纳米多孔双金属氧化物在镍钛合金纤维上的原位生长及其对多环芳烃的选择性固相微萃取

采用阳极氧化法在镍钛合金(NiTi)纤维上原位生长了双金属氧化物纳米孔(NiTiONPs)涂层,通过扫描电镜(SEM)和能谱(EDS)考察了电解质组成和电压对形貌的影响。将NiTiONPs涂层的NiTi纤维与高效液相色谱-紫外检测器联用,研究了4种典型芳香分析物的萃取性能。结果表明,富含TiO2的NiTiONPs涂层对多环芳烃(PAHs)具有良好的萃取效率,尤其对苯并[a]芘的萃取选择性优于市售聚二甲基硅氧烷纤维和聚丙烯酸酯纤维。在优化条件下,PAHs的线性范围为0.05~200μg/L,相关系数均大于0.999,检出限为0.012~0.134μg/L。对单支纤维日内和日间分析的相对标准偏差(RSDs)分别为4.0%~5.5%和6.0%~6.8%,使用分批组装的5支纤维分析的RSDs为6.4%~7.6%。实际水样分析的加标回收率为84.5%~111.5%。所制备NiTi纤维至少可重复使用250次以上,重现性好。     

Selective solid-phase microextraction of polycyclic aromatic hydrocarbons in water based on oriented phosphorus-containing titanium oxide nanofibers grown on titanium support prior to high-performance liquid chromatography with ultraviolet detection

A novel solid-phase microextraction coating of phosphorous-containing titanium oxide composite was developed using titanium fiber as a support and a titanium source by hydrothermal oxidation in a phosphoric acid solution containing hydrogen peroxide. The morphology of the fiber coatings was controlled by the conditions of the hydrothermal oxidation reaction. The oriented nanofiber coating was employed to extract several types of representative aromatic analytes. The experimental results demonstrated that the as-prepared fiber exhibited excellent extraction efficiency toward polycyclic aromatic hydrocarbons. Combined with high-performance liquid chromatography with ultraviolet detection, main extraction conditions were optimized, including pH, ionic strength, extraction temperature, stirring rate, extraction time and desorption time. The established method presented good linearity from 0.05 to 200 μg/L with limit of detection ranging from 0.012 to 0.126 μg/L. This convenient and green procedure was suitable for the selective extraction and determination of typical polycyclic aromatic hydrocarbons in environmental water samples. The relative recoveries of 85.8–112% were obtained for the determination of target polycyclic aromatic hydrocarbons in water samples spiked with 5.0 and 15.0 μg/L. Moreover, the as-prepared fiber showed at least 210 extraction/desorption cycles due to its high mechanical and chemical stability.     

A smoothing Newton-type method for generalized nonlinear complementarity problem

By using a new type of smoothing function, we first reformulate the generalized nonlinear complementarity problem over a polyhedral cone as a smoothing system of equations, and then develop a smoothing Newton-type method for solving it. For the proposed method, we obtain its global convergence under milder conditions, and we further establish its local superlinear (quadratic) convergence rate under the BD-regular assumption. Preliminary numerical experiments are also reported in this paper.     

A zinc(II) benzenetricarboxylate metal organic framework with unusual adsorption properties,and its application to the preconcentration of pesticides

The authors describe a zinc(II) benzenetricarboxylate (Zn-BTC) based metal-organic framework (MOF) with chrysanthemum-like structure, and its application to the adsorption of pesticides from real water samples. The Zn-BTC MOF was characterized by XRD, TGA, SEM, nitrogen adsorption-desorption analysis and FT-IR spectroscopy. The MOF was used in dispersive solid-phase extraction of six aromatic pesticides from various wastewater samples prior to their quantification by HPLC. Extraction times, extraction temperature, amount of adsorbent, and oscillation rate were optimized. Under the optimal conditions, the method has relative standard deviations (RSDs) of 6.1–10.1%, and good linearity (correlation coefficients higher than 0.9974). The LODs and LOQs for seven pesticides are found to be 0.20–1.60 μg·L^?1 and 0.66–5.28 μg·L^?1, respectively. The RSDs of within batch extraction are 1.6–9.5% and 3.9–12%.

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Graphical abstract Schematic of a zinc-benzenetricarboxylate (Zn-BTC) based metal-organic framework (MOF) for use as an adsorbent of dispersive solid phase extraction (DSPE) of pesticides prior to their determination by HPLC.

     

Growth of cedar-like Au nanoparticles coating on an etched stainless steel wire and its application for selective solid-phase microextraction

A novel cedar-like Au nanoparticles (AuNPs) coating was fabricated on an etched stainless steel (SS) wire by direct chemical deposition and used as an efficient and unbreakable solid phase microextraction (SPME) fiber. The etched SS wire offers a rough surface structure for subsequent growth of AuNPs in chloroauric acid solution. As a result, the uniform cedar-like AuNPs coating with larger surface area was tightly attached to the etched SS wire substrate. The AuNPs coated etched SS fiber (AuNPs/SS) was examined for SPME of ultraviolet (UV) filters, phthalate esters and aromatic hydrocarbons coupled to high-performance liquid chromatography with UV detection. The fabricated fiber exclusively exhibited excellent extraction efficiency and selectivity for some aromatic hydrocarbons. Influential parameters of extraction and desorption time, temperature, stirring rate and ionic strength were investigated and optimized. The limits of detection ranged from 0.008 μg L⁻¹ to 0.037 μg L⁻¹. The single fiber repeatability varied from 3.90% to 4.50% and the fiber-to-fiber reproducibility ranged from 5.15% to 6.87%. The recovery of aromatic hydrocarbons in real water samples spiked at 2.0 μg L⁻¹ and 20 μg L⁻¹ ranged from 94.38% to 106.2% with the relative standard deviations below 6.44%. Furthermore the growth of the cedar-like AuNPs coating can be performed in a highly reproducible manner. This fabricated fiber exhibits good stability and withstands at least 200 extraction and desorption replicates.     

Biquadratic tensors,biquadratic decompositions,and norms of biquadratic tensors

Biquadratic tensors play a central role in many areas of science.Examples include elastic tensor and Eshelby tensor in solid mechanics,and Riemannian curvature tensor in relativity theory.The singular values and spectral norm of a general third order tensor are the square roots of the M-eigenvalues and spectral norm of a biquadratic tensor,respectively.The tensor product operation is closed for biquadratic tensors.All of these motivate us to study biquadratic tensors,biquadratic decomposition,and norms of biquadratic tensors.We show that the spectral norm and nuclear norm for a biquadratic tensor may be computed by using its biquadratic structure.Then,either the number of variables is reduced,or the feasible region can be reduced.We show constructively that for a biquadratic tensor,a biquadratic rank-one decomposition always exists,and show that the biquadratic rank of a biquadratic tensor is preserved under an independent biquadratic Tucker decomposition.We present a lower bound and an upper bound of the nuclear norm of a biquadratic tensor.Finally,we define invertible biquadratic tensors,and present a lower bound for the product of the nuclear norms of an invertible biquadratic tensor and its inverse,and a lower bound for the product of the nuclear norm of an invertible biquadratic tensor,and the spectral norm of its inverse.     

Oriented ZnO nanoflakes on nickel-titanium alloy fibers for solid-phase microextraction of polychlorinated biphenyls and polycyclic aromatic hydrocarbons

ZnO nanoflakes (ZnONFs) were electrochemically grown on a nickel-titanium alloy (NiTi) wire for use in solid-phase microextraction. Prior to the growth of ZnONFs, the NiTi wire was hydrothermally treated for in-situ growth of TiO₂/NiO nanoflakes as a seeding base. The applied potential was used to control the dimensions of vertically oriented hexagonal ZnONFs. After annealing at 600 °C, the resulting fiber display fairly selective affinity for polychlorinated biphenyls (PCBs) and polycyclic aromatic hydrocarbons. The fibers were applied to the preconcentration of PCBs which then were quantified by HPLC with UV detection. Compared to commercial polydimethylsiloxane coatings, the new coating displays high extraction capability, rapid extraction kinetics and superior cycling stability. This is assumed to be due to its high surface-to-volume ratio, double-sided open access structure, and enhanced structural stability. The assay excels by (a) a wide analytical range (0.10 to 200 μg L^?1 of PCBs), (b) low limits of detection (20–17 ng L^?1), and (c) low standard deviations for the single fiber repeatability (<9.8%) and for the fiber-to-fiber reproducibility (<7.5%). Satisfactory accuracy and precision were achieved when PCBs were determined by this method in spiked rain water, river water and wastewater samples.

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Graphical abstract ZnO nanoflakes were fabricated on a superelastic nickel-titanium alloy wire in desired orientation with enhanced extraction capability and good extraction selectivity. The fabricated fiber was suitable for the determination of PCBs in environmental water samples

     

Rapid in situ growth of oriented titanium‐nickel oxide composite nanotubes arrays coated on a nitinol wire as a solid‐phase microextraction fiber coupled to HPLC–UV

An oriented titanium‐nickel oxide composite nanotubes coating was in situ grown on a nitinol wire by direct electrochemical anodization in ethylene glycol with ammonium fluoride and water for the first time. The morphology and composition of the resulting coating showed that the anodized nitinol wire provided a titania‐rich coating. The titanium‐nickel oxide composite nanotubes coated fiber was used for solid‐phase microextraction of different aromatic compounds coupled to high‐performance liquid chromatography with UV detection. The titanium‐nickel oxide composite nanotubes coating exhibited high extraction capability, good selectivity, and rapid mass transfer for weakly polar UV filters. Thereafter the important parameters affecting extraction efficiency were investigated for solid‐phase microextraction of UV filters. Under the optimized conditions, the calibration curves were linear in the range of 0.1–300 μg/L for target UV filters with limits of detection of 0.019–0.082 μg/L. The intraday and interday precision of the proposed method with the single fiber were 5.3–7.2 and 5.9–7.9%, respectively, and the fiber‐to‐fiber reproducibility ranged from 6.3 to 8.9% for four fibers fabricated in different batches. Finally, its applicability was evaluated by the extraction and determination of target UV filters in environmental water samples.     

Standard bi-quadratic optimization problems and unconstrained polynomial reformulations

A so-called Standard Bi-Quadratic Optimization Problem (StBQP) consists in minimizing a bi-quadratic form over the Cartesian product of two simplices (so this is different from a Bi-Standard QP where a quadratic function is minimized over the same set). An application example arises in portfolio selection. In this paper we present a bi-quartic formulation of StBQP, in order to get rid of the sign constraints. We study the first- and second-order optimality conditions of the original StBQP and the reformulated bi-quartic problem over the product of two Euclidean spheres. Furthermore, we discuss the one-to-one correspondence between the global/local solutions of StBQP and the global/local solutions of the reformulation. We introduce a continuously differentiable penalty function. Based upon this, the original problem is converted into the problem of locating an unconstrained global minimizer of a (specially structured) polynomial of degree eight.