Quantitative Determination of Octamethylcyclotetrasiloxane (D4) in Extracts of Biological Matrices by Gas Chromatography-Mass Spectrometry

Abstract

A method was developed and validated to measure octamethylcyclotetrasiloxane (D₄)^? quantitatively by gas chromatography-mass spectrometry (GC-MS) at low level in extracts of several biological matrices that include plasma, liver, lung, feces and fat from rats. The key to the successful determination lay in the use of extracts dried with anhydrous magnesium sulfate. This was necessary in view of the propensity of the methyl siloxane based GC-stationary phase to generate D₄ by its reaction with water present in the extracts. To enable quantiiation of D₄ at parts per billion (μg/L) levels, the base ion m/z 281 resulting from the loss of a methyl group from the parent molecule was selected for monitoring by SIM mode in GC-MS. The recovery of D₄ from any of the biological matrices was determined to be greater than 90% in three extractions. The D₄ response for the standards in GC-MS was linear (R² > 0.9900) and reproducible at concentrations ranging from 1—16,000 ng D₄/g solvent. Precision was less than 5%.     

Comparison of membrane assisted liquid–liquid microextraction devices applied to a series of volatile organic compounds in aqueous environmental matrices

An extraction device has been investigated for the separation and preconcentration of a series of volatile organic compounds (CHCl₃, CHCl₂Br, CHClBr₂ and CHBr₃) in aqueous matrices. The device consisted of a microporous membrane system utilising a hollow fibre tube filled with organic solvent directly immersed into the sample solution. The hollow fibre containing 160 µL organic solvent was immersed in a glass vial with 10 mL capacity, and the extraction took place through diffusive transport between the aqueous sample and the small amount of solvent. For validation of the method, some operational conditions, such as extraction solvent, temperature, stirring rate and separation time, were optimised. Limit of detection was at low ppb levels, with GC-MS analysis under selected ion monitoring (SIM), whereas enrichment factors between 22 and 35 were obtained. Good reproducibility with RSDs between 7.2% and 9.8% and large linear dynamic ranges with R ² between 0.996 and 0.998 were also achieved. In addition, the performance of the membrane assisted solvent extraction (MASE) system was compared with two existing configurations: a non-porous membrane separation device, as well as with a comparable microporous configuration. The comparison considered the extraction mechanism and the underlying transport processes. The application to real samples showed a good concordance with classical analytical methods.     

Ionic liquids as stationary phases in gas chromatography: Determination of chlorobenzenes in soils

The present research focuses on the evaluation of different ionic liquid (IL) stationary phases in gas chromatography. The different IL columns were evaluated in terms of peak resolution (R_s) and peak symmetry for the separation of the chlorobenzenes. The determination of chlorobenzenes in soil samples by means of the optimal IL stationary phase (SLB‐IL82) is proposed as an application. Soil pretreatment was based on a simplified quick, easy, cheap, effective, rugged, and safe extraction procedure and a large injection volume via a programed temperature vaporizer working in solvent vent mode. The retention time of the chlorobenzenes increased as the polarity of the IL column decreased. SLB‐IL82 is the stationary phase that provides the best values as regards R_s and asymmetry factor. Soil sample blanks were spiked with the analytes before subjecting the sample to the extraction process. The existence of a matrix effect was checked and the analytical characteristics of the method were determined in a fortified garden soil sample. The method provided good linearity, good repeatability and reproducibility values, and the LODs were in the 0.1–4.7 μg/kg range. Two fortified soil samples were applied to validate the proposed methodology.     

Engineering of Supported Nanomaterials

This brief review analyzes the parameters that can be used to guide the generation of hierarchic systems that include inorganic and/or biological nanoscale objects. Importance of interface effects and geometrical factors are underlined. The mutual influence between the substrate and the deposited material is an important factor to determine the most appropriate set of parameters for the synthesis of nanomaterials with desirable properties for industrial applications.     

Solid-phase extraction techniques based on nanomaterials for mycotoxin analysis: An overview for food and agricultural products

Mycotoxin contamination is a globally concerned problem for food and agricultural products since it may directly or indirectly induce severe threats to human health. Sensitive and selective screening is an efficient strategy to prevent or reduce human and animal exposure to mycotoxins. However, enormous challenges exist in the determination of mycotoxins, arising from complex sample matrices, trace-level analytes, and the co-occurrence of diverse mycotoxins. Appropriate sample preparation is essential to isolate, purify, and enrich mycotoxins from complicated matrices, thus decreasing sample matrix effects and lowering detection limits. With the cross-disciplinary development, new solid-phase extraction strategies have been exploited and integrated with nanotechnology to meet the challenges of mycotoxin analysis. This review summarizes the advance and progress of solid-phase extraction techniques as the methodological solutions for mycotoxin analysis. Emphases are paid on nanomaterials fabricated as trapping media of solid-phase extraction techniques, including carbonaceous nanoparticles, metal/metal oxide-based nanoparticles, and nanoporous materials. Advantages and limitations are discussed, along with the potential prospects.     

An analysis of cross-correlations in an emerging market

We apply random matrix theory to compare correlation matrix estimators C$C$ obtained from emerging market data. The correlation matrices are constructed from 10 years of daily data for stocks listed on the Johannesburg stock exchange (JSE) from January 1993 to December 2002. We test the spectral properties of C$C$ against random matrix predictions and find some agreement between the distributions of eigenvalues, nearest neighbour spacings, distributions of eigenvector components and the inverse participation ratios for eigenvectors. We show that interpolating both missing data and illiquid trading days with a zero-order hold increases agreement with RMT predictions. For the more realistic estimation of correlations in an emerging market, we suggest a pairwise measured-data correlation matrix. For the data set used, this approach suggests greater temporal stability for the leading eigenvectors. An interpretation of eigenvectors in terms of trading strategies is given, as opposed to classification by economic sectors.     

确定性矩阵可分离压缩成像

针对可分离压缩传感使用的可分离随机正交矩阵在处理大尺度图像等高维信号感知时难度太大或成本过高的问题,引入确定性测量矩阵,提出确定性矩阵可分离压缩传感,可将如托普利兹矩阵及循环矩阵等具有确定性结构的矩阵作为可分离压缩传感的左、右可分离矩阵.该方案可以降低独立元素的数目,从而显著降低前端物理实现的难度与成本.数值模拟实验分别评估了该方法在不同采样率及不同图像尺寸下的压缩重建性能,结果表明该方法在独立元素非常少的情形下得到与原随机正交矩阵相近的重建质量,证明了其可行性.     

Functional Differential Equations With Delay and Random Effects

The authors study the existence of mild solutions to a functional differential equation with delay and random effects. They use a random fixed point theorem with a stochastic domain. An example is included to illustrate their results.     

Joint distributions of random sets and their relation to copulas

Random sets are set-valued random variables. They have been applied in various fields like stochastic geometry, statistics, economics, engineering or computer science, and are often used for modeling uncertainty. In an earlier paper the author has defined joint capacity and joint containment functionals which are multivariate set functions describing the joint distribution of random sets. This paper is concerned with the question how copulas can be used to describe or model the dependence of random sets. It is demonstrated that a joint containment functional can be related to its margins by a family of copulas. Furthermore, the paper provides a first insight how copulas can be used to define joint containment functionals.