微量气体大小球三步同位素稀释质谱法理论探讨与实验模型设计

提出了一种适用于微量气体定量分析的大小球三步同位素稀释质谱法,并给出其实验模型和不确定度理论分析结果。通过引入三步稀释过程,不涉及稀释剂的纯度、丰度、添加质量等方面的数据,仅需测定各步稀释剂质量之比,在其中的两步反稀释过程中使用了基标准纯物质,从而使微量气体的定量分析结果可溯源至基标准纯物质。该方法解决了已有同位素稀释质谱法在微量气体定量分析中的难题。     

粉末压饼LA-ICP-MS测定土壤样品中微量元素

研究了采用粉末压饼制样LA-ICP-MS测定土壤样品中多元素的分析方法.在土壤样品中事先加入已知含量的In,并以聚四氟乙烯(PTFE)为粘合剂,在200 KN的压力下制备用于激光剥蚀的压饼.详细讨论了粉末压饼样品中元素的均一性及元素相对信号响应.所建立的方法用于土壤标准参考物质固体样品的直接分析,测定值与参考值具有较好的一致性.     

Use of complex displacement reactions in photometric analysis

The theoretical requirements for the quantitative photometric determination of trace amounts of metal ions by use of complex displacement reactions are discussed and a calculation method using conditional equilibrium constants and side-reaction functions defined and used by Ringbom is recommended. As an example, the requirements in the determination of erbium(III) by using copper(II)-EDTA complex and PAN indicator in ammonium lactate buffer solutions are calculated.     

电感耦合等离子体发射光谱法测定柑桔类水果及果皮中多种微量元素

采用HNO_3-HClO_4体系湿法消解样品,利用电感耦合等离子体发射光谱仪同时测定了柑桔类水果及果皮中Al、B、Ba、Ca、Cu、Fe、K、Mg、Mn、Na、Sr、Zn 12种微量元素的含量。分析结果的相对标准偏差0.35%~3.26%,加标回收率85.5%~107.0%,该法简单、快速、可靠、灵敏度高。实验表明,大部分柑桔类水果果皮中微量元素含量高于其果肉中含量。柚子内皮和外皮中微量元素含量有少许差异,柚子外皮中的K、Ca、Mg含量最高,而柚子内皮中Fe、Na的含量较高。该结果为有效利用柑桔类水果果皮的药用功效提供了定量参考依据。     

Development of an orthogonal method for mometasone furoate impurity analysis using supercritical fluid chromatography

While supercritical fluid chromatography (SFC) has received great popularity in chiral separation and purification, it has rarely been used for trace level pharmaceutical impurity analysis, partially due to the limitation of instrument sensitivity. In this study, a packed column SFC method has been developed for the quantitative analysis of mometasone furoate and its trace level impurities. The UV detection was optimized to improve the sensitivity by 2-4 fold. In combination with an increased sample concentration, this SFC method is capable of trace level (0.05% of the active) analysis of the impurities. The SFC method used a silica column and a mobile phase consisting of CO(2) and methanol. The new method provides an orthogonal selectivity complementary to the reversed phase HPLC (RP-HPLC) method. All of the impurities and the active were baseline separated within 12 min on SFC, which is less than one third of the RP-HPLC method run time. The method was also partially validated for linearity, accuracy, precision (repeatability), and limit of quantitation. This study demonstrated that the SFC method, with improved sensitivity, can be a valuable tool to provide orthogonal selectivity for trace level impurity separation. With further validation, the method may be suitable for release testing and stability testing for mometasone furoate drug substance.     

Determination of enantiomeric excess by capillary electrophoresis

Capillary electrophoresis (CE) is becoming an established method for the determination of chiral trace impurities. This paper provides an overview of the state of the art of CE for such determinations. Detection limits of 0.1% impurity is widely accepted as a minimum requirement for chiral trace impurity determinations. This can be relatively easily achieved with CE. However, determination of lower concentrations requires careful optimization of the separation system. Four factors that are of particular significance for trace enantiomeric determinations: resolution, limit of detection, linear range and type of detection, are discussed. Further, the advantages and disadvantages of derivatization in this context are treated as well as the separation approach, ie., direct chiral separation or separation after the formation of diastereomers. It is concluded that the limit of impurity detection can be about 0.05% when UV detection is employed. Using laser-induced fluorescence detection, a quantitative determination at the 0.005% level is often possible.     

Crystallization of chiral compounds 4. Simple physical model for reconstruction of post-eutectic DSC traces for melting of binary enantiomeric mixtures

A theoretical model reproducing qualitative and quantitative characteristics of DSC traces for melting of eutectic enantiomeric mixtures was proposed. The method for reconstruction of an idealized trace from a fragment of the real experimental melting curve was developed. When studying a sample of intermediate enantiomeric composition, the reconstruction of the trace makes it possible to avoid ambiguity in determination of the liquidus temperature, determine the melting temperature for an enantiopure compound, and estimate the composition of the sample. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1288–1293, July, 2007.     

Spektralanalytische Spurenbestimmung in hochreinen Silberhalogeniden unter Verwendung spezieller Auswerteverfahren

A method is given for the quantitative determination of trace elements in silver halides by spectral analysis down to concentrations of 0.01 ppm. A method of evaluation is described, which allows to use reference lines of different wave-lengths and density curves. For a rough estimation or in the case of low impurity concentrations two other methods are used taking the background as reference value.     

基质固相分散-高效液相色谱法测定痕量异丙威和溴氰菊酯

研究了基质固相分散（MSPD）处理复杂样品技术与高效液相色谱法相结合测定食物中痕量异丙威和溴氰菊酯残留物的新方法。研究了MSPD技术进行前处理的实验条件并讨论了与传统残留分析的区别。首次将MSPD技术应用于水果、粮食等食物中异丙威和溴氰菊酯残留物的高效液相色谱分析,并对定量检测条件作了详细的研究。     

A novel solid-phase extraction method for separation and preconcentration of zirconium

This work assesses the use of modified natural clinoptilolite as an adsorptive material for separation and preconcentration of trace amounts of zirconium ions. A simple, rapid and economical method was developed for the preconcentration of trace amounts of zirconium in aqueous medium using 1-(2-pyridylazo)-2-naphthol as a complexing agent. Effect of sample pH, flow rate of sample and elution solutions, breakthrough volume and interference of several ions were studied. Determination of zirconium was made by ICP-AES technique. The sorption was quantitative in the pH range from 3.0 to 4.0, whereas quantitative desorption occurred instantaneously with 2 mol L^?1 hydrochloric acid. Linearity was maintained between 0.05 and 9.0 μg mL^?1. Relative standard deviations range from ±0.9% to ±2.3% (n?=?5). The detection limit was 0.1 ng mL^?1. Because of good recovery (>97%), this method is suitable for preconcentration and determination of zirconium in effluents containing trace amount of zirconium.     

Supercritical water decomposition of polyethylene samples for the determination of their trace cadmium content.

A novel pretreatment method has been developed for determination of toxic metals in plastic materials by their decomposition under supercritical water conditions. Particularly, quantitative analysis of cadmium in polyethylene has been demonstrated using inductively coupled plasma atomic emission spectrometry combined with supercritical water treatment. All the cadmium in a polyethylene sample was obtained as an aqueous solution by the treatment with supercritical water containing 12.4% of hydrogen peroxide at 673 K. Although a complete recovery of the aqueous solution from the reactors has not yet been attained, we verified that the present method was effective and promising for quantitative analysis of trace amounts of hazardous metals in plastic materials.     

Rapid laser fluorometric method for the determination of uranium in soil, ultrabasic rock, plant ash, coal fly ash and red mud samples

A simple and rapid laser fluorometric determination of trace and ultra trace level of uranium in a wide variety of low uranium content materials like soil, basic and ultra basic rocks, plant ash, coal fly ash and red mud samples is described. Interference studies of some common major, minor and trace elements likely to be present in different, geological materials on uranium fluorescence are studied using different fluorescence enhancing reagents like sodium pyrophosphate, orthophosphoric acid, penta sodium tri-polyphosphate and sodium hexametaphosphate. The accurate determination of very low uranium content samples which are rich in iron, manganese and calcium, is possible only after the selective separation of uranium. Conditions suitable for the quantitative single step extraction of 25 ng to 20 μg uranium with tri-n-octylphosphine oxide and single step quantitative stripping with dilute neutral sodium pyrophosphate, which also acts as fluorescence enhancing reagent is studied. The aqueous strip is used for the direct laser fluorometric measurement without any further pretreatment. The procedure is applied for the determination of uranium in soil, basalt, plant ash, coal fly ash and red mud samples. The accuracy of the proposed method is checked by analyzing certain standard reference materials as well as synthetic sample with known quantity of uranium. The accuracy and reproducibility of the method are fairly good with RSD ranging from 3 to 5% depend upon the concentration of uranium.     

三氟氯氰菊酯农药中微量杂质的液相色谱－质谱法鉴定

用高效液相色谱－质谱联用技术研究了三氟氯氰菊酯农药的杂质及含量,并用源内碰撞诱导解离（CID）技术鉴别了所存在的微量杂质。方法实用性强,色谱分离效果好,可用于该农药各成分的定性、定量分析。     

Gas-chromatographische Bestimmung von Wasser

The methods for the determination of trace amounts of water are discussed and the utilization of Porapak as a column material for quantitative analysis of trace water by adsorption gas-chromatography is described. The detection limit for quantitative analysis without preceding concentration is 150 vol.-ppm for the analysis of gases and 1 vol.-ppm for the analysis of liquids.     

磷酸酯螯合纤维富集—AES测定微量镓和铟铟

研究了胺基膦酸酯螯合纤维对于微量Ga~(3 )、In~(3 )的吸附性能,确定了定量吸附和解脱酸度,讨论了吸附机理和共存离子的干扰。低浓度离子的吸附及废水样的分析亦获得了满意的结果。     

Edman-Abbau als analytische methode in der ‘Solid phase’-Peptidsynthese. Vorläufige Mitteilung

The systematic analysis of solid phase peptide synthesis by Edman degradation becomes possible by the development of a technique (high pressure liquid chromatography) for the determination of phenylthiohydantoins in trace amounts. By its qualitative beside the quantitative results the degradation method offers the possibility to follow formation and propagation of failure sequences over more than one synthetic cycle. Scope and limitations of the method are discussed.     

Quantitative analysis of trace metal ions in ice using laser-induced breakdown spectroscopy

This work reports on a simple, quick-freeze method for the quantitative analysis of trace metal ions in liquids applying the laser-induced breakdown spectroscopy (LIBS) technique. Using this procedure with calibrated samples, well-characterized linear working curves were determined for Na and Al water solutions over the 0.01–1% concentration range. This allowed detection limits of the order of ppm. In addition, optimum experimental conditions were found that allow the analysis to be carried out in a fast and very easy manner, without the limitations and difficulties found with liquid samples. The advantages of this simple and direct method, developed and patented by the Instituto Pluridisciplinar–UCM, are discussed, and potential applications for industrial analysis are also suggested.     

A Duffing oscillator algorithm to detect the weak chromatographic signal

Based on the Duffing equation, a Duffing oscillator algorithm (DOA) to improve the signal-to-noise ratio (SNR) was presented. By simulated and experimental data sets, it was proven that the signal-to-noise ratio (SNR) of the weak signal could be greatly enhanced by this method. Using signal enhancement by DOA, this method extends the SNR of low concentrations of methylbenzene from 2.662 to 29.90 and the method can be used for quantitative analysis of methylbenzene, which are lower than detection limit of an analytical system. The Duffing oscillator algorithm (DOA) might be a promising tool to extend instrumental linear range and to improve the accuracy of trace analysis. The research enlarged the application scope of Duffing equation to chromatographic signal processing.     

Quantitative analysis of trace‐level benzene,toluene, ethylbenzene,and xylene in cellulose acetate tow using headspace heart‐cutting multidimensional gas chromatography with mass spectrometry

This study describes a method for the quantification of trace‐level benzene, toluene, ethylbenzene, and xylene in cellulose acetate tow by heart‐cutting multidimensional gas chromatography with mass spectrometry in selected ion monitoring mode. As the major volatile component in cellulose acetate tow samples, acetone would be overloaded when attempting to perform a high‐resolution separation to analyze trace benzene, toluene, ethylbenzene, and xylene. With heart‐cutting technology, a larger volume injection was achieved and acetone was easily cut off by employing a capillary column with inner diameter of 0.32 mm in the primary gas chromatography. Only benzene, toluene, ethylbenzene, and xylene were directed to the secondary column to result in an effective separation. The matrix interference was minimized and the peak shapes were greatly improved. Finally, quantitative analysis of benzene, toluene, ethylbenzene, and xylene was performed using an isotopically labeled internal standard. The headspace multidimensional gas chromatography mass spectrometry system was proved to be a powerful tool for analyzing trace volatile organic compounds in complex samples.