阻抑动力学光度法测定白鼠肝脏中的超痕量镍(Ⅱ)

在 NH3- H2 O- NH4 Cl介质中 ,超痕量镍 ( )能阻抑 H2 O2 氧化甲基紫褪色的指示反应 ,研究了阻抑褪色反应的最佳条件和动力学参数 ,建立了测定超痕量镍 ( )的新方法。方法检出限为 4.4× 1 0 -11g/m L Ni( ) ,测定范围为 0～1 .0μg/2 5m L。方法已用于测定生物样品中的 Ni( )。     

阻抑动力学光度法测定痕量铅

在氨水介质中, 痕量Cu(Ⅱ)对H2O2 氧化茜素红S的褪色反应具有催化作用, 而Pb(Ⅱ)对此褪色反应具有明显的阻抑作用, 由此建立了测定痕量Pb(Ⅱ)的新催化动力学光度法. 应用正交试验法确定了反应的最佳条件, 测定了有关动力学参数. 方法的检出限为7.5 ng/mL, 线性范围为0.0～0.35 μg/mL, 并应用于皮蛋和茶叶样品中Pb(Ⅱ)含量的测定, 同时还探讨了阻抑反应机理.     

阻抑乙基橙褪色动力学光度法测定痕量铁(Ⅲ)

在H2SO4介质中,痕量铁(Ⅲ)对KBrO3氧化乙基橙褪色反应有很强的阻抑作用,利用光度法检测阻抑反应过程中乙基橙浓度的变化,建立了铁(Ⅲ)-溴酸钾-乙基橙体系阻抑动力学光度法测定痕量铁(Ⅲ)的方法。在选定条件下,方法的线性范围为0.006～0.32μg/mL,检出限(3s/k)为0.0031μg/mL。     

阻抑动力学光度法测定乳品中的痕量碘

研究了在稀H2SO4介质中,痕量I-对KBrO3氧化酸性品红的阻抑作用及其动力学条件,建立了测定痕量I-的阻抑动力学光度分析的新方法.测定I-的线性范围为0～0.04 μg/mL,检出限为1.1×10-9 g/mL.已用于乳品中痕量碘的测定.     

阻抑动力学光度法测定痕量间二硝基苯

在硫酸介质中,痕量间二硝基苯能灵敏地阻抑Fe3+催化H2O2氧化中性红染料褪色的反应,由此建立了一种测定痕量间二硝基苯的阻抑动力学光度法。采用固定时间法,在λmax=530 nm处,对阻抑体系和非阻抑体系进行光度测定,应用正交试验法确定该阻抑褪色反应的最佳实验条件,并测定了其反应级数。该方法线性范围为0～48μg/L,检出限0.103μg/L,回收率为97.8%～98.9%,测定结果的相对标准偏差为1.5%～2.1%。该方法用于环境水样中间二硝基苯含量的测定,测定结果可靠。     

阻抑动力学光度法测定粮食中痕量砷(Ⅴ)

研究发现,在硫酸介质中,痕量砷(Ⅴ)能灵敏地阻抑铬(Ⅴ)催化高碘酸钾氧化间磺酸基偶氮氯膦褪色的指示反应.研究了阻抑褪色反应的最佳条件及动力学参数,建立了一种测定痕量砷(Ⅴ)的新方法.其测定范围为0.0～16 μg砷(Ⅴ)/L;检测限为4.0×10-7 g/L砷(Ⅴ).该法用于大米、黄豆、豌豆和玉米中痕量砷(Ⅴ)的测定,结果满意.     

停留-反相流动注射阻抑光度法测定超痕量铋(Ⅲ)

基于在B-R缓冲溶液介质中,Bi(Ⅲ)对H2O2氧化孔雀石绿(MG)褪色反应的显著阻抑作用,建立了一种停留-反相流动注射阻抑光度法测定超痕量Bi(Ⅲ)的新分析方法,该方法的线性范围为0.001～0.54 ng/L,检出限为9.9×10-4ng/L,相关系数为0.9992。对0.001 ng/LBi(Ⅲ)平行测定11次的标准偏差为1.3%,进样频率为20.9次/h。该方法可直接用于人发和水中的超痕量Bi(Ⅲ)的测定,回收率为96.0%～102.0%。     

KIO4-四硼酸钠系统阻抑亮绿褪色动力学光度法测定痕量Ir（Ⅳ）

基于H2SO4介质及四硼酸钠缓冲溶液中,80℃水浴中,Ir(Ⅳ)对KIO4氧化亮绿褪色反应具有阻抑作用,据此建立了阻抑动力学光度法测定痕量Ir(Ⅳ)的新方法。阻抑反应(吸光度A)与非阻抑反应(吸光度A0)吸光度差值△A与Ir(Ⅳ)的质量浓度ρ在0.0002～0.08μg/mL范围内呈良好的线性关系,检出限为2.969×10-10g/mL。对1μg/25 mL Ir(Ⅳ)标准溶液测定的相对标准偏差为1.7%(n=11)。测定了动力学参数,反应对Ir(Ⅳ)为一级反应,试验条件下,总反应为准一级反应,表观速率系数为2.883×10-4/s,表观活化能为52.2 kJ/mol。方法用于分子筛和活性炭样品中痕量Ir(Ⅳ)测定,加标回收率在98.1%～104.9%范围,符合痕量分析要求。     

阻抑动力学光度法测定环境水样中的痕量苯酚

基于在稀硫酸介质中，痕量苯酚能灵敏地阻抑高碘酸氧化苯胺蓝褪色，研究了该阻抑褪色反应的最佳条件及动力学参数，建立了测定痕量苯酚的新方法。该方法的线性范围为0-40.0μg/L，线性回归方程为1g(A1/A2)=0.638c 0.00117，相关系数r=0.9996，检出限为1.2μg/L。该方法简便，灵敏，选择性好，用于环境水样中痕量苯酚的测定，结果准确。     

阻抑动力学光度法测定痕量铌(Ⅴ)

研究发现,在硫酸介质中,痕量铌(Ⅴ)能灵敏地阻抑溴酸钾氧化二甲基黄褪色。研究了该阻抑褪色反应的最佳条件及动力学参数,建立了一种测定痕量铌(Ⅴ)的新方法。该法测定线性范围为0~30 ng/10mL,检出限为4.21×10-11 g/ mL。方法用于矿石中铌的测定,结果满意。     

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.

     

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.     

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。     

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。