邻菲哕啉-Fe(Ⅱ)光度法间接测定盐酸吡硫醇

在酸性介质中,盐酸吡硫醇可将Fe(Ⅲ)还原为Fe(Ⅱ),邻菲啰啉能与Fe(Ⅱ)显色,最大吸收波长为508 nm,通过测定Fe(1Ⅰ)的量间接的测定了盐酸吡硫醇的量.建立了测定盐酸吡硫醇质量浓度的新方法.盐酸吡硫醇在0.010～6.0 μg/mL范围内与吸光度呈良好的线性关系,线性回归方程为△A=-0.00373+0.1...     

柱前衍生反相离子对高效液相色谱法测定Fe(Ⅱ)

建立了将PDT作为柱前衍生试剂,用反相离子对高效液相色谱法分离和测定Fe(Ⅱ)的新方法.样品经柱前衍生后,以ODS C8色谱柱进行分离,以含60%(体积分数)乙腈、60mmol/L的高氯酸钠和20mmol/L的乙酸-乙酸钠水溶液(pH 4.65)作为流动相,流速为1mL/min,检测波长为295nm,整个分离过程在14min内完成.考察了Fe(Ⅱ)在不同水样中的回收率,当Fe(Ⅱ)的添加量为20μg/L时,其回收率为99%～102%.峰高、峰面积和保留时间的相对标准偏差分别为1.06%、2.87%和0.45%.方法的检出限为0.35μg/L(S/N=3).该法成功应用于环境水样中Fe(Ⅱ)含量的测定.     

邻菲啰啉计算光度法同时测定生物浸出样品中Fe(Ⅱ)和Fe(Ⅲ)

邻菲啰啉光度法常用于Fe(Ⅱ)测定,但受到试样中Fe(Ⅲ)对测定的影响,因此不能直接用于生物浸出样品中Fe(Ⅱ)和Fe(Ⅲ)的同时测定.为此,基于Fe(Ⅱ)邻菲啰啉特征吸收曲线以及混合铁中Fe(Ⅲ)对Fe(Ⅱ)测定的线性影响关系,建立了基于Fe(Ⅱ)和全铁同时测定Fe(Ⅱ)和Fe(Ⅲ)的计算光度法,并研究了生物浸出样品中典型金属离子(Cu2+、Ni2+、Cd2+、Co2+)以及试样溶解与储放对测定的影响.方法可准确地测定含铁次生矿物和生物浸出液中铁价态组成,应用于生物浸出矿渣、细胞表面中常量或微量的Fe(Ⅱ)和Fe(Ⅲ)组成分析,具有简便快速的特点.     

内蒙古地区沙生植物--沙枣中维生素C含量的测定

在 pH 6.0的 HAc-NaAc缓冲溶液中,用活性炭吸附沙枣中的色素,Cu(Ⅱ)催化氧化维生素C,在λmax=268 nm处可直接测定沙枣中维生素C含量.与传统碘量法相比,测定结果基本一致.为内蒙古地区沙枣天然植物资源的药用开发、食品加工等提供了参考数据.     

偶合反应流动注射化学发光法测定汞

基于Hg(Ⅱ)置换Fe(Ⅱ)-DETA配合物中的Fe(Ⅱ)和Fe(Ⅱ)-鲁米诺-溶解氧产生化学发光的反应,建立了置换偶合反应,流动注射化学发光测定痕量汞的新方法.方法线性范围为1×10~(-7)～1×10~(-5)g·ml~(-1)相对标准偏差为3.5%(n=11,C=1×10~(-6)g·ml~(-1)),检出限为3×10~(-8)g·ml~(-1),方法用于工业废水中汞的测定,结果令人满意.     

邻菲啰啉-Fe(Ⅱ)体系光度法间接测定硫普罗宁

在酸性介质中硫普罗宁可将Fe(Ⅲ)还原为Fe(Ⅱ),邻菲啰啉能与生成的Fe(Ⅱ)显色,最大吸收波长为508 nm。基于此,通过测定Fe(Ⅱ)的量间接测定了硫普罗宁的含量。硫普罗宁在0.08~20μg/mL范围内与ΔA呈良好的线性关系,线性回归方程为ΔA=0.01283+0.06516c(μg/mL),线性相关系数为0.9998,检出限为0.042μg/mL。本方法可用于实际药品中硫普罗宁含量的测定。     

超痕量Fe(Ⅱ)的高效液相色谱测定及其在大气化学研究中的应用

建立了怏速灵敏的反卡相高效液相色谱法用于测定气溶胶、雨水、雪水、海水中超痕量Fe(Ⅱ)。Fe(Ⅱ）与Ferrozille（FZ)络合，在pH4～10形成稳定络合物离子[Fe（FZ）3]2，由[Fe(FZ)3]^2在254nm的色谱峰测定相应的Fe(Ⅱ)浓度。利用反相C18 Sep-Pak固相萃取柱预浓缩水样可使Fe(Ⅱ)检出限达0．1nmol／L。5min内完成一次测定利用此法首次系统测定了中国大气溶胶、雨水和雪样中的痕量Fe(Ⅱ)。连续3年测定了由我国传输到北太平洋的沙尘暴颗粒物中的Fe(Ⅱ)，提供了火气和海洋中的铁疏耦合反馈机制的重要征据。     

流动注射离子交换分离-火焰原子吸收光谱法连续测定铁的形态

研究了一种以NH4F为掩蔽剂掩蔽Fe(Ⅲ),用732型阳离子交换树脂(CSR)吸附Fe(Ⅱ),从而分离测定Fe(Ⅲ)与Fe(Ⅱ)的试验体系。设计了一套新颖的用于该体系的全自动流动注射流路,实现了Fe(Ⅲ)与Fe(Ⅱ)的连续测定。Fe(Ⅲ)和Fe(Ⅱ)的相对标准偏差(n=7)分别为3.37%和1.95%,检出限分别为0.07和0.01 mg.L-1,分析速度为25个样/h。     

用流动注射停流技术-动力学法同时光度测定铁(Ⅱ)和铁(Ⅲ)

在pH5.6的HAc-NaAc缓冲介质中,钛铁试剂(tiron)与Fe(Ⅲ)立即显色而不与Fe(Ⅱ)反应,但tiron的存在能加速Fe(Ⅱ)的氧化进而生成有色络合物.利用不同价态Fe与tiron反应速度的差异,可实现Fe(Ⅱ)和Fe(Ⅲ)的动力学同时测定.本文用流动注射停流技术研究了此反应的动力学行为、估算 Fe(Ⅲ)反应的条件速率常数,并对络合物的吸收光谱、反应酸度、试剂加入量、流路参数及停留时间和反应动力学特性等条件进行了探讨.所拟定的方法用于合成试样分析,获得满意结果.     

铁氰化钾-Fe(Ⅲ)体系测定盐酸异丙肾上腺素

本文建立了以铁氰化钾-Fe(Ⅲ)体系测定盐酸异丙肾上腺素的方法。研究表明,在pH 3.0,盐酸异丙肾上腺素可使Fe(Ⅲ)还原为Fe(Ⅱ),生成的Fe(Ⅱ)可以与K_3[Fe(CN)_6]反应生成可溶性普鲁士蓝(KFe~(Ⅲ)[Fe~(Ⅱ)(CN)_6)。盐酸异丙肾上腺素的浓度在0.03~5.00μg·m L~(-1)范围内与吸光度呈现良好线性关系,线性回归方程A=0.017+0.57779C(μg·m L~(-1)),相关系数R=0.9997,检出限为0.025μg·m L~(-1),相对标准偏差R.S.D.=1.05%(n=11),间接测定盐酸异丙肾上腺素的摩尔吸光系数ε=1.4×105L·mol~(-1)·cm~(-1)。本方法成功用于药物制剂和生物样品中盐酸异丙肾上腺素含量的测定,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。     

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.     

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.     

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.     

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。     

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。