A novel second-order standard addition analytical method based on data processing with multidimensional partial least-squares and residual bilinearization

In the presence of analyte-background interactions and a significant background signal, both second-order multivariate calibration and standard addition are required for successful analyte quantitation achieving the second-order advantage. This report discusses a modified second-order standard addition method, in which the test data matrix is subtracted from the standard addition matrices, and quantitation proceeds via the classical external calibration procedure. It is shown that this novel data processing method allows one to apply not only parallel factor analysis (PARAFAC) and multivariate curve resolution-alternating least-squares (MCR-ALS), but also the recently introduced and more flexible partial least-squares (PLS) models coupled to residual bilinearization (RBL). In particular, the multidimensional variant N-PLS/RBL is shown to produce the best analytical results. The comparison is carried out with the aid of a set of simulated data, as well as two experimental data sets: one aimed at the determination of salicylate in human serum in the presence of naproxen as an additional interferent, and the second one devoted to the analysis of danofloxacin in human serum in the presence of salicylate.     

Fast chromatographic method for the determination of dyes in beverages by using high performance liquid chromatography—Diode array detection data and second order algorithms

A fast chromatographic methodology is presented for the analysis of three synthetic dyes in non-alcoholic beverages: amaranth (E123), sunset yellow FCF (E110) and tartrazine (E102). Seven soft drinks (purchased from a local supermarket) were homogenized, filtered and injected into the chromatographic system. Second order data were obtained by a rapid LC separation and DAD detection. A comparative study of the performance of two second order algorithms (MCR-ALS and U-PLS/RBL) applied to model the data, is presented. Interestingly, the data present time shift between different chromatograms and cannot be conveniently corrected to determine the above-mentioned dyes in beverage samples. This fact originates the lack of trilinearity that cannot be conveniently pre-processed and can hardly be modelled by using U-PLS/RBL algorithm. On the contrary, MCR-ALS has shown to be an excellent tool for modelling this kind of data allowing to reach acceptable figures of merit. Recovery values ranged between 97% and 105% when analyzing artificial and real samples were indicative of the good performance of the method. In contrast with the complete separation, which consumes 10 mL of methanol and 3 mL of 0.08 mol L⁻¹ ammonium acetate, the proposed fast chromatography method requires only 0.46 mL of methanol and 1.54 mL of 0.08 mol L⁻¹ ammonium acetate. Consequently, analysis time could be reduced up to 14.2% of the necessary time to perform the complete separation allowing saving both solvents and time, which are related to a reduction of both the costs per analysis and environmental impact.     

A new variant of L-curve for Tikhonov regularization

In this paper we introduce a new variant of L-curve to estimate the Tikhonov regularization parameter for the regularization of discrete ill-posed problems. This method uses the solution norm versus the regularization parameter. The numerical efficiency of this new method is also discussed by considering some test problems.     

Establishment of a knowledge base for identification of residual solvents in pharmaceuticals

A knowledge base for identification of residual solvents in pharmaceuticals has been established using gas chromatograph-mass spectrometry (GC-MS) and gas chromatograph-Fourier transform infrared spectrometry (GC-FTIR). Sixty solvents were studied according to the guideline for residual solvents regulated by the International Conference on Harmonization of Technical Requirements for Registration of Pharmaceuticals for Human Use (ICH). The standard mass spectra library, the limit of detection (LOD) mass spectra library, the standard vapor-phase infrared spectra library, and the limit of detection (LOD) vapor-phase infrared spectra library were established and constituted the knowledge base. Using the knowledge base, the problem of qualitation, which was the difficulty of determining residual solvents, can be resolved.     

Residual stability of polyurethane automotive coatings measured by chemiluminescence and equivalence of Xenotest and Solisi ageing tests

Degradation of poly(ester-urethanes) and poly(acrylic-urethanes), as a base for automotive paintings in interior applications, has been studied by chemiluminescence. The samples were clearcoat and black-pigmented paints, unstabilised and stabilized with HALS Tinuvin 292 and UV absorber Tinuvin 1130, exposed to various doses of artificial weathering in Xenotest and Solisi equipment. Chemiluminescence has appeared a powerful tool to evaluate the oxidation stability of various polyurethane systems. From the dependences of oxidation onset temperature on heating rate, the kinetic parameters describing the dependence of induction periods on temperature have been obtained. The kinetic parameters enabled us to calculate the length of the induction period for a chosen temperature, the protection factors of various additives and the residual stability of the polymer after an artificial ageing stress. It has been found that the loss of residual stability with ageing dose obeys a first-order relationship. Equivalence between the two methods of artificial ageing has been determined. The results indicate that the equivalence depends on the polymer composition. The procedure presented here can also be applied for the determination of equivalence of accelerated and field tests so contributing to establishing a reliable correlation between them.     

皖南牌坊传统灰浆的科技研究

采用FTIR,XRD,SEM等技术,对皖南牌坊上的传统灰浆材料配方进行了初步研究。结果表明,牌坊灰浆样品为石灰掺桐油或糯米而形成的有机-无机复合材料。桐油灰浆强度的形成主要源于灰浆中石灰的碳化反应、桐油与氧气的交联反应和Ca2+与—COO-的配位反应以及由此而形成的致密片层状有机-无机复合结构。糯米淀粉对灰浆碳化过程的调控作用而形成的细密的微观结构是糯米灰浆具有良好性能的微观解释。     

基于实时样本采集的个性化手写汉字输入系统设计

手写汉字识别是手写汉字输入的基础。目前智能设备中的手写汉字输入法无法根据用户的汉字书写习惯,动态调整识别模型以提升手写汉字的正确识别率。通过对最新深度学习算法及训练模型的研究,提出了一种基于用户手写汉字样本实时采集的个性化手写汉字输入系统的设计方法。该方法将采集用户的手写汉字作为增量样本,通过对服务器端训练生成的手写汉字识别模型的再次训练,使识别模型能够更好地适应该用户的书写习惯,提升手写汉字输入系统的识别率。最后,在该理论方法的基础上,结合新设计的深度残差网络,进行了手写汉字识别的对比实验。实验结果显示,通过引入实时采集样本的再次训练,手写汉字识别模型的识别率有较大幅度的提升,能够更有效的满足用户在智能设备端对手写汉字输入系统的使用需求。     

Geochemical Anomaly Characteristics of Cd in Soils around Abandoned Lime Mines: Evidence from Multiple Technical Methods

Lime mines are a potential source of pollution, and the surrounding soil environment is generally at threat, especially in abandoned lime mines. This paper focuses on the study area in eastern Anhui, attempting to analyze whether Cd enrichment is related to abandoned mines. On the basis of geological investigation, this study systematically used XRD, XRF, GTS and universal Kriging interpolation to determine the distribution law of Cd in the study area, and evaluated the potential ecological risk of Cd. The results showed that the main mineral types of soil samples of red clastic rock soil parent material (RdcPm) and soil samples of carbonate soil parent material (CPm) were not completely the same. Correlation analysis showed that CaO, MgO and Cd were positively correlated with the CPm. Human activities led to the accumulation of Cd in the study area. High Cd was mainly concentrated in the northwest of the study area, which was correlated with abandoned mines and soil parent materials. The study area was dominated by slight potential risks, although some areas had medium potential risks and high potential risks. All potential high risks were in the CPm field. This study provides a scientific basis for the comprehensive utilization and development planning of soil in the study area.     

Residual stress in the cylindrical drawing cup of SUS304 stainless steel evaluated by split-ring test

The residual stresses in the wall of a SUS304 stainless steel cylindrical drawing cup were evaluated by split-ring tests, and the influences of stamping die parameters on the residual stress were investigated. A new theoretical model of a split-ring test was developed to evaluate the residual stress in a ring, which was verified to be reasonable and reliable by numerical simulations with ABAQUS code and by nanoindentation tests. Seven groups of split-ring tests were completed, and the residual stresses were calculated according to the theoretical model. The split-ring test results showed that the circumferential residual stress in the wall of the SUS304 stainless steel cylindrical drawing cup was very large and did not change with the different die corner radius.The circumferential residual stress first increased with the increase of drawing punch–die clearance, then was almost unchanged when the clearance increased greater than blank thickness 1 mm. Thus, a smaller clearance was suggested to be chosen to reduce the residual stress in the wall of the SUS304 stainless steel drawing cup.     

Polarization maintaining holey fibers for residual dispersion compensation over S + C + L wavelength bands

We report on a highly birefringent holey fiber for broadband dispersion compensation covering the S, C, and L telecommunication bands i.e. wavelength ranging from 1460 to 1625 nm. The finite element method with circular perfectly matched layer boundary condition is used to investigate the guiding properties. Numerical analysis demonstrates that it is possible to obtain negative dispersion coefficient of about −470 to −850 ps/nm/km over S to L-bands and a relative dispersion slope perfectly matched with single mode fiber (SMF) of about 0.0036 nm⁻¹ at 1550 nm. At the same time birefringence of the order 2.53 × 10⁻² is realized at 1550 nm wavelength. Owing to superior optical properties of the proposed holey fiber, this can be a promising candidate for broadband dispersion compensation and sensing applications.