Simple HPLC‐UV for the quantification of a new leishmanicidal candidate (E)‐1‐4(trifluoromethyl) benzylidene)‐5‐(2‐4‐dichlorozoyl) carbonylhydrazine (LASSBio‐1736) in rat plasma for pharmacokinetics assessment

In this study, a sensitive HPLC‐UV assay was developed and validated for the determination of LASSBio‐1736 in rat plasma with sodium diclofenac as internal standard (IS). Liquid–liquid extraction using acetonitrile was employed to extract LASSBio‐1736 and IS from 100 μL of plasma previously basified with NaOH 0.1 M. Chromatographic separation was carried on Waters Spherisorb^®S5 ODS2 C₁₈ column (150 × 4.6 mm, 5 μm) using an isocratic mobile phase composed by water with triethylamine 0.3% (pH 4), methanol and acetonitrile grade (45:15:40, v/v/v) at a flow rate of 1 mL/min. Both LASSBio‐1736 and IS were eluted at 4.2 and 5 min, respectively, with a total run time of 8 min only. The lower limit of quantification was 0.2 μg/mL and linearity between 0.2 and 4 μg/mL was obtained, with an R² > 0.99. The accuracy of the method was >90.5%. The relative standard deviations intra and interday were <6.19 and <7.83%, respectively. The method showed the sensitivity, linearity, precision, accuracy and selectivity required to quantify LASSBio‐1736 in preclinical pharmacokinetic studies according to the criteria established by the US Food and Drug Administration and European Medicines Agency. Copyright © 2016 John Wiley & Sons, Ltd.     

Nonlinear Boundary Value Problems on Sequence Spaces

In this paper we study the solvability of nonlinear, discrete-time boundary value problems for functional equations. Conditions are established for the existence of solutions to problems of the form $$x(k + 1) = f(k, x(k)) + \lambda g(k, x(k)); \quad k = 0, 1, 2, \ldots$$     

Heuristic approaches for support vector machines with the ramp loss

Recently, Support Vector Machines with the ramp loss (RLM) have attracted attention from the computational point of view. In this technical note, we propose two heuristics, the first one based on solving the continuous relaxation of a Mixed Integer Nonlinear formulation of the RLM and the second one based on the training of an SVM classifier on a reduced dataset identified by an integer linear problem. Our computational results illustrate the ability of our heuristics to handle datasets of much larger size than those previously addressed in the literature.     

Surface Properties of Anatase TiO2 Nanowire Films Grown from a Fluoride‐Containing Solution

Controlling the surface chemistry of nucleating seeds during wet‐chemical synthesis allows for the preparation of morphologically well‐defined nanostructures. Synthesis conditions play a key role in the surface properties, which directly affect the functional properties of the material. Therefore, it is important to establish post‐synthesis treatments to facilitate the optimization of surface properties with respect to a specific application, without losing the morphological peculiarity of the nanostructure. We studied the surface properties of highly crystalline and porous anatase TiO₂ nanowire (NW) electrodes, grown by chemical‐bath deposition in fluoride‐containing solutions, using a combined electrochemical and spectroscopic approach. As‐deposited films showed low capacity for catechol adsorption and a poor photoelectrocatalytic activity for water oxidation. Mild thermal annealing at 200 °C resulted in a significant improvement of the electrode photoelectrocatalytic activity, whereas the bulk properties of the NWs (crystal structure, band‐gap energy) remained unchanged. Enhancement of the functional properties of the material is discussed on the basis of adsorption capacity and electronic properties. The temperature‐induced decrease of recombination centers, along with the concomitant increase of adsorption and reaction sites upon thermal annealing are called to be responsible for such improved performance.     

Determination of five booster biocides in seawater by stir bar sorptive extraction–thermal desorption–gas chromatography–mass spectrometry

Stir bar sorptive extraction (SBSE) and thermal desorption (TD)–gas chromatography–mass spectrometry (GC–MS) have been optimized for the determination of five organic booster biocides (Chlorothalonil, Dichlofluanid, Sea-Nine 211, Irgarol 1051 and TCMTB) in seawater samples. The parameters affecting the desorption and absorption steps were investigated using 10 mL seawater samples. The optimised conditions consisted of an addition of 0.2 g mL⁻¹ KCl to the sample, which was extracted with 10 mm length, 0.5 mm film thickness stir bars coated with polydimethylsiloxane (PDMS), and stirred at 900 rpm for 90 min at room temperature (25 °C) in a vial. Desorption was carried out at 280 °C for 5 min under 50 mL min⁻¹ of helium flow in the splitless mode while maintaining a cryotrapping temperature of 20 °C in the programmed-temperature vaporization (PTV) injector of the GC–MS system. Finally, the PTV injector was ramped to a temperature of 280 °C and the analytes were separated in the GC and detected by MS using the selected-ion monitoring (SIM) mode. The detection limits of booster biocides were found to be in the range of 0.005–0.9 μg L⁻¹. The regression coefficients were higher than 0.999 for all analytes. The average recovery was higher than 72% (R.S.D.: 7–15%). All these figures of merit were established running samples in triplicate. This simple, accurate, sensitive and selective analytical method may be used for the determination of trace amounts of booster biocides in water samples from marinas.