Direct determination of trans-resveratrol in human plasma by spectrofluorimetry and second-order standard addition

Trans-resveratrol (RVT) is an antioxidant found in red grapes and their derivatives, which has been related to the reduction of cardiovascular diseases and cancer incidence.This work developed a new spectrofluorimetric-chemometric method for the direct determination of RVT in human plasma. For each measurement, excitation-emission matrices were obtained from 280 to 360 nm (excitation) and from 380 to 550 nm (emission). The strategy adopted in this work combined data treatment with parallel factor analysis (PARAFAC), for extracting the pure analyte signal, using the standard addition method, which permits determinations in the presence of a strong matrix effect caused by plasma analyte-protein binding. Plasma samples were diluted 10 times and, for each, four standard additions of RVT were performed, in triplicate. A specific PARAFAC model was built for the three replicates of each sample, from three-way arrays formed by five measurements (initial sample plus four additions), 17 excitation wavelengths and 86 emission wavelengths. The best models were selected with four factors and accounted for more than 99.90% of the data variance. The loadings obtained were related to RVT and three interferences. The scores related to the analyte were used for linear regressions and all standard addition curves presented correlation coefficients equal or greater than 0.99. Good results were obtained in the concentration range from 0.10 to 5.00 μg mL⁻¹, with recoveries between 94.0 and 110.0%. The proposed method was also validated through the estimates of several figures of merit: sensitivity, analytical sensitivity, selectivity, precision, and limits of detection and quantitation.     

Effect of Na‐ionomer on dynamic rheological,dynamic mechanical and creep properties of acrylonitrile styrene acrylate (ASA)/Na+1 poly (ethylene‐co‐methacrylic acid) ionomer blend

A special class of engineered copolymers, called ionomers, comprising both electrically neutral repeating units and a fraction of ionized units was melt blended to weather resistant acrylonitrile/styrene/acrylate (ASA) terpolymer for improved electrical conductivity, heat sealing ability, direct adhesion to several polymers, glass and metals without affecting the aesthetics and colorability of ASA. The similar chemical nature of one of the components of each blended materials viz. acrylate rubber in ASA and acrylic acid of Na‐ionomer in addition to the presence of ionic crosslinking within Na‐ionomer, polar acrylonitrile group in ASA affects chain dynamics as compared to neat polymers. In this context, dynamic rheological properties, DMA properties, creep behavior and DSC of the newly developed ASA/Na‐ionomer blends were analyzed. Based on Na‐ionomer content, the blend system either forms “mushroom” or “brush” type conformation and formation of ionic crosslinking in “brush regime” leads to three tiers Caylay tree conformation. The different chain topology resulted into characteristic loss modulous (G″) curve during stress relaxation process. The chain conformation as well as ionic crosslinking and ion–dipole interaction between the blend components also affected DSC endotherm peak and glass transition temperature. The tan δ peak temperature from DMA also revealed the similar observation. The creep compliance of the blends was dependent on Na‐ionomer content and with temperature. The Findley model analysis of creep compliance suggested that the creep compliance was depended on Na‐ionomer content and ionic crosslinking controlled the creep. The findings can be utilized to design weather resistant smart polymer using suitable filler system. Copyright © 2014 John Wiley & Sons, Ltd.     

Non-chromatographic speciation of toxic arsenic in fish

A rapid, sensitive and economic method has been developed for the direct determination of toxic species of arsenic present in fish and mussel samples. As(III), As(V), dimethylarsinic acid (DMA), and monomethylarsonic acid (MMA) were determined by hydride generation-atomic fluorescence spectrometry using a series of proportional equations without the need of a chromatographic previous separation. The method is based on the extraction of arsenic species from fish through sonication with HNO₃ 3 mol l⁻¹ and 0.1% (m/v) Triton and washing of the solid phase with 0.1% (m/v) EDTA, followed by direct measurement of the corresponding hydrides in four different experimental conditions. The limit of detection of the method was 0.62 ng g⁻¹ for As(III), 2.1 ng g⁻¹ for As(V), 1.8 ng g⁻¹ for MMA and 5.4 ng g⁻¹ for DMA, in all cases expressed in terms of sample dry weight. The mean relative standard deviation values (R.S.D.) in actual sample analysis were: 6.8% for As(III), 10.3% for As(V), 8.5% for MMA and 7.4% for DMA at concentration levels from 0.08 mg kg⁻¹ As(III) to 1.3 mg kg⁻¹ DMA. Recovery studies provided percentages greater than 93% for all species in spiked samples. The analysis of SRM DORM-2 and CRM 627 certified materials evidenced that the method is suitable for the accurate determination of arsenic species in fish.     

Phosphonyl/hydroxyl hydrogen bonding–induced miscibility of poly(arylene ether phosphine oxide/sulfone) statistical copolymers with poly(hydroxy ether) (phenoxy resin): Synthesis and characterization

High molecular weight bisphenol A or hydroquinone‐based poly(arylene ether phosphine oxide/sulfone) homopolymer or statistical copolymers were synthesized and characterized by thermal analysis, gel permeation chromatography, and intrinsic viscosity. Miscibility studies of blends of these copolymers with a (bisphenol A)‐epichlorohydrin based poly(hydroxy ether), termed phenoxy resin, were conducted by infrared spectroscopy, dynamic mechanical analysis, and differential scanning calorimetry. All of the data are consistent with strong hydrogen bonding between the phosphonyl groups of the copolymers and the pendent hydroxyl groups of the phenoxy resin as the miscibility‐inducing mechanism. Complete miscibility at all blend compositions was achieved with as little as 20 mol % of phosphine oxide units in the bisphenol A poly(arylene ether phosphine oxide/sulfone) copolymer. Single glass transition temperatures (T_g) from about 100 to 200°C were achieved. Replacement of bisphenol A by hydroquinone in the copolymer synthesis did not significantly affect blend miscibilities. Examination of the data within the framework of four existing blend T_g composition equations revealed T_g elevation attributable to phosphonyl/hydroxyl hydrogen bonding interactions. Because of the structural similarities of phenoxy, epoxy, and vinylester resins, the new poly(arylene ether phosphine oxide/sulfone) copolymers should find many applications as impact‐improving and interphase materials in thermoplastics and thermoset composite blend compositions. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 1849–1862, 1999     

Speciation of organic and inorganic arsenic by HPLC-HG-ICP

This paper deals with the application of high performance liquid chromatography (HPLC), hydride generation (HG) and inductively coupled plasma atomic emission spectrometry (ICP) to determine four species of arsenic: As(III), As(V), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The coupling conditions of HPLC-HG-ICP are given. Two anionic exchange columns (Nucleosil-5SB and Hamilton PRP X-100) are tested and the separation conditions optimized. Two acids (H₂SO₄ and HCl at different concentrations) are tested to obtain the hydrides. The proposed method is applied to determine four arsenic species in a synthetic matrix simulating a fish extract.     

On a bi-stability regime and the existence of odd subharmonics in a Comb-drive MEMS model with cubic stiffness

In this paper we study two different problems. First we present a novel result about the existence of a family of odd subharmonics with prescribed nodal properties for a general nonlinear oscillator with bounded domain and symmetries. Then we apply the general existence result to the Comb-drive finger MEMS model with a cubic nonlinear stiffness term, and prove analytically that the odd positive subharmonic of order two is linearly stable whenever the AC load of the input voltage is small enough. Moreover, we demonstrate a bi-stability regime for this model because the trivial solution $x\equiv 0$ is also linearly stable. The general existence result was obtained through a generalization of the Ortega’s variational principle (Ortega, 2016), and the stability assertions were obtained by following the perturbation approach in Cen et al. (2020) for the linear stability of a nontrivial periodic solution that emanates from the autonomous problem, and the well-known Zukovskii criterion.