Estimation of the uncertainty of mass measurements from in-house calibrated analytical balances

The uncertainty evaluation of mass measurements when using “in-house” calibrated analytical balances is revisited according to the Guide to the expression of Uncertainty Measurement (GUM). The calibration of analytical balances is discussed according to the guidelines of several bodies such as ASTM, UKAS and DKD/PTB. The remainder components of uncertainty can be estimated from the balance data sheet specifications.     

凝胶渗透色谱法测定聚丙烯腈共聚物分子量中宽分布校正法的应用

应用宽分布校正法对凝胶渗透色谱(GPC)进行了校正，将校正曲线用于聚丙烯腈(PAN)共聚物分子量的计算。对扣除色谱峰扩展效应前后的测试结果与乌氏粘度法测得的数据进行比较。结果表明，应用宽分布校正法时，必须扣除色谱峰扩展效应，才能得到较为准确的测试结果。     

Interference-free determination of Sudan dyes in chilli foods using second-order calibration algorithms coupled with HPLC-DAD

This paper presents a new method for the determination of Sudan dyes contained in hot chilli samples. The method employs second-order calibration algorithms to handle the recorded data. The second-order calibration algorithms are based on the popular parallel factor analysis (PARAFAC), alternating trilinear decomposition (ATLD) and self-weighted alternating trilinear decomposition (SWATLD), respectively. These chemometric methodologies have the second-order advantage, which is the ability to get accurate concentration estimates of interested analytes even in the presence of uncalibrated interfering components. The results on a set of spiked chilli test shows that low contents of Sudan I and Sudan II in complex chilli mixtures can be accurately determined using the new method. The sample preparation was based on solvent extraction, and internal standard was not required. Quantification was carried out with simple mobile phase.     

Calibration coefficient of a heat-flow DSC; Part II. Optimal calibration procedure

One-point (Mettler) and many-point (Netzsch) heat flow calibration of a DSC is discussed. It is shown that the two types of calibration are the alternative extremes between quick but rough procedure and time-consuming but accurate one. One-point calibration compares a typical function k(T) at the melting point of indium with the measured value for particular DSC and multiplies k(T) by a scaling factor. Many-point calibration is based on general mathematical procedure, namely fitting a set of experimental values of sensitivity to a polynomial. The polynomial coefficients are evaluated by the method of least squares. Based on the relationship between the sensitivity of a thermocouple and calibration coefficient of a DSC sensor made from it, two-point heat flow calibration is suggested. This is an optimal calibration procedure, for the relationship contains only two unknown coefficients. An example of how to perform the two-point calibration with Netzsch-Proteus Software is described in the Appendix.     

A class of multiple shrinkage estimators

Based on a sample of size n, we investigate a class of estimators of the mean of a p-variate normal distribution with independent components having unknown covariance. This class includes the James-Stein estimator and Lindley's estimator as special cases and was proposed by Stein. The mean squares error improves on that of the sample mean for p3. Simple approximations imations for this improvement are given for large n or p. Lindley's estimator improves on that of James and Stein if either n is large, and the coefficient of variation of is less than a certain increasing function of p, or if p is large. An adaptive estimator is given which for large samples always performs at least as well as these two estimators.     

Development of B‐doped Si multiple delta‐layer reference materials for SIMS profiling

B‐doped Si multiple delta‐layers (MDL) were developed as certified reference materials (CRM) for secondary ion mass spectrometry (SIMS) depth profiling analysis. Two CRMs with different delta‐layer spacing were grown by ion beam sputter deposition (IBSD). The nominal spacing of the MDL for shallow junction analysis is 10 nm and that for high energy SIMS is 50 nm. The total thickness of the film was certified by high resolution transmission electron microscopy (HR‐TEM). The B‐doped Si MDLs can be used to evaluate SIMS depth resolution and to calibrate the depth scale. A consistency check of the calibration of stylus profilometers for measurement of sputter depth is another possible application. The crater depths measured by a stylus profilometer showed a good linear relationship with the thickness measured from SIMS profiling using the calibrated film thickness for depth scale calibration. The sputtering rate of the amorphous Si thin film grown by sputter deposition was found to be the same as that of the crystalline Si substrate, which means that the sputtering rate measured with these CRMs can be applied to a real analysis of crystalline Si. Copyright © 2005 John Wiley & Sons, Ltd.     

通用模拟退火用于稳健多元分析校正

模拟退火是一种全局优化算法，具有跨越局部最优点的机制，最小一乘是一种较常用的最小二乘更为稳健的优化准则，更适用于可能偏离正态分布的实际数据集，本文探讨了用最小一乘为准则并利用模拟退火方法同时测定多组分体系的可能性。应用于2－3组分药物体系分析，获得了满意的结果，本文还探讨了改变步长提高模拟退火算法优化精度的方法。     

2D Burgers equation with large Reynolds number using POD/DEIM and calibration

Model order reduction of the two‐dimensional Burgers equation is investigated. The mathematical formulation of POD/discrete empirical interpolation method (DEIM)‐reduced order model (ROM) is derived based on the Galerkin projection and DEIM from the existing high fidelity‐implicit finite‐difference full model. For validation, we numerically compared the POD ROM, POD/DEIM, and the full model in two cases of Re = 100 and Re = 1000, respectively. We found that the POD/DEIM ROM leads to a speed‐up of CPU time by a factor of O(10). The computational stability of POD/DEIM ROM is maintained by means of a careful selection of POD modes and the DEIM interpolation points. The solution of POD/DEIM in the case of Re = 1000 has an accuracy with error O(10^?3) versus O(10^?4) in the case of Re = 100 when compared with the high fidelity model. For this turbulent flow, a closure model consisting of a Tikhonov regularization is carried out in order to recover the missing information and is developed to account for the small‐scale dissipation effect of the truncated POD modes. It is shown that the computational results of this calibrated ROM exhibit considerable agreement with the high fidelity model, which implies the efficiency of the closure model used. Copyright © 2016 John Wiley & Sons, Ltd.     

Carbon dots with strong excitation-dependent fluorescence changes towards pH. Application as nanosensors for a broad range of pH

In this study, preparation of novel pH-sensitive N-doped carbon dots (NCDs) using glucose and urea is reported. The prepared NCDs present strong excitation-dependent fluorescence changes towards the pH that is a new behavior from these nanomaterials. By taking advantage of this unique behavior, two separated ratiometric pH sensors using emission spectra of the NCDs for both acidic (pH 2.0 to 8.0) and basic (pH 7.0 to 14.0) ranges of pH are constructed. Additionally, by considering the entire Excitation–Emission Matrix (EEM) of NCDs as analytical signal and using a suitable multivariate calibration method, a broad range of pH from 2.0 to 14.0 was well calibrated. The multivariate calibration method was independent from the concentration of NCDs and resulted in a very low average prediction error of 0.067 pH units. No changes in the predicted pH under UV irradiation (for 3 h) and at high ionic strength (up to 2 M NaCl) indicated the high stability of this pH nanosensor. The practicality of this pH nanosensor for pH determination in real water samples was validated with good accuracy and repeatability.     

Simultaneous Determination of Acetaminophen and Phenobarbital in Suppositories by Partial Least-Squares Spectrophotometric Calibration

Abstract

The use of partial least-squares spectrophotometric calibration for the simultaneous determination of suppositories in a multicomponent formulation is presented. This method is applied to the deternination of acetaminophen and phenobarbital in suppository preparations. The results show that these components in a molar ratio of about 61:1 in suppositories have been determined simultaneously with high precision.