Adsorptive stripping square wave voltammetry (Ad-SSWV) accomplished with second-order multivariate calibration determination of fenitrothion and its metabolites in river water samples

A method, using stripping square wave voltammetry (Ad-SSWV), for the simultaneous determination of fenitrothion (FEN) and its metabolites: fenitrooxon (OXON) and 3-methyl-4-nitrophenol (3-MET) in environmental samples is reported. All three compounds produce, at mercury electrode (HMDE), an electrochemical signal due to an adsorptive-reductive process. The electrochemical approach shows a very high overlap degree for FEN and OXON voltammograms, however the adsorption kinetic profile could be used as an additional differential variable between both analytes. Second-order multivariate calibration has been tested to solve the mixture of the three compounds. The second-order assayed methods were parallel factor analysis (PARAFAC), unfolded partial least squares (U-PLS), multidimensional partial least squares (N-PLS) and the latest ones were used in combination with the residual bilinearization procedure RBL. U-PLS/RBL model was stated as the best second-order algorithm for the simultaneous determination of these three compounds up to 50 ng mL⁻¹ for each analyte. The detection limits and recovery values were 1.6 ng mL⁻¹ and 92 ± 7% for FEN; 3.7 ng mL⁻¹ and 101 ± 9% for OXON and 0.6 ng mL⁻¹ and 97 ± 8% for 3-MET.     

Comparative chemometric analyses of geographic origins and compositions of lavandin var. Grosso essential oils by mid infrared spectroscopy and gas chromatography

Lavandin, a sterile hybrid of Lavandula angustifolia P. Mill. × Lavandula latifolia (L.f.) Medikus (Lamiaceae) is a plant widely cultivated for essential oil production in the South of France. Chemometric treatment by mid-infrared (MID-IR) spectroscopy data was assessed for the differentiation of Grosso Lavandin Essential Oils of Controlled Area (GLEOCA) and results were compared to those obtained by gas chromatography for MID-IR short time technique validation. The quantification of the main 13 hydrocarbons and oxygenated compounds generally controlled by industrial perfumers in GLEOCA samples (n = 83) of three geographic origins: “Simiane”, “Puimoisson” (with two producers) and “Richerenches” and their classification were successfully obtained by partial least square discriminant analysis (PLS-DA) by comparison with gas chromatography. The best prediction results were obtained using first derivate spectral data in the 1800-700 cm⁻¹ range. The spectroscopic interpretation of regression vectors showed that each geographic origin was correlated to components of GLEOCA. Chemometric MID-IR spectra treatments allowed us to obtain similar results than those obtained by time consuming analytical techniques such as GC and therefore constitute a robust and help fast method for authentication of GLEOCA and should be extended to other essential oils for authentication of geographic origin.     

Osteryoung square wave voltammetric determination of lactose in food samples by a derivative procedure

A method for determination of lactose in food samples by Osteryoung square wave voltammetry （OSWV） was developed. It was based on the nucleophilic addition reaction between lactose and aqua ammonia. The carbonyl group of lactose can be changed into imido group, and this increases the electrochemical activity in reduction and the sensitivity. The optimal condition for the nucleophilic addition reaction was investigated and it was found that in NH4C1-NH3 buffer of pH 10.1, the linear range between the peak current and the concentration of lactose was 0.6-8.4 mg L-l, and the detection limits was 0.44 mg L- 1. The proposed method was applied to the ＇determination of lactose in food samples and satisfactory results were obtained.     

Strong limit theorems for quasi-orthogonal random fields

This is a systematic and unified treatment of a variety of seemingly different strong limit problems. The main emphasis is laid on the study of the a.s. behavior of the rectangular means ζ_mn = 1/(λ₁(m) λ₂(n)) Σ_i=1^m Σ_k=1ⁿ X_ik as either max{m, n} → ∞ or min{m, n} → ∞. Here {X_ik: i, k ≥ 1} is an orthogonal or merely quasi-orthogonal random field, whereas {λ₁(m): m ≥ 1} and {λ₂(n): n ≥ 1} are nondecreasing sequences of positive numbers subject to certain growth conditions. The method applied provides the rate of convergence, as well. The sufficient conditions obtained are shown to be the best possible in general. Results on double subsequences and 1-parameter limit theorems are also included.     

Comparison of Voltammetric Techniques for Ammonia Sensing in Ionic Liquids

In electroanalytical chemistry, it is often observed that square wave voltammetry (SWV) and differential pulse voltammetry (DPV) are more sensitive techniques compared to linear sweep voltammetry (LSV), due to their method of sampling which minimises the charging current (non‐faradaic processes). In this work, a comparison of the three techniques (LSV, DPV and SWV) is performed for ammonia (NH₃) gas oxidation (a chemically and electrochemically irreversible redox process) in an ionic liquid over a concentration range of 10–100 ppm. Four different platinum electrodes are employed: a screen‐printed electrode (SPE), a thin‐film electrode (TFE), a microarray thin‐film electrode (MATFE) and a Pt microdisk electrode (μ‐disk). Calibration plots (current vs concentration) for all three different electrochemical techniques on all four surfaces showed excellent linearity with increased concentrations of NH₃ gas and relatively low limits of detection (LODs). On the larger mm‐sized surfaces (SPE and TFE), the current responses for LSV and SWV were quite similar, but DPV gave the lowest currents. Whereas for the smaller micron sized electrodes (MATFE and μ‐disk), currents were of the order LSV>SWV>DPV, with LSV being far superior to the pulse techniques. These findings suggest that the pulse techniques of SWV and DPV may not be the optimum methods, particularly on microelectrodes, for the detection of analytes such as ammonia in RTILs.     

The full power of the half-power

We use the complex square root to define a very simple homotopic invariant over the non-vanishing functions defined on the circle. As a consequence we provide easy proofs of the plane Brouwer fixed point theorem and the Fundamental Theorem of Algebra. The relation of this new invariant with the winding number and the Brouwer degree will be fully unveiled.     

Negative Latin square type partial difference sets in nonabelian groups of order 64

There exist few examples of negative Latin square type partial difference sets (NLST PDSs) in nonabelian groups. We present a list of 176 inequivalent NLST PDSs in 48 nonisomorphic, nonabelian groups of order 64. These NLST PDSs form 8 nonisomorphic strongly regular graphs. These PDSs were constructed using a combination of theoretical techniques and computer search, both of which are described. The search was run exhaustively on 212/267 nonisomorphic groups of order 64.     

相位恢复:理论、模型与算法

相位恢复在多个不同领域均被提出,如量子力学、光学成像等.相位恢复即具有多种应用背景,亦具有丰富的数学内涵,因而近期该问题吸引了多个不同领域专家的关注,如计算数学、数据科学、最优化、代数几何等.本文将主要介绍相位恢复中的理论基础问题,特别是最少观测次数问题,并介绍求解相位恢复的模型性能,以及求解算法等.本文也介绍了一些当前相位恢复中研究的热点方向.     

平面四方型混合配体配合物[Pd(γ-CH_3py)_2(mnt)_2]的合成和晶体结构

本文报道标题化合物（其中γＣＨ３ｐｙ是对甲基吡啶，ｍｎｔ＝ＣＮＣＮＳ－Ｓ－）的合成、鉴定和单晶结构。化合物晶体属三钭晶系，Ｐ１空间群，晶胞内分子数为２。分子中与Ｐｄ（Ⅱ）配位的四个原子呈平面四方形。讨论了结构与二阶、三阶非线性光学效应的关系。     

基于移动窗口-迭代遗传算法的近红外光谱波长选择方法

光谱样本数据常会受到环境噪声和其它组分的干扰，应作波长选择，以提高分析精度。近红外光谱谱区宽，搜索空间过大，难以直接采用遗传算法进行波长选择。为此本研究提出先用移动窗口偏最小二乘法（MWPLS）从宽谱区中初选出信息区间，再采用改进的迭代遗传算法（IGA）从中选出最优的信息子区间。MWPLS用移动窗口沿全谱区扫描，对信息区间的定位效果好，而IGA将顾及光谱数据的连续相关特性，运行多轮GA，并以上轮选择结果平滑处理后作为先验知识支持下轮的种群初始化。由此选出的连续相邻的波长点作为自变量，进行PLS建模，既可显著地简化模型，又保留一定的数据冗余，模型的稳健性好、分析精度高。将其用于小麦水分的近红外分析，效果良好，预测性能明显优于其它方法。