Synthesis of 9,11-secoestradiol.

9,11-Secoestradiol (9) and 11-hydroxy-9,11-secoestradiol (12) have been synthesized starting from 17-acetoxyestradiol 3-methyl ether (1) and found to possess significant antifertility activity in rats. 3-Methoxy-9,11-seco-9-oxo-17beta-acetoxyestra-1,3,5(10)-trien-11-oic acid (2), prepared by CrO3 oxidation of 1, on hydrogenolysis gave methyl 17beta-hydroxy-3-methoxy-9,11-secoestra-1,3,5(10)-triene-11-carboxylate (3). The 17-O-THP derivative of 3 was treated with LiAlH4 to give 17beta-(O-tetrahydropyranyl)-3-methoxy-11-hydroxy-9,11-secoestra-1,3,5(10)-triene (5). The 11-O-mesylate of 5 on LiAlH4 reduction followed by mild acid treatment and demethylation under alkaline conditions gave 9. LiAlH4 reduction of 3 gave 9,11-seco-11-hydroxyestradiol 3-methyl ether (11) which on demethylation gave 9,11-seco-11-hydroxyestradiol (12).     

Metabolism of papaverine. II. Species differences.

1. The urinary and biliary excretion of radioactive products in a 6 hr period after intravenous administration of [3H]papaverine was studied in rat, guinea-pig, rabbit, cat and dog. All species excreted metabolites extensively in the bile; only in rabbit and guinea-pig is urinary excretion important. 2. Metabolites in urine and bile of all species studied are mainly monophenolic compounds conjugated to glucuronic or sulphuric acid. Differences in the excretion patterns of the metabolites between different species are only quantitative. 3. Blood or plasma levels of papaverine after intravenous injection decreased with half-lives of approximately 12, 15, 22, 60 and 60 min for rabbit, rat, guinea-pig, cat and dog, respectively. The metabolites disappeared much more slowly than papaverine from the plasma. 4. Binding of papaverine to plasma proteins, as studied by equilibrium dialysis, was more than 90% in all species.