Electrochemical Oxidation of Sanguinarine and of Its Oxidation Products at a Glassy Carbon Electrode – Relevance to Intracellular Effects

The electrochemical behavior of sanguinarine, a quaternary benzophenanthridine glycoside alkaloid with antimicrobial, anti‐inflammatory, antioxidant and/or immune‐stimulatory activities, was studied at a glassy carbon electrode using cyclic, differential pulse, and square wave voltammetry. The oxidation of sanguinarine is a quasireversible, diffusion‐controlled process and occurred in a cascade mechanism with the formation of several oxidation products which adsorbed at the electrode surface. The oxidation of sanguinarine is pH dependent and involves the transfer of the same number of electrons and protons. The adsorbed sanguinarine oxidation products are reversibly oxidized at the glassy carbon electrode surface and their oxidation for a wide range of pHs was also studied by differential pulse and square wave voltammetry. A mechanism for the oxidation of sanguinarine at glassy carbon electrode is proposed.     

Selective isolation-detection of two different positively charged peptides groups by strong cation exchange chromatography and matrix-assisted laser desorption/ionization mass spectrometry: application to proteomics studies

We report here a procedure for the independent analysis of two groups of peptides by liquid chromatography-matrix-assisted laser desorption/ionization mass spectrometry (LC-MALDI MS/MS), using a selective isolation-detection procedure. In this procedure all primary amino groups of tryptic peptides derived from mouse liver proteins are blocked, restricting their positive charge, at acidic pH, to the presence of histidine and arginine residues. After strong cation exchange chromatography, multiply charged peptides (R + H > 1) are retained on the column and separated with high selectivity from singly (R + H = 1) and neutral peptides (R + H = 0) which are together collected in the flow-through. Using LC-MALDI-MS/MS analysis, the retained fraction displayed a 94% of enrichment of multiply charged peptides while in the flow-through; peptides with at least one arginine or histidine residue were exclusively identified, which suggests that MS detection in this fraction is restricted only to those peptides with ionizable side chains, arginine and histidine amino acids.     

Time-resolved and high-resolution MRA in a rabbit model of pulmonary embolism at 7 T: preliminary results

Purpose

Evaluate feasibility of using time-resolved and high-resolution, contrast-enhanced magnetic resonance angiography (MRA) at 7 T for characterization of an animal model of pulmonary embolism.

Methods

MRAs were performed in five rabbits using a 7-T MR scanner. Preceding the MR studies, each rabbit underwent a pulmonary artery catheterization with balloon placement. Two doses of gadodiamide were injected: first during a time-resolved MRA, immediately followed by a high-resolution acquisition. Balloon was then deflated, permitting reperfusion for 5 min. A second dose was then injected and another high-resolution MRA acquired. Measurements of signal-to-noise ratio (SNR), contrast-to-noise ratio (CNR) and vessel cross-sections down to fourth-order branches were made, among other parameters.

Results

Occlusion was detected in all rabbits. Despite a TE of 0.58 ms for the time-resolved MRA, regions of nonuniform enhancement attributed to susceptibility effects at the 7-T field were observed in perfused lung. Mean SNR=7.5±3.3 and 134.2±46.5 for the lung and aorta, respectively, and mean CNR=126.7±46.4 for aorta versus lung were obtained. Diameters of vessels in lung that was never occluded were not statistically different from those in reperfused lung.

Conclusion

Results show that time-resolved and high-resolution MRA of the lung are feasible at 7 T and provide high SNR, CNR and resolution, but TEs smaller than 0.58 ms are required to avoid susceptibility artifacts in time-resolved MRAs.     

Kinetic study of crystallization of PHB in presence of hydroxy acids

Poly(3-hydroxybutyrate), PHB, has been structurally modified through reaction with hydroxy acids (HA) such as tartaric acid (TA) and malic acid (MA). The crystallization kinetic of the samples was evaluated by isoconversional method through nonlinear fitting to obtain the estimation for activation energy (E _a ) and pre-exponential (A) values. The thermal behavior of the crystallization temperature, 44.8 and 58.9 °C at 5 °C/min, and results obtained to the average activation energy, 73 ± 9 kJ mol⁻¹ and 63 ± 1 kJ mol⁻¹, to PHB/MA and PHB, respectively, are suggesting that malic acid may be deriving plasticizer units from its own PHB chain. PHB/TA show increase in the medium value of E _a, 119 ± 2 kJ mol⁻¹ and T _c = 48.2 °C (at 5 °C/min), indicating that tartaric acid is probably interacts in different way to the of PHB chain (E _a=73 ± 9 kJ mol⁻¹, T _c = 44.8 °C at 5 °C/min).     

Preparation and characterization of Ca1 − x Ce x MnO3 perovskite electrodes

The electrochemical properties of Ca_1 − x Ce _x MnO₃ perovskite-type oxide electrode have been investigated by cyclic voltammetry in Na₂SO₄ aqueous solutions with pH 14. The structural and morphological characterizations have also been investigated and the information used to interpret the electrochemical behavior. An estimation of the electrode’s capacitance and roughness factor has been obtained by means of cyclic voltammetry. The specific capacitance and consequently the roughness factor values are affected by the presence of Ce ions in the oxide. These findings are in agreement with the increase of the oxide-specific surface area by the introduction of Ce ion. The open-circuit potential and the voltammetric patterns are dependent on the presence of Ce ion in the electrodes and support that the surface electrochemistry of the perovskite oxide electrodes is governed by the Mn⁴⁺–Mn³⁺ redox couple.     

Development of a sequential injection chromatography (SIC) method for determination of simazine,atrazine, and propazine

This paper describes the development of a sequential injection chromatography (SIC) procedure for separation and quantification of the herbicides simazine, atrazine, and propazine exploring the low backpressure of a 2.5 cm long monolithic C₁₈ column. The separation of the three compounds was achieved in less than 90 s with resolution >1.5 using a mobile phase composed by ACN/1.25 mmol/L acetate buffer (pH 4.5) at the volumetric ratio of 35:65 and flow rate of 40 μL/s. Detection was made at 223 nm using a flow cell with 40 mm of optical path length. The LOD was 10 μg/L for the three triazines and the quantification limits were of 30 μg/L for simazine and propazine and 40 μg/L for atrazine. The sampling frequency is 27 samples per hour, consuming 1.1 mL of ACN per analysis. The proposed methodology was applied to spiked water samples and no statistically significant differences were observed in comparison to a conventional HPLC–UV method. The major metabolites of atrazine and other herbicides did not interfere in the analysis, being eluted from the column either together with the unretained peak, or at retention times well‐resolved from the studied compounds.     

The influence of the boundary behavior on isometric immersions in the hyperbolic space

This paper studies how the behavior of a proper isometric immersion into the hyperbolic space is influenced by its behavior at infinity. Our first result states that a proper isometric minimal immersion into the hyperbolic space with the asymptotic boundary contained in a sphere reduces codimension. This result is a corollary of a more general one that establishes a sharp lower bound for the sup-norm of the mean curvature vector of a Proper isometric immersion into the Hyperbolic space whose Asymptotic boundary is contained in a sphere. We also prove that a properly immersed hypersurface with mean curvature satisfying sup _{p∈Σ ||H(p)|| < 1} has no isolated points in its asymptotic boundary. Our main tool is a Tangency principle for isometric immersions of arbitrary codimension. This work is partially supported by CAPES, Brazil.     

On the principal eigenvalue of some nonlocal diffusion problems

In this paper we analyze some properties of the principal eigenvalue λ₁(Ω) of the nonlocal Dirichlet problem (J∗u)(x)−u(x)=−λu(x) in Ω with u(x)=0 in RN?Ω. Here Ω is a smooth bounded domain of RN and the kernel J is assumed to be a C¹ compactly supported, even, nonnegative function with unit integral. Among other properties, we show that λ₁(Ω) is continuous (or even differentiable) with respect to continuous (differentiable) perturbations of the domain Ω. We also provide an explicit formula for the derivative. Finally, we analyze the asymptotic behavior of the decreasing function Λ(γ)=λ₁(γΩ) when the dilatation parameter γ>0 tends to zero or to infinity.     

Homoclinic tangencies versus uniform hyperbolicity for conservative 3-flows

We prove that a volume-preserving three-dimensional flow can be C¹-approximated by a volume-preserving Anosov flow or else by another volume-preserving flow exhibiting a homoclinic tangency. This proves the conjecture of Palis for conservative 3-flows and with respect to the C¹-topology.