Characterizing nonconstant instrumental variance in emerging miniaturized analytical techniques

Measurement variance is a crucial aspect of quantitative chemical analysis. Variance directly affects important analytical figures of merit, including detection limit, quantitation limit, and confidence intervals. Most reported analyses for emerging analytical techniques implicitly assume constant variance (homoskedasticity) by using unweighted regression calibrations. Despite the assumption of constant variance, it is known that most instruments exhibit heteroskedasticity, where variance changes with signal intensity. Ignoring nonconstant variance results in suboptimal calibrations, invalid uncertainty estimates, and incorrect detection limits. Three techniques where homoskedasticity is often assumed were covered in this work to evaluate if heteroskedasticity had a significant quantitative impact—naked-eye, distance-based detection using paper-based analytical devices (PADs), cathodic stripping voltammetry (CSV) with disposable carbon-ink electrode devices, and microchip electrophoresis (MCE) with conductivity detection. Despite these techniques representing a wide range of chemistries and precision, heteroskedastic behavior was confirmed for each. The general variance forms were analyzed, and recommendations for accounting for nonconstant variance discussed. Monte Carlo simulations of instrument responses were performed to quantify the benefits of weighted regression, and the sensitivity to uncertainty in the variance function was tested. Results show that heteroskedasticity should be considered during development of new techniques; even moderate uncertainty (30%) in the variance function still results in weighted regression outperforming unweighted regressions. We recommend utilizing the power model of variance because it is easy to apply, requires little additional experimentation, and produces higher-precision results and more reliable uncertainty estimates than assuming homoskedasticity.     

新型微型电导池的研制及共地效应的消除

使用简便的方法制作了电极面积大、无死体积、分辨率高、检测限低的微型电导池;较好地消除了毛细管电泳(CE)在柱电导检测装置中存在的共地效应,排除了在线检测时高压分离回路对电导检测回路的干扰.并对制作的微型电导池的性能进行了测试.     

Properties of silicas chemically modified by monodentate amines studied by conductometry

The protonation of aminoalkyl groups covalently bonded on the silica surface was studied by the conductometric titration method. Porous varieties of silica can adsorb HCl from an aqueous solution. Conductometric titration was proposed for the determination of concentrations and constants of protolytic equilibrium of grafted amino groups. During HCl chemisorption the effect of temperature on the electric conductivity of suspensions of the modified silicas was studied. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1789–1793, August, 2005.     

Potentiometric and Conductometric Studies on the Complexes of Some Rare Earth Metals with Rhodanine Azosulfonamide Derivatives, XII

Stability constants for La³⁺, Ce³⁺, UO₂ ²⁺, and Th⁴⁺ metal ion complexes with rhodanine azosulfonamide derivatives have been determined potentiometrically in 0.1 M KCl in a 30% (v/v) ethanol–water mixture. The order of the stability constants of the complexes found was to La³⁺ < Ce ²⁺ < UO ₂ ²⁺ < Th ⁴⁺. The influence of substituents on the stability of the complexes was examined on the basis of electron-repelling property of the substituent. The effect of temperature on the stability constants was studied and the Gibbs energy, the enthalpy, and entropy of complexation thermodynamic parameters were derived and are discussed. The stoichiometries of these complexes were determined conductometrically and the results indicated the formation of 1:1 and 1:2 (metal:ligand) complexes.     

Roundoff-induced attractors and reversibility in conservative two-dimensional maps

We numerically study two conservative two-dimensional maps, namely the baker map (whose Lyapunov exponent is known to be positive), and a typical one (exhibiting a vanishing Lyapunov exponent) chosen from the generalized shift family of maps introduced by C. Moore [Phys. Rev. Lett. 64 (1990) 2354] in the context of undecidability. We calculate the time evolution of the entropy (). We exhibit the dramatic effect introduced by numerical precision. Indeed, in spite of being area-preserving maps, they present, well after the initially concentrated ensemble has spread virtually all over the phase space, unexpected pseudo-attractors (fixed-point like for the baker map, and more complex structures for the Moore map). These pseudo-attractors, and the apparent time (partial) reversibility they provoke, gradually disappear for increasingly large precision. In the case of the Moore map, they are related to zero Lebesgue-measure effects associated with the frontiers existing in the definition of the map. In addition to the above, and consistent with the results by V. Latora and M. Baranger [Phys. Rev. Lett. 82 (1999) 520], we find that the rate of the far-from-equilibrium entropy production of baker map numerically coincides with the standard Kolmogorov-Sinai entropy of this strongly chaotic system.     

精密数字式STC衰减组件的设计

主要介绍了某型号雷达接收前端中精密数字式STC衰减组件的设计。其优点是具有数字式可编程、精度高、曲线误差小。     

靶丸表面轮廓形貌AFM精密测量及特性评价

 建立了由改造的原子力显微镜(AFM)、精密回转气浮轴系、辅助转位轴系等组成的靶丸表面形貌精密测量系统,气浮轴系的回转精度达0.049 μm,实现了对激光核聚变靶丸3个正交方向上完整圆周迹线的测量。对选定靶丸的测量数据进行了球度、表面粗糙度及功率谱分析。结果表明：其球度值为0.42 μm;模数范围为2~10,11~50,51~100及101~1 000对应的表面粗糙度值平均为105.7, 12.2, 6.2, 18.25 nm;并得出了平均1维功率谱-模数关系曲线。     

基于K-S算法的水质硝酸盐含量光谱检测方法研究

应用紫外光谱对水体中的总氮进行测定,常规的测定方法在分析精度上依赖于所建立的光谱数学模型.测量过程中所依据的紫外光谱数据波段较多,模型的建立所依据的测试样本也比较多,因而很容易引入干扰光谱信息.对水质样本的原始光谱进行一阶微分处理后,采用Kennard-Stone算法对41个样本进行优选,选出30个作为训练集,剩余11...     

Hepatic CT image retrieval based on the combination of Gabor filters and support vector machine

Content-based image retrieval has been an active area of research for more than ten years.Gabor schemes and support vector machine (SVM) method have been proven effective in image representation and classification. In this paper,we propose a retrieval scheme based on Gabor filters and SVMs for hepatic computed tomography (CT) images query.In our experiments,a batch of hepatic CT images containing several types of CT findings are used for the retrieval test.Precision comparison between our scheme and existing methods is presented.     

Precision and variance components in quantitative gel electrophoresis

The error in quantitative gel electrophoresis/Western blotting was investigated considering the purity testing of erythropoietin. The overall error was over 35% relative standard deviation. However, an analysis of variance elucidated that the interoperator variability was the dominant error source, which already explained almost 80% of the total variance. Careful compilation and investigation of the possible error sources strongly indicates that the immunoreaction after blotting and the subsequent color reaction are the major error sources in this case.