Optimization of a solid-phase extraction procedure in the fluorimetric determination of sulfonamides in milk using the second-order advantage of PARAFAC and D-optimal design

The objective of this work is to optimize a solid-phase extraction procedure for the simultaneous determination of sulfadiazine, sulfamerazine, and sulfamethazine in milk by fluorimetric detection. For this task, an alternative strategy is employed, which allows one to reduce noticeably the number of experiments without losing the quality of the estimations. It consists of the use of a D-optimal design together with PARAFAC decomposition for the calculation of the response in the experimental design. Effects of amount of cartridge sorbent, kind of milk, volume of conditioning solutions, kind of wash and elution, and kind of mixture of sulfonamides have been evaluated, for maximizing sulfonamide mean recovery and minimizing its standard deviation. Since milk without sulfonamides may give some matrix effect over the fluorescence signal, its behavior has also been studied. Optimal conditions have been selected where the ratio between sulfonamide recovery and milk without sulfonamides was the highest, which are 500 mg of cartridge sorbent, acid wash, and elution and 3 mL of conditioning solutions. The type of milk and mixture of sulfonamides not significant. This makes the procedure suitable for the combined determination of sulfadiazine, sulfamerazine, and sulfamethazine in any kind of milk. Finally, an experimental procedure is proposed, obtaining a sulfonamide mean recovery equal to 68.5% with values of standard deviation between 7 and 8 μg kg⁻¹.     

An SPR biosensor for the detection of microcystins in drinking water

A surface plasmon resonance (SPR) biosensor for the detection of microcystins (MCs) in drinking water has been developed. Several assay formats have been evaluated. The selected format is based on a competitive inhibition assay, in which microcystin-LR (MCLR) has been covalently immobilized onto the surface of an SPR chip functionalized with a self-assembled monolayer. The influence of several factors affecting sensor performance, such as the nature and concentration of the antibody, the composition of the carrier buffer, and the blocking and regeneration solutions, has been evaluated. The optimized SPR biosensor provides an IC₅₀ 0.67 ± 0.09 μg L⁻¹, a detection limit of 73 ± 8 ng L⁻¹, and a dynamic range from 0.2 to 2.0 μg L⁻¹ for MCLR. Cross-reactivity to other related MCs, such as microcystin-RR (88%) and microcystin-YR (94%), has also been measured. The SPR biosensor can perform four simultaneous determinations in 60 min, and each SPR chip can be reused for at least 40 assay–regeneration cycles without significant binding capacity loss. The biosensor has been successfully applied to the direct analysis of MCLR in drinking water samples, below the provisional guideline value of 1 μg L⁻¹ established by the World Health Organization for drinking water.     

Synthesis and characterization of WO3 nanoparticles prepared by the precipitation method: Evaluation of photocatalytic activity under vis-irradiation

WO₃ nanoparticles were synthesized by the precipitation method varying the time employed in the formation of their precursor in aqueous media and the calcination temperature. The WO₃ crystallization process and morphology of the synthesized samples were followed by the XRD, TEM and SEM techniques. The effects of the calcination temperature on the surface area and optical properties of the WO₃ nanoparticles were also investigated. Nanoparticles with morphologies such as square and rectangular plates and ovoid forms were observed for the different experimental conditions. WO₃ nanoparticles with different morphologies were tested for the photocatalytic degradation of organic dyes. In general, the photocatalysts showed a capacity to bleach the dye solution in the following sequence: indigo carmine (IC) > rhodamine B (rhB) > congo red (CR). The extent of mineralization was determined by means of total organic carbon (TOC) measurements, which showed a satisfactory TOC reduction (93%, within 75 h) only for IC. This value was even better than the one concerning the P-25 Degussa reference.     

Adapting decarbonylation chemistry for the development of prodrugs capable of in vivo delivery of carbon monoxide utilizing sweeteners as carrier molecules

Carbon monoxide as an endogenous signaling molecule exhibits pharmacological efficacy in various animal models of organ injury. To address the difficulty in using CO gas as a therapeutic agent for widespread applications, we are interested in developing CO prodrugs through bioreversible caging of CO in an organic compound. Specifically, we have explored the decarboxylation–decarbonylation chemistry of 1,2-dicarbonyl compounds. Examination and optimization of factors favorable for maximal CO release under physiological conditions led to organic CO prodrugs using non-calorific sweeteners as leaving groups attached to the 1,2-dicarbonyl core. Attaching a leaving group with appropriate properties promotes the desired hydrolysis–decarboxylation–decarbonylation sequence of reactions that leads to CO generation. One such CO prodrug was selected to recapitulate the anti-inflammatory effects of CO against LPS-induced TNF-α production in cell culture studies. Oral administration in mice elevated COHb levels to the safe and efficacious levels established in various preclinical and clinical studies. Furthermore, its pharmacological efficacy was demonstrated in mouse models of acute kidney injury. These studies demonstrate the potential of these prodrugs with benign carriers as orally active CO-based therapeutics. This represents the very first example of orally active organic CO prodrugs with a benign carrier that is an FDA-approved sweetener with demonstrated safety profiles in vivo.

1,2-Dicarbonyl compounds with FDA-approved sweeteners as leaving groups deliver CO for protection against acute kidney injury in mice.     

Yb-doped strictly all-fiber laser actively Q-switched by intermodal acousto-optic modulation

We show an actively Q-switched ytterbium-doped strictly all-fiber laser. Cavity loss modulation is achieved in a tapered optical fiber by core-to-cladding mode-coupling induced by travelling flexural acoustic waves. When the acoustical signal is switched-off, the optical power losses within the cavity are reduced, and then a laser pulse is emitted. Trains of Q-switched pulses were successfully obtained at repetition rates in the range 1–10 kHz, with pump powers between 59 and 88 mW, at the optical wavelength of 1064.1 nm. Best results were for laser pulses of 118 mW peak power, 1.8 μs of time width, with a pump power of 79 mW, at 7 kHz repetition rate.     

Fermions on deformed thick branes

In this work we investigate the issue of fermion localization and resonances in (4,1)-deformed branes constructed with one scalar field coupled with gravity. Such models provide us branes with internal structures that turns the gravitational interaction more effective for fermions aside the brane, increasing their lifetime. The coupling between the scalar field and spinors is a necessary condition for fermions to be localized on such branes. After performing a chiral decomposition of the five-dimensional spinor we found resonances with both chiralities. The correspondence between the spectra for left and right chirality is guaranteed and Dirac fermions are realized on the brane.     

Combination of Raman, Infrared, and X-Ray Energy-Dispersion Spectroscopies and X-Ray Diffraction to Study a Fossilization Process

X-ray diffraction was combined with X-ray energy-dispersion, Fourier-transform infrared, and Raman spectroscopies to study the fossilization of a Cretaceous specimen of the plant Brachyphyllum castilhoi, a fossil from the Ipubi Formation, in the Araripe Sedimentary Basin, Northeastern Brazil. Among the possible fossilization processes, which could involve pyrite, silicon oxide, calcium oxide, or other minerals, we were able to single out pyritization as the central mechanism producing the fossil, more than 100 million years ago. In addition to expanding the knowledge of the Ipubi Formation, this study shows that, when combined with other experimental techniques, Raman spectroscopy is a valuable tool at the paleontologist’s disposal.     

Modeling of astigmatic-elliptical beam shaping during fs-laser waveguide writing including beam truncation and diffraction effects

In this work, we report a model for accurately calculating the focal volumes corresponding to astigmatic elliptical beams used in fs-laser waveguide writing. The model is based on the use of the ABCD matrix formalism for the propagation of a Gaussian beam. The code includes the effects of propagation on the astigmatic elliptical beam, and the effects of beam truncation and diffraction at the entrance pupil of the focusing objective due to beam clipping when overfilling the pupil. The results predict that for a given astigmatism value and propagation distance it is possible to efficiently suppress the astigmatic focus closer to the surface. This explains previous experimental results where single structure waveguides with controllable aspect-ratio were fabricated using astigmatic-elliptical beams. Furthermore, we investigate the respective roles of astigmatism and beam propagation, as well as the strong impact of truncation and diffraction effects caused by clipping the beam at the pupil of the focusing optics. Finally, based on the results from our model, we present some practical considerations in terms of beam propagation and phase wrapping constraints.     

Monogenic pseudo‐complex power functions and their applications

The use of a non‐commutative algebra in hypercomplex function theory requires a large variety of different representations of polynomials suitably adapted to the solution of different concrete problems. Naturally arises the question of their relationships and the advantages or disadvantages of different types of polynomials. In this sense, the present paper investigates the intrinsic relationship between two different types of monogenic Appell polynomials. Several authors payed attention to the construction of complete sets of monogenic Appell polynomials, orthogonal with respect to a certain inner product, and used them advantageously for the study of problems in 3D‐elasticity and other problems. Our goal is to show that, as consequence of the binomial nature of those generalized Appell polynomials, their inner structure is determined by interesting combinatorial relations in which the central binomial coefficients play a special role. As a byproduct of own interest, a Riordan–Sofo type binomial identity is also proved. Copyright © 2013 John Wiley & Sons, Ltd.     

A Direct Splitting Method for Nonsmooth Variational Inequalities

We propose a direct splitting method for solving a nonsmooth variational inequality in Hilbert spaces. The weak convergence is established when the operator is the sum of two point-to-set and monotone operators. The proposed method is a natural extension of the incremental subgradient method for nondifferentiable optimization, which strongly explores the structure of the operator using projected subgradient-like techniques. The advantage of our method is that any nontrivial subproblem must be solved, like the evaluation of the resolvent operator. The necessity to compute proximal iterations is the main difficulty of other schemes for solving this kind of problem.