川芎中重金属元素镉含量测定的研究进展

川芎中有毒重金属元素镉含量超过国家GAP标准,严重影响其出口创汇,也成为制约川芎走向现代化和国际化的瓶颈。介绍了目前对川芎的消化及重金属元素镉的检测方法,并对各方法的利弊进行了分析,从而为准确、高效地检测药材中重金属元素镉的含量提供了有力的参考依据。     

川芎和抚芎的多糖和重金属含量分析

为提高川芎质量,控制重金属含量,采用苯酚-硫酸法测定了川芎和抚芎中的多糖含量,采用原子吸收光谱法测定了其中重金属含量。结果表明,川芎和抚芎多糖含量分别为(25.35±0.23)和(23.52±0.51)mg/g,重金属铅、汞、镉的含量分别为(1.28±0.12)、(0.21±0.22)、(0.25±0.11)μg/g和(2.24±0.21)、(0.16±0.22)、(0.35±0.20)μg/g。苯酚-硫酸法简单、快速、准确度高,重现性好,用于测定川芎和抚芎多糖结果可靠。川芎汞含量有一定超标,抚芎镉含量超标,应引起注意。     

川芎栽培土壤中重金属镉的动态监测

目的：连续多年监测彭州敖平镇川芎药材栽培土壤中重金属镉的含量,分析其对川芎药材中镉含量的影响。方法根据前期研究结果选取敖平镇部分川芎种植地固定采集样品。按照国家标准方法,采取0～20 cm连续根系土柱和川芎药材。采用火焰法对抽样土壤及川芎药材中镉的含量进行检测分析。结果采样区域内土壤中镉含量均符合国家二级土壤环境质量标准;部分土壤中镉的含量呈明显增长趋势。结论川芎种植土壤中镉含量与环境有较高关联,水泥厂粉尘等污染源是土壤中镉含量增加的重要来源。     

川芎水蒸气蒸馏和超临界CO2提取物化学成分的GC-MS分析鉴别

用水蒸气蒸馏和超临界CO2提取方法对川芎药材中的化学成分进行提取,用气相色谱-质谱联用技术(GC-MS)对提取物进行分析,分别鉴定出30和34个化合物,测定了其相对含量。 结果表明,水蒸气蒸馏和超临界CO2提取物的主要成分均为(Z)-藁本内酯。 超临界CO2提取方法能提取出较多的川芎药效物质,如丁基酞内酯、丁烯基酞内酯、川芎内酯A、(Z)-藁本内酯、(E)-藁本内酯和川芎内酯I。 而水蒸气蒸馏提取物中除了川芎药效物质外,还含有较多的萜烯类化合物。 结果表明,超临界CO2对川芎药效物质的提取比水蒸气蒸馏法的效率高。 通过对川芎中带不饱和侧链与饱和侧链内酯类化合物质谱裂解规律的解析归纳,鉴别了川芎中不饱和侧链内酯类化合物如(Z)-藁本内酯、(E)-藁本内酯、丁烯基酞内酯和川芎内酯I以及饱和侧链内酯类化合物如丁基酞内酯和川芎内酯A。     

川芎对大鼠心肌缺血再灌注NF-κB的影响作用

目的探讨川芎治疗心肌缺血再灌注的作用机理。方法将SD大鼠50只,随机分为5组,每组各10只、以及空白组10只。共60只大鼠。即空白对照组(生理盐水20 mL/kg)、模型组(生理盐水20 mL/kg)、川芎高剂量(100 mg/kg)、川芎中剂量(50 mg/kg)、川芎低剂量(25mg/kg)组。采用放免法检测血清TNF-α含量,免疫组化法测定心肌组织中核因子κB的表达。结果川芎对各组及治疗组血清TNF-α含量与正常组比较显著降低(P0.01),NF-κB的活化程度正常组比较显著降低(P0.01)。其中以中剂量治疗组效果最为显著。结论川芎可降低血清中TNF-α含量,减少心肌组织中NF-κB活化程度,达到对心肌缺血再灌注作用。     

石柱黄连及根际土壤中矿质元素特征分析

研究石柱黄连不同器官及其根际土壤中矿质元素特征,探究黄连根茎矿质元素间及其与土壤环境的相关性。采用电感耦合等离子体质谱法(ICP-MS)、电感耦合等离子体发射光谱法(ICP-OES)及原子荧光光谱法(AFS)测定了15组石柱黄连植株和根际土壤中18种矿质元素含量,所得数据运用SPSS 22.0统计软件分析。石柱黄连根际土壤中锰、磷、镁、镉、汞等元素含量的变异性较大,部分采样点土壤中镉含量超过农用地土壤污染风险筛选值。在检测的18种元素中,黄连植株中钙、镁、磷、钾含量最高,其次是铁、锰、锌,再次是锶、铜、镍,最后是铅、钒、钴、镉、钼、铬、砷、汞。须根对大部分矿质元素的富集能力强于根茎或地上部;黄连根茎对锌的富集能力强于须根或地上部;地上部对钙、磷、钾、铬的富集能力强于须根或根茎。Spearman分析表明黄连根茎矿质元素间、黄连根茎与土壤中矿质元素有一定相关性,部分具有统计学意义(P＜0.05)。石柱黄连不同器官中矿质元素含量有明显差异,以此建立的指纹图谱可用于区分黄连根茎及须根的粉末样品;黄连根茎中矿质元素间主要表现为协同作用,黄连根茎与土壤中矿质元素既有协同作用又有拮抗作用。     

红外光谱法对肉苁蓉径向不同部位的分析与评价

采用傅里叶变换红外光谱、二阶导数谱和二维相关红外光谱技术对肉苁蓉由表及里3个部位的药材粉末及其水提物和醇提物进行了分析与评价研究.结果表明,肉苁蓉不同部位的一维光谱非常相似,三者相似系数分别为0.9605,0.944和0.976;二阶导数谱中峰位和峰强的差异明显.1430～1700 cm-1范围内的二维相关谱中皮部自动峰有3个,而中部及髓部均为4个,更直观的反映出三者的差异.不同部位水提物和醇提物的分析结果进一步明确了肉苁蓉皮部芳香类、环烯醚萜类及糖苷类物质与中部和髓部存在明显不同,而髓部的水溶性多糖、半乳糖醇和苯乙醇苷类物质均高于其它部位.可见红外光谱法结合二维相关红外光谱技术为同种药材不同部位的细微差异分析和评价提供了一种快速、全面和客观的方法和手段.     

全二维气相色谱/飞行时间质谱分析不同产地的川芎挥发油

建立了川芎挥发油的全二维气相色谱/飞行时间质谱(GC×GC/TOF MS)指纹图谱,并结合聚类分析评价了川芎药材的质量。4种萜类和苯酞类物质在DB-Petro×DB-17柱系统上实现了明显的族组分分离。从新都市的1个样品中分离出375种组分,其中相似度、反相似度皆大于800的化合物215个;根据质谱库检索和保留指数验证,或参照标准化合物及文献报道,从中定性了43个化合物。结合偏最小二乘法-判别分析,可以很好地将4个产区的挥发油样品加以区分,并找出20种差异最大的化合物,其中包括4种苯酞类物质。在此基础上,进一步应用正交偏最小二乘法,关联化学成分和抗氧化活性,结果发现,苯酞类物质(如藁本内酯、川芎内酯A和新蛇床内酯)对川芎挥发油样品地区差异的影响最大,其中彭州产川芎样品中苯酞类物质的含量最高。本文通过高分辨色谱技术研究了相邻产地的药物化学组成差异,并将化学指纹及生物学活性相关联,建立了系统的中药质量评价及活性化合物筛选研究模式。     

高效液相色谱与质谱联用分析测定川芎中有效成分阿魏酸与藁本内酯

采用HPLC-MS系统地研究了中药川芎有效成分阿魏酸(ferykuc acid)和藁本内酯(liguatilide)的定量分析方法。利用制备色谱制备了藁本内酯对照品,并对其进行了紫外光谱、质谱、红外光谱等结构鉴定。分别考察了水、甲醇、乙醇、95％乙醇4种溶剂以及提取时间对川芎中阿魏酸和藁本内酯提取量的影响。结果表明：水是阿魏酸的最佳提取溶剂,提取时间45min为宜;乙醇是适合提取藁本内酯的溶剂,提取时间75min为宜。以外标法对市售川芎中的阿魏酸与藁本内酯进行了定量分析,二者含量分别是0．15％(m／m)和0．82％(m/m)。     

电感耦合等离子体质谱同位素稀释法测定菜园土壤中微量镉

用电感耦合等离子体质谱同位素稀释法,测定了菜园土壤中微量镉的含量。土壤样品中加入一定量的112Cd富集同位素试剂后,用硝酸-氢氟酸-高氯酸混合酸预消解后再经微波消解,冷却后样品溶液在130℃蒸发近干,然后加入硼酸1 mL,以硝酸(2+98)溶液定容至20 mL,利用电感耦合等离子体质谱法测定溶液中的同位素比值R(112Cd/111Cd),用同位素稀释法计算出样品中镉的含量。试验对仪器参数1、12Cd富集同位素试剂的加入量、质量歧视因素、仪器死时间及同量异位素和多原子离子峰的干扰等因素对测定产生的影响进行了试验和校正。在优化的条件下测定了土壤标准物质(GBW 07423)中镉的含量,测定值与标准值相符。     

利用手持技术改进测定乙醇分子结构实验

利用压强传感器代替排水集气法,改进测定乙醇分子结构实验的仪器装置,并探索最佳反应条件。另外,设计两个空白实验,结合压强变化曲线对实验误差进行相关讨论。     

光谱仪测试范围的扩展

由于石化行业的生产需要，其材质的使用具有多样性和广泛性，经常会出现顾客委托的测试样品的一个或几个元素跨越光谱仪现有测试程序测量范围的情况。本法通过对光谱仪测试原理的认识，根据光谱仪的测试能力及标样的采集，实现了一个或几个元素测量范围的扩展，并对其测量的影响因素进行了研究。     

Influence of viscosity of medium on processes of oxygen quenching of excited states of mesoporphyrin

The oxygen quenching rate constants for singlet and triplet excited states of the dimethyl ester of mesoporphyrin IX increase with decreasing viscosity of the medium and reach a maximum at a viscosity of approximately 0.4 mPa·sec, after which the rate constants begin to decrease. The drop in rate constant with increasing fluidity of the medium may be related to a nonequilibrium character of the elementary act in the interaction of the reactants in the solvent cage. In viscous media such as isopropyl alcohol, isobutyl alcohol, and isoamyl alcohol, the reaction radius is greater than the sum of the radii of the reacting particles. The long-range character of these processes is due to the relatively weak dependence of the quenching probability on distance.Translated from Teoreticheskaya i Éksperimental'naya Khimiya, Vol. 25, No. 2, pp. 161–167, March–April, 1989.     

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.     

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.

     

物质分配系数的测定实验改进

实验教学目的是从解决实际问题出发,以实验技术训练和实验设计思想培养为目标。介绍了将单一的物质分配系数测定实验改进为综合实验,提高了实验效果及实验资源利用率。     

Neutral diterpenoids of oleoresins of five species of conifers of Transcarpathia

The compositions of the neutral diterpenoids of the oleoresins of five species of conifers growing in the Transcarpathia have been studied. It has been found that the oleoresins ofAbies alba M.,Larix decidua M., andPicea excelsa L. contain more than 50% of neutral diterpenoids. The group and qualitative compositions of the oxygen-containing diterpenoids have been determined. In the oleoresins ofAbies alba,Picea excelsa, andPicea abies tertiary alcohols — cis-abienol and isocembrol — predominate, while inLarix decidua the main component is the hydroxy ester larixyl acetate. Primary alcohols related to the resin acids have been found in all the oleoresins investigated. Features of the distribution of diterpenoids according to the species of conifers have been revealed. The results obtained are necessary for the chemotaxonomy of conifers of the family Pinceae.Novosibirsk Institute of Organic Chemistry, Siberian Branch, Academy of Sciences of the USSR. Translated from Khimiya Prirodynkh Soedinenii, No. 6, pp. 812–816, November–December, 1988.     

Calculation of enthalpies of hydrogenation of hydrocarbons

Sets of hydrogen molecule equivalents have been developed which permit the calculation of hydrogenation of different types of carbon-carbon bonds from ab initio total energies (3-21G and 6-31G* basis sets, and, to a more limited extent, for MP2/6-31G* data) of reactants and products. The calculated enthalpies of hydrogenation are in good agreement with experiment for unstrained molecules, with average errors on the order of 2 kcal/mol. The 6-31G* equivalents allow the enthalpies for strained molecules to be calculated accurately, but the 3-21G equivalents do not. The equivalents for both basis sets have been tested by calculating the enthalpies of hydrogenation of carbon-carbon bonds in nitrogen- and oxygen-containing organic molecules, free radicals, and classical carbocations. The results are in good agreement with experiment in most cases.     

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。