Rapid analysis of multicomponent pesticide mixture by GC-MS with the aid of chemometric resolution

Applications of hyphenated chromatographic techniques, especially GC-MS technique, have been reported in chemical, biological, environmental, agricultural and medical analysis. The complexity of the samples in these fields is still an obstacle for the technique to be practical and the overlapping of the multicomponent signals induces chemometric methods widely employed. In this work, taking the rapid analysis of pesticide mixture as an example, a chemometric approach was proposed for resolution of multicomponent overlapping GC-MS signal. In the method, a mass spectral library of pesticides was organized at first, then target factor analysis (TFA) was employed for testing the existence of a specific pesticide in the multicomponent overlapping GC-MS signal, and finally the chromatographic information of the pesticide was extracted by a non-negative immune algorithm (IA). A GC-MS signal of a 40-component pesticide mixture eluted within 9 min was analyzed by the method. It was found that the mass spectra and chromatographic profiles of almost all the pesticides can be obtained.     

Gas chromatography coupled to high-resolution time-of-flight mass spectrometry to analyze trace-level organic compounds in the environment, food safety and toxicology

Gas chromatography coupled to high-resolution time-of flight mass spectrometry (GC-HR-TOF-MS) is a powerful analytical technique with excellent capabilities due to its high sensitivity in full-spectrum-acquisition mode together with its resolving power and accurate-mass measurements. These features make this technique very attractive in qualitative analysis, especially for wide-scope screening of a large number of organic contaminants and residues at trace levels.Full-spectrum MS allows data processing, in principle, of an unlimited number of compounds in samples, as no analyte-specific information is required before the injection. Also, as all data remain available, retrospective analysis is always possible without the need to reinject the sample - an important advantage of full-spectrum MS techniques. Despite these advantages, GC-HR-TOF-MS has rarely been applied, so we expect promising results in different applied fields in the years ahead.We discuss in detail the characteristics and the potential of GC-HR-TOF-MS. We describe different analytical strategies from wide-scope target screening to investigation of unknowns in biology, the environment and food safety. Recent instrumental developments (e.g., high-speed analog-to-digital converter or soft ionization sources) and advances in software for processing the huge amount of data available open up new prospects, making GC-TOF-MS one of the most promising techniques to investigate the presence of organic compounds in different fields.     

Multiwavelength Spectrophotometric Determination of Acid Dissociation Constants. Deconvolution of Binary Mixtures of Ionizable Compounds

ABSTRACT

A spectral deconvolution method based on target factor analysis has been developed to determine pK_a values of binary mixtures of monoprotic and/or diprotic ionizable compounds. The technique makes use of the approach of Frans and Harris, which has been implemented previously for mixtures of monoprotic compounds (Anal. Chem. 1985, 57, 1718-1721), to extract the unknown pK_a values. The method has been illustrated by using the multiwavelength spectrophotometrictitation data of binary mixtures of: I. benzoic acid and phenol, 2. benzoic acid and nicotinic acid, 3. p-aminosalicylic acid and phthalic acid. It was demonstrated that the pK_a values as determined in this study are in good agreement with the literature.     

多层防御模式下武器目标分配决策的群体智能优化算法

武器目标分配(WTA)是军事运筹学中经典的NP完全问题,迄今为止未找到求精确解的多项式时间算法.针对武器数量、布防空间、运行维护成本以及人力资源等多约束下的多层防御WTA问题,采用粒子群优化(PSO)和蚁群优化(ACO)两种群体智能算法求解.给出了PSO和ACO算法实现方案,通过一个算例评估两个算法的性能.结果表明,两种算法都能给出高质量的近似最优解,对求解WTA问题是有效的.PSO在解的质量、算法鲁棒性和计算效率方面均优于ACO.     

Incorporating performance measures with target levels in data envelopment analysis

Data envelopment analysis (DEA) is a technique for evaluating relative efficiencies of peer decision making units (DMUs) which have multiple performance measures. These performance measures have to be classified as either inputs or outputs in DEA. DEA assumes that higher output levels and/or lower input levels indicate better performance. This study is motivated by the fact that there are performance measures (or factors) that cannot be classified as an input or output, because they have target levels with which all DMUs strive to achieve in order to attain the best practice, and any deviations from the target levels are not desirable and may indicate inefficiency. We show how such performance measures with target levels can be incorporated in DEA. We formulate a new production possibility set by extending the standard DEA production possibility set under variable returns-to-scale assumption based on a set of axiomatic properties postulated to suit the case of targeted factors. We develop three efficiency measures by extending the standard radial, slacks-based, and Nerlove–Luenberger measures. We illustrate the proposed model and efficiency measures by applying them to the efficiency evaluation of 36 US universities.     

Volatility Targeting Using Delayed Diffusions

ABSTRACT

A target volatility strategy (TVS) is a risky asset-riskless bond dynamic portfolio allocation which makes use of the risky asset historical volatility as an allocation rule with the aim of maintaining the instantaneous volatility of the investment constant at a target level. In a market with stochastic volatility, we consider a diffusion model for the value of a target volatility fund (TVF) which employs a system of stochastic delayed differential equations (SDDEs) involving the asset realized variance. First we prove that under some technical assumptions, contingent claim valuation on a TVF is approximately of Black-Scholes type, which is consistent with and supports the standing market practice. In second place, we develop a computational framework using recent results on Markovian approximations of SDDEs systems, which we then implement in the Heston variance model using an ad hoc Euler scheme. Our framework allows for efficient numerical valuation of derivatives on TVFs, whose typical purpose is the assessment of the guarantee costs of such funds for insurers.     

Setting staffing requirements for time dependent queueing networks: The case of accident and emergency departments

An incentive scheme aimed at reducing patients’ waiting times in accident and emergency departments was introduced by the UK government in 2000. It requires 98% of patients to be discharged, transferred, or admitted to inpatient care within 4 hours of arrival. Setting the minimal hour by hour medical staffing levels for achieving the government target, in the presence of complexities like time-varying demand, multiple types of patients, and resource sharing, is the subject of this paper. Building on extensive body of research on time dependent queues, we propose an iterative scheme which uses infinite server networks, the square root staffing law, and simulation to come up with a good solution. The implementation of this algorithm in a typical A&E department suggests that significant improvement on the target can be gained, even without increase in total staff hours.     

Synthesis of magnetic rhenium sulfide composite nanoparticles

Rhenium sulfide nanoparticles are associated with magnetic iron oxide through coprecipitation of iron salts with tetramethylammonium hydroxide. Sizes of the formed magnetic rhenium sulfide composite particles are in the range 5.5-12.5 nm. X-ray diffraction and energy-dispersive analysis of X-rays spectra demonstrate the coexistence of Fe₃O₄ and ReS₂ in the composite particle, which confirm the formation of the magnetic rhenium sulfide composite nanoparticles. The association of rhenium sulfide with iron oxide not only keeps electronic state and composition of the rhenium sulfide nanoparticles, but also introduces magnetism with the level of 24.1 emu g^-1 at 14 kOe. Surface modification with monocarboxyl-terminated poly(ethylene glycol) (MPEG-COOH) has the role of deaggregating the composite nanoparticles to be with average hydrodynamic size of 27.3 nm and improving the dispersion and the stability of the composite nanoparticles in water.     

ICF靶场中光束口径与列阵间隔的研究

从靶场反射镜架模块的机械结构设计布局所需几何空间的角度出发,根据大口径、列阵器件的特殊要求,给出符合“神光III”装置总体技术要求的ICF靶场光束口径与列阵间隔之间的关系,得出靶场Δ纵、Δ横应满足的公式.     

A strategy for the systematic development of a liquid chromatographic mass spectrometric screening method for polymer electrolyte membrane degradation products using isocratic and gradient phase optimized liquid chromatography

Within the scope of research for target and non-target LC–MS/MS analysis of membrane degradation products of polymer electrolyte membrane fuel cells, a systematic method development for the separation of structurally similar compounds was performed by phase optimized liquid chromatography. Five different stationary phases with different selectivities were used. Isocratic separation for 4-hydroxybenzoic acid, isophthalic acid, terephthalic acid, 4-hydroxybenzaldehyde and 4-formylbenzoic acid was achieved on a C18 and a Phenyl phase. Using the PRISMA model the separation efficiency was optimized. This was achieved on a serially connected mixed stationary phase composed of 30 mm C18, 150 mm Phenyl and 60 mm C30. For the LC–MS screening of unknown degradation products from polymer electrolyte membranes in the product water of a fuel cell, a solvent gradient is mandatory for less polar or later eluting compounds. By means of 4-mercaptobenzoic acid it could be shown that a solvent gradient can be applied in order to elute later eluting compounds in a short time. The adaptability of this method for the qualitative analysis by target and non-target LC–MS/MS screening has been shown by means of 4-hydroxybenzoic acid. The combination of solvent gradient and isocratic conditions makes this approach attractive for the purpose of a screening method for known and unknown analytes in a water sample.