Tutorial review on validation of liquid chromatography–mass spectrometry methods: Part I

This is the part I of a tutorial review intending to give an overview of the state of the art of method validation in liquid chromatography mass spectrometry (LC–MS) and discuss specific issues that arise with MS (and MS/MS) detection in LC (as opposed to the “conventional” detectors). The Part I briefly introduces the principles of operation of LC–MS (emphasizing the aspects important from the validation point of view, in particular the ionization process and ionization suppression/enhancement); reviews the main validation guideline documents and discusses in detail the following performance parameters: selectivity/specificity/identity, ruggedness/robustness, limit of detection, limit of quantification, decision limit and detection capability. With every method performance characteristic its essence and terminology are addressed, the current status of treating it is reviewed and recommendations are given, how to determine it, specifically in the case of LC–MS methods.     

Further study of alternating iterations for rectangular matrices

Theory of matrix splittings is a useful tool in the analysis of iterative methods for solving systems of linear equations. When two splittings are given, it is of interest to compare the spectral radii of the corresponding iteration matrices. This helps to arrive at the conclusion that which splitting should one choose so that one can reach the desired solution of accuracy or the exact solution in a faster way. In the case of many splittings are provided, the comparison of the spectral radii is time-consuming. Such a situation can be overcome by introducing another iteration scheme which converges to the same solution of interest in a much faster way. In this direction, the theory of alternating iterations for real rectangular matrices is recently proposed. In this note, some more results to the theory of alternating iterations are added. A comparison result of two different alternating iteration schemes is then presented which will help us to choose the iteration scheme that will guarantee the faster convergence of the alternating iteration scheme. In addition to these results, a comparison result for proper weak regular splittings is also obtained.     

Sturmian comparison theory for half‐linear and nonlinear differential equations via Picone identity

In this paper, Sturmian comparison theory is developed for the pair of second‐order differential equations; first of which is the nonlinear differential equations of the form (1) and the second is the half‐linear differential equations (2) where Φ_α (s ) = |s |^{α  ? 1}s and α ₁ > ? > α _m  > β  > α _{m  + 1} > ? > α _n  > 0. Under the assumption that the solution of  2 has two consecutive zeros, we obtain Sturm–Picone type and Leighton type comparison theorems for  1 by employing the new nonlinear version of Picone formula that we derive. Wirtinger type inequalities and several oscillation criteria are also attained for  1 . Examples are given to illustrate the relevance of the results. Copyright © 2016 John Wiley & Sons, Ltd.     

GARCH(1,1)模型的稳健估计比较及应用

首先阐述了GARCH(1,1)模型稳健估计的构造方法,然后在模型有无异常值扩散效应约束和异常值比例不同的情况下,比较了传统QMLE估计和多种稳健M估计的表现,结果表明:在数据无异常值下,QMLE估计较优;随着异常值比例增加,稳健Andrew估计表现更好;模型施加异常值扩散效应约束对估计有一定改善但不显著.最后选取波动程度不同的两个阶段沪深300指数的收益率,用模型拟合进行了实例比较,在波动程度较大时,Andrew估计效果较优,在波动相对平稳时,LAD估计较优.     

Technical stability of stationary automatic control systems of variable structure with switched filters

Sufficient conditions for the technical stability in measure of a nonstationary control system with variable structure are established. The controller of the system has feedback-switched filters functioning together with shaper and actuator. It is assumed that the nonstationary parameters of the system vary within given ranges, at a finite rate, with appropriate control laws, with adjustment against mismatch signal, its derivatives of finite order, and all variable parameters of the filter. The parameters of the switching hyperplane remain constant. This approach for analysis of technical stability does not involve sliding mode conditions. Criteria of technical instability in measure for the control system under consideration are formulated using the properties of systems of comparison from below. The general criteria of technical stability and instability are applied to nonstationary filtered-control systems of variable structure of the third order. The comparison method based on normalized Lyapunov functions is used __________ Translated from Prikladnaya Mekhanika, Vol. 42, No. 6, pp. 110–127, June 2006.     

Improved operator comfort and off-road capability through pendulum arm technology

The Nordic forest industry requires just-in-time wood deliveries. Operations must continue regardless of season, weather and terrain. Soil compaction and deep ruts must be avoided while providing high performance and a reasonable working environment for operators.The Xt28 pendulum arm forwarder is a full-size concept forwarder with six hydrostatic propelled wheels on pendulum arms built on a three-piece frame connected with two articulation joints. The Xt28 concept machine was tested according to Skogforsk standard machine tests. Rut depth test focused on soil interaction where rut depth was measured related to number of passes. Machine dynamics were measured using standardized test track with focus on operator comfort.The project proved the potential of pendulum arm technology in off-road transportation. Automatic pendulum arm levelling, equalized ground pressure between wheels and improved operator comfort through reducing adverse vibrations and roll angles, simultaneously reducing dynamic forces transferred to the forest floor. Pendulum arm technology improves travel speed in adverse terrain, providing unparalleled side slope capability and enhanced productivity.     

IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organised the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimise the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

IMEP-24 analysis of eight trace elements in toys

The International Measurement Evaluation Program (IMEP) organized the IMEP-24 interlaboratory comparison after reports in the media about high levels of lead in toys. The aim of this comparison was to verify the laboratories’ capacity to evaluate trace-element levels in a possible toy-like material according to the European Standard EN 71-3:1994. As test material, it used a former certified reference material containing levels of antimony, arsenic, barium, cadmium, chromium, mercury, lead and selenium around the limits set in the standard.Four expert laboratories confirmed the reference values (Xref) for all elements but Hg, and established a reference value for Hg. The scatter of the results reported by the participants was large, as expected, but showed a close to normal distribution around the reference values for five of the eight trace elements. The spread of results was mainly attributed to sampling and sample preparation.One major issue observed in this exercise was the lack of legislative rules about how to report the result, or, more specifically, the use of the analytical correction, which was introduced in EN 71-3:1994 to achieve consistent interpretation of results and which is to be applied when values are equal to or above the maximum limits set in the standard. Its application by the participants was very inconsistent and led to problems in their evaluation. There is clearly a need for clarification and for more formal regulations with regard to result reporting in order to minimize the risk of confusion.Participants were also asked to give their opinion with regard to the acceptability of the test material for the market. The majority correctly considered the material as non-compliant. However, almost one-third incorrectly assessed the material as compliant.     

Electrochemical speciation of dissolved Cu, Pb and Zn in an estuarine ecosystem (Ria de Vigo, NW Spain): comparison between data treatment methods

The total concentration and chemical speciation of Cu, Pb and Zn were determined by square wave anodic stripping voltammetry (SWASV) in the Ría de Vigo, an estuarine area located in NW Spain. Surface and bottom waters from 6 locations were collected in two seasons during 3 years. The total Pb was below 1 nM, and Cu and Zn concentrations, ranged from 3 to 44 nM and from 9 to 300 nM respectively. A gradient from sampling points located in the port of Vigo to external areas was observed. The speciation of the metals (ligand concentration and apparent complex formation constant K′) was calculated using several methods: The Langmuir and Scatchard linear fits for one and two ligands, the Lorenzo non-linear fit for one ligand and Langmuir non-linear fit for two ligands. The capability of the different methods to achieve reliable results have been discussed and Langmuir linear fit as well as Lorenzo non-linear fit are the most suitable. Cu presented the highest ligand concentrations, followed by Zn and Pb, while mean log K′ values fell in the range 5-9 (±0.6) for all metals and samples. The adjustment of the data treatment methods used to calculate the speciation parameters was found to vary depending on the extent of complexation and on whether one or two ligands needed to be considered.