Fast sequential multi-element determination of Ca,Mg, K,Cu, Fe,Mn and Zn for foliar diagnosis using high-resolution continuum source flame atomic absorption spectrometry: Feasibility of secondary lines,side pixel registration and least-squares background correction

The fast sequential multi-element determination of Ca, Mg, K, Cu, Fe, Mn and Zn in plant tissues by high-resolution continuum source flame atomic absorption spectrometry is proposed. For this, the main lines for Cu (324.754 nm), Fe (248.327 nm), Mn (279.482 nm) and Zn (213.857 nm) were selected, and the secondary lines for Ca (239.856 nm), Mg (202.582 nm) and K (404.414 nm) were evaluated. The side pixel registration approach was studied to reduce sensitivity and extend the linear working range for Mg by measuring at wings (202.576 nm; 202.577 nm; 202.578 nm; 202.580 nm; 202.585 nm; 202.586 nm; 202.587 nm; 202.588 nm) of the secondary line. The interference caused by NO bands on Zn at 213.857 nm was removed using the least-squares background correction. Using the main lines for Cu, Fe, Mn and Zn, secondary lines for Ca and K, and line wing at 202.588 nm for Mg, and 5 mL min^− 1 sample flow-rate, calibration curves in the 0.1–0.5 mg L^− 1 Cu, 0.5–4.0 mg L^− 1 Fe, 0.5–4.0 mg L^− 1 Mn, 0.2–1.0 mg L^− 1 Zn, 10.0–100.0 mg L^− 1 Ca, 5.0–40.0 mg L^− 1 Mg and 50.0–250.0 mg L^− 1 K ranges were consistently obtained. Accuracy and precision were evaluated after analysis of five plant standard reference materials. Results were in agreement at a 95% confidence level (paired t-test) with certified values. The proposed method was applied to digests of sugar-cane leaves and results were close to those obtained by line-source flame atomic absorption spectrometry. Recoveries of Ca, Mg, K, Cu, Fe, Mn and Zn in the 89–103%, 84–107%, 87–103%, 85–105%, 92–106%, 91–114%, 96–114% intervals, respectively, were obtained. The limits of detection were 0.6 mg L^− 1 Ca, 0.4 mg L^− 1 Mg, 0.4 mg L^− 1 K, 7.7 µg L^− 1 Cu, 7.7 µg L^− 1 Fe, 1.5 µg L^− 1 Mn and 5.9 µg L^− 1 Zn.     

Exploratory analysis and inductively coupled plasma optical emission spectrometry (ICP OES) applied in the determination of metals in soft drinks

A 2³ factorial design and a CCD (Central Composite Design) were employed to optimize the operational conditions for determining Al, Ba, Ca, Cd, Cr, Cu, K, Mg, Na, Ni, Pb, Sn and Zn in soft drink samples by inductively coupled plasma optical emission spectrometry (ICP OES). Satisfactory parameters of merit were obtained (Plasma stability, linearity, SBR, BEC, LOD and LOQ). The accuracy was evaluated by means of a recovery study. Thirty five soft drink samples were analyzed. The results obtained were used in an exploratory analysis, in which principal component analysis and cluster analysis were applied in order to differentiate the several soft drink classes. Adequate LOQ values were obtained for all elements (0.34 μg L^− 1 for Ca to 88.7 μg L^− 1 for Mg) and the recovery study results ranged between 80 and 100%. Cluster analysis revealed four sample classes characterized by flavor and other characteristics, such as being light, diet, low calorie or regular beverages. A model with 4 PCs was obtained by means of a principal component analysis, which explained 99.8% of the total variance.     

Automated microcolumn-switching system for drug analysis by direct injection of human plasma

This study presents the application of a system that joins the known advantages of capillary liquid chromatography (e.g., higher concentration of the analytes and lower consumption of mobile phase) with those of column-switching using restricted access material (RAM) (sample clean up and extraction) to the analysis of fluoxetine in plasma samples. Automatically, the system loads the biological sample, while a RAM-BSA-C18 column (50 mm x 520 microm) excludes the macromolecules and focuses the analytes; afterwards, a second mobile phase elutes the analytes, in backflush mode, and provides the separation in a C18 analytical column (100 mm x 520 microm). We optimized the procedure for a total analysis time of 25 min. Using this approach the calibration curve shows r=0.998 with a linearity range from 20 to 500 ng ml(-1). Precision, calculated as relative standard deviation (RSD), was<20%. The developed miniaturized system showed to be adequate and attractive, demonstrating a large potential for sample preparation.     

Voltammetric studies on the electrochemical determination of methylmercury in chloride medium at carbon microelectrodes

Electroanalytical techniques have been used to determine methylmercury at low levels in environmental matrices. The electrochemical behaviour of methylmercury at carbon microelectrodes in a hydrochloric acid medium using cyclic, square wave and fast-scan linear-sweep voltammetric techniques has been investigated. The analytical utility of the methylmercury reoxidation peak has been explored, but the recorded peak currents were found to be poorly reproducible. This is ascribed to two factors: the adsorption of insoluble chloromercury compounds on the electrode surface, which appears to be an important contribution to hinder the voltammetric signal of methylmercury; and the competition between the reoxidation of the methylmercury radical and its dimerization reaction, which limits the reproducibility of the methylmercury peak. These problems were successfully overcome by adopting the appropriate experimental conditions. Fast-scan rates were employed and an efficient electrochemical regeneration procedure of the electrode surface was achieved, under potentiostatic conditions in a mercury-free solution containing potassium thiocyanate—a strong complexing agent. The influence of chloride ion concentration was analysed. Interference by metals, such as lead and cadmium, was considered. Calibration plots were obtained in the micromolar and submicromolar concentration ranges, allowing the electrochemical determination of methylmercury in trace amounts. An estuarine water sample was analysed using the new method with a glassy carbon microelectrode.     

A Landau‐Lifshitz‐Gilbert‐Type equation and torsion effects on the dynamics of magnetization

Based on the non‐relativistic regime of electrons described by a Dirac equation coupled to a torsion pseudo‐vector, we study the dynamics of magnetization and how it may be affected by the presence of this (background) torsion field. The latter describes some anisotropy of the bulk and it may be accounted for in two ways: by means of a minimal coupling in a covariant derivative endowed with spin connection and a gauge magnetic field; in addition, through a non‐minimal interaction term with the spin density. We show, within this framework, that it is possible to attain a version of the Landau‐Lifshitz equation in presence of the torsion background where its effects are included, re‐enforcing that torsion corresponds to a geometric anisotropy with relevant unfolds on the spin coupling mechanism. We also conclude that the torsion terms can open up two important landscapes in the magnetization dynamics: one of them, related with a damping effect; the other, related with the screw dislocation that gives us a global effect like a sharped‐helix damping. The whole effort here is then to pursue an investigation of torsion in connection with the precession dynamics of the magnetization.

     

Energy Propagation in Classical Harmonic Lattices with Diluted Disorder

We consider the problem of a harmonic lattice in which masses’ distribution is a superposition of a random and a periodic distribution. Classical equations for the mass displacement and velocities are solved using a second-order Euler formalism. Energy flow was investigated on two distinct experiments: (i) We injected an initial wave-packet with energy E ₀ and analyzed the dynamics of the resulting energy pulse; (ii) we pumped one of the sides of the lattice with a external signal and then we observed the propagation of the pulse until the other side of chain. Our calculations suggest that the diluted disordered mass distribution promotes energy dynamics at high frequency limit.     

Simulation and design of a bandpass filter on metasubstrates

This work presents an analysis of the microstrip bandpass filter on metamaterial substrates. The filter is composed of two ring resonators with quarter-wavelength side-coupled sections. The filter input is provided, as well as the output port, using a quarter-wavelength side-coupled microstrip line section. Simulations by finite element method have been carried out to verify the effect of the metamaterial substrate properties on the filter performance, and to compare these results to those obtained considering isotropic substrate.     

Control of Crystallization Kinetics and Study of the Thermal, Structural and Morphological Properties of an Li2O–B2O3–Al2O3 Vitreous System

A glass matrix with nominal composition 50Li₂O·45B₂O₃·5Al₂O₃ (mol%) was synthesized, and its physical properties were investigated by differential thermal analysis (DTA), X-ray diffraction (XRD), and atomic force microscopy (AFM). The glass transition temperature T _g, the crystallization-onset temperature T _x,, the crystallization peak temperatures T _c1 and T _c2, and the fusion peak temperatures T _m1 and T _m2 were determined from at least two glass matrix phases to be approximately 382, 457, 486, 574, 761, and 787?°C, respectively, at 5?°C/min heating rate. Heat treatments at 450?°C for an increasing sequence of time intervals allowed control over the amount of crystallization. Additional information on the crystallization kinetics for the LBA glass matrix was gathered from AFM images, DTA thermograms, and XRD diffractograms. The latter technique showed that LiBO₂ (ICDD-16568) and Li₃AlB₂O₆ (ICDD-51754) phases are formed in the glass?Cceramic system. Debye?CScherrer analysis of the XRD peaks revealed a competition between the evolutions of crystal phases during heat treatment. Activation energies for crystallization, obtained from theoretical models applied to the DTA data showed that the crystallization is heterogeneous. The AFM images demonstrated that this heterogeneous crystallization starts at the surface of the LBA glass matrix and identified crystal sizes in agreement with the results of the Debye?CScherrer analysis. Our study shows that thermal and structural characterization techniques can be combined with theoretical results drawn from well-tested models to offer a unified view of crystallization in a glass?Cceramics system.     

Prediction of properties of biodiesel-diesel blends using spectrofluorimetry and multivariate calibration

Regressions based on fluorescence spectroscopy were developed to provide relatively inexpensive and rapid measurements of the concentration, viscosity, and specific gravity of biodiesel-diesel blends. The methods involved obtaining a mathematical model from spectrofluorimetric data and data from a given property (concentration, dynamic viscosity, or specific gravity) using partial least squares (PLS) regression, which was then applied as a model for predicting properties of interest. The predicted concentrations, dynamic viscosities, and specific gravities of the biodiesel-diesel blends were compared with actual values and agreed reasonably well with the obtained results. The models showed high correlation between real and predicted values. The R-square values near 1 indicated excellent model accuracy for predicting concentrations, specific gravities, and dynamic viscosities of biodiesel-diesel blends. The residual distribution did not follow a trend with respect to the predicted variables, indicating an excellent fit to the data.      

Lectin from Canavalia brasiliensis seeds (ConBr) is a valuable biotechnological tool to stimulate the growth of Rhizobium tropici in vitro

To study the interactions between a Rhizobium tropici strain and lectins isolated from the seeds of Canavalia ensiformis (ConA) and Canavalia brasiliensis (ConBr), a lectin fluorescence assay was performed. In addition, an experiment was designed to evaluate the effect of the two lectins on bacterial growth. Both lectins were found to bind to R. tropici cells, but the interactions were inhibited by D-mannose. Interestingly, only ConBr stimulated bacterial growth in proportion to the concentrations used (15.6-500 μg/mL), and the bacterial growth stimulation was inhibited by D-mannose as well. Structure/Function analyses by bioinformatics were carried out to evaluate the volume and carbohydrate recognition domain (CRD) configuration of ConA and ConBr. The difference of spatial arrangement and volume of CRD may indicate the variation between biological activities of both lectins. The results suggest that ConBr could be a promising tool for studies focusing on the interactions between rhizobia and host plants.