Capillary gas chromatography of pesticide residues in foods: Application of a split/splitless inlet system

Residue mixtures of pesticides in foods which were difficult to separate by packed-column gas chromatography were determined by capillary gas chromatography and electron capture detection. Manual injections of sample and reference standard were made with a 10 μL syringe on a septum-enclosed, split/ splitless inlet system. Optimal peak height repeatability (± 3%( was achieved with three-μL injections which were made within time periods of four hours or less. The average linearity coefficient (slope( obtained for detector response as a function of solution concentration was 1.1.     

Robust estimates of the theoretical standard deviation to be used in interlaboratory precision experiments

Interlaboratory experiments often contain results that strongly deviate from other results obtained in the same laboratory under repeatability conditions, or laboratory means that strongly deviate from other laboratory means. In ISO 5725-2 [1] and IUPAC [2], the basic standards for the organisation and analysis of interlaboratory experiments for the determination of precision of a measurement method, outlier tests are performed in order to detect such situations and to finally decide whether these values are retained in the analysis or discarded as outliers. This outlier treatment, which always has a subjective aspect, becomes unnecessary by using robust estimates of the repeatability and reproducibility standard deviation. This paper proposes to use Rousseeuw’s Q _n as an extremely robust and efficient estimate of the standard deviation. Two examples show the performance of the new method.     

Inverse colloidal crystal membranes for hydrophobic interaction membrane chromatography

A collaborative study on the robustness and portability of a capillary electrophoresis‐mass spectrometry method for peptide mapping was performed by an international team, consisting of 13 independent laboratories from academia and industry. All participants used the same batch of samples, reagents and coated capillaries to run their assays, whereas they utilized the capillary electrophoresis‐mass spectrometry equipment available in their laboratories. The equipment used varied in model, type and instrument manufacturer. Furthermore, different types of sheath‐flow capillary electrophoresis–mass spectrometry interfaces were used. Migration time, peak height and peak area of ten representative target peptides of trypsin‐digested bovine serum albumin were determined by every laboratory on two consecutive days. The data were critically evaluated to identify outliers and final values for means, repeatability (precision within a laboratory) and reproducibility (precision between laboratories) were established. For relative migration time the repeatability was between 0.05 and 0.18% RSD and the reproducibility between 0.14 and 1.3% RSD. For relative peak area repeatability and reproducibility values obtained were 3–12 and 9–29% RSD, respectively. These results demonstrate that capillary electrophoresis‐mass spectrometry is robust enough to allow a method transfer across multiple laboratories and should promote a more widespread use of peptide mapping and other capillary electrophoresis‐mass spectrometry applications in biopharmaceutical analysis and related fields.     

Diffusion tensor magnetic resonance imaging of the normal breast

Purpose

The objective of this study was to evaluate diffusion anisotropy of the breast parenchyma and assess the range and repeatability of diffusion tensor imaging (DTI) parameters in normal breast tissue.

Materials and Methods

The study was approved by our institutional review board and included 12 healthy females (median age, 36 years). Diffusion tensor imaging was performed at 1.5 T using a diffusion-weighted echo planar imaging sequence. Diffusion tensor imaging parameters including tensor eigenvalues (λ₁, λ₂, λ₃), fractional anisotropy (FA) and apparent diffusion coefficient (ADC) were measured for anterior, central and posterior breast regions.

Results

Mean normal breast DTI measures were λ₁=2.51×10⁻³ mm²/s, λ₂=1.89×10⁻³ mm²/s, λ₃=1.39×10⁻³ mm²/s, ADC=1.95±0.24×10⁻³ mm²/s and FA=0.29±0.05 for b=600 s/mm². Significant regional differences were observed for both FA and ADC (P<.05), with higher ADC in the central breast and higher FA in the posterior breast. Comparison of DTI values calculated using b=0, 600 s/mm² vs. b=0, 1000 s/mm², showed significant differences in ADC (P<.001), but not FA. Repeatability assessment produced within-subject coefficient of variations of 4.5% for ADC and 11.4% for FA measures.

Conclusion

This study demonstrates anisotropy of water diffusion in normal breast tissue and establishes a normative range of breast FA values. Attention to the influence of breast region and b value on breast DTI measurements may be important for clinical interpretation and standardization of techniques.     

Do we need to rethink collaborative trials?

The currently recommended design of collaborative trials (interlaboratory method performance studies) is examined in relation to the usefulness of the resulting statistics. It is suggested that larger experiments, without duplicate analysis, would be more informative.

Precision of Raman depolarization and optical attenuation measurements of sound tooth enamel

The demineralization of enamel that is associated with early caries formation affects the optical properties of the enamel. Polarized Raman spectroscopy and optical coherence tomography have been used to detect these changes and potentially offer a means to detect and monitor early caries development. The total optical attenuation coefficient as measured by optical coherence tomography and the polarization anisotropy of the Raman peak arising from the symmetric ν₁ vibration of at approximately 959 cm⁻¹ have been demonstrated as being sensitive markers of early caries. This ex vivo study on extracted human teeth demonstrates that these measurements can be made with reasonable precision with concomitantly good repeatability and reproducibility in sound enamel. Such reliability is crucial for these techniques to have a practical clinical value.     

Replicated observations in metrology and testing: modelling repeated and non-repeated measurements

In order to choose the right statistical tool, a basic issue for an accurate analysis of each specific problem is to understand whether the set of replicated measurement results under examination is to be considered as pertaining to repeated measurements or not. This issue is particularly important, since most of the traditional tools are valid only for repeated measurements, but, in many cases, such as laboratory comparisons (in metrology and in testing), the measurements necessary to assess correctly the measurand value and the associated uncertainty do not represent repeated measurements. The analysis performed in this paper aims to shine some light on these issues, starting with a review of the basic concepts, such as repeatability, reproducibility, accuracy, systematic error and bias, as defined in international documents and as used in the literature. The paper shows that, currently, a full consensus on a common language and understanding has not yet been achieved, and then shows how this fact reflects on the basic data models, especially those concerning inter-comparison data.

小麦品质近红外检测系统的设计与试验研究

为实现快速无损地检测小麦品质设计了基于光栅技术的近红外检测系统,测试了该系统的准确性、重复性和稳定性,选取MPA光谱仪为参比仪器,分别采集56份小麦样品的光谱,建立偏最小二乘回归模型并验证。该系统的四个模型的决定系数R2分别为92.38%,93.48%,93.16%,94.44%,交叉验证标准差RESECV为0.405,0.374,0.383,0.346,相对分析误差RPD为3.62,3.39,3.82,4.24;预测集验证模型的R2为96.97%,94.22%,96.62%,96.34%,预测标准差RMSEP为0.221,0.305,0.233,0.243。MPA光谱仪的建模结果R2 为95.99%,RESECV 为0.293,RDP为5;预测集验证模型的R2为98.31%,RMSEP为0.165。实验表明：小麦品质近红外检测系统所得模型具有良好的预测性,稳定性和重复性;所得光谱波长与吸光度具有重现性;其模型对平均光谱的预测效果优于单张光谱;该系统工作稳定,性能优良,可应用于小麦品质质量检测。     

两位置球面面形检测方法研究

三位置球面面形绝对检测方法在一定的条件下可以简化为两位置球面面形检测方法.本文在研究三位置绝对检测原理的基础上,提出了基于菲索干涉系统新的两位置球面面形检测方法.该方法的简化条件分为参考面面形误差偶对称或被检面面形误差偶对称两种不同的情况.实验结果表明,两位置检测方法可以有效实现PVr值λ/30的高准确度检测,且检测结果PVr值重复性在±λ/300范围内,RMS值重复性在±λ/4 000范围内.采用两位置检测方法得到的面形误差分布结果与三位置绝对检测方法非常接近,PVr值相差小于λ/300,RMS值相差小于λ/2 500.因此在一定条件下,两位置检测方法可以有效简化实验装置和检测步骤,且不失三位置绝对检测方法的准确度和重复性.     

Comparison of Single Pulse and Double Simultaneous Pulse Laser Induced Breakdown Spectroscopy

A simple and cost-effective variant of laser induced breakdown spectroscopy is presented that involves a double simultaneous pulse configuration employing a single laser source. Its performance is compared with conventional single pulse configuration. Double simultaneous pulses were accomplished by splitting a Nd:YAG laser (1064 nm, 6 ns, 360 mJ) beam into two components that were focused on the sample surface to produce two concurrent breakdowns. Experiment was repeated for single pulse and double simultaneous pulses under different ambient pressures. The performance was evaluated on the basis of self-absorption, signal-to-noise ratio (SNR), and relative standard deviation (RSD) of the Mg II doublet (280.2704 nm, 279.553 nm). Optically thin emission lines of better profiles with higher signal-to-noise ratio resulted from double simultaneous pulses. The lowest relative standard deviations obtained by single pulse and double simultaneous pulse configurations were 18.89% and 12.01%, respectively. In fact, double simultaneous pulses have performed better than single pulse in all respects within the studied regime.