Quantification of endocrine disruptors and pesticides in water by gas chromatography–tandem mass spectrometry. Method validation using weighted linear regression schemes

A multi-residue methodology based on a solid phase extraction followed by gas chromatography–tandem mass spectrometry was developed for trace analysis of 32 compounds in water matrices, including estrogens and several pesticides from different chemical families, some of them with endocrine disrupting properties. Matrix standard calibration solutions were prepared by adding known amounts of the analytes to a residue-free sample to compensate matrix-induced chromatographic response enhancement observed for certain pesticides. Validation was done mainly according to the International Conference on Harmonisation recommendations, as well as some European and American validation guidelines with specifications for pesticides analysis and/or GC–MS methodology. As the assumption of homoscedasticity was not met for analytical data, weighted least squares linear regression procedure was applied as a simple and effective way to counteract the greater influence of the greater concentrations on the fitted regression line, improving accuracy at the lower end of the calibration curve. The method was considered validated for 31 compounds after consistent evaluation of the key analytical parameters: specificity, linearity, limit of detection and quantification, range, precision, accuracy, extraction efficiency, stability and robustness.     

Discrete Orbits,Recurrence and Solvable Subgroups of $${{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}$$

We discuss the local dynamics of a subgroup of \({{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}\) possessing locally discrete orbits as well as the structure of the recurrent set for more general groups. It is proved, in particular, that a subgroup of \({{\mathrm{Diff}}\, ({{\mathbb {C}}}^2, 0)}\) possessing locally discrete orbits must be virtually solvable. These results are of considerable interest in problems concerning integrable systems.     

Aqueous biphasic systems involving alkylsulfate-based ionic liquids

The specific effects of K₃PO₄, K₂CO₃, Na₂CO₃, and (NH₄)₂SO₄, as high charge-density inorganic salts and thus inducers of the formation of aqueous biphasic systems (ABS) containing several ethyl-methylimidazolium alkylsulfate ionic liquids, C₂MIM C_nSO₄ (n = 2, 4, 6, or 8), have been assessed at T = 298.15 K. The results are analyzed in the light of the Hofmeister series. The influence of different alkyl chain lengths in the anion, together with the ability of the selected inorganic salts to induce the formation of ABS, is discussed. Phase diagrams have been determined through turbidimetry, including tie lines assignments from mass phase ratios according to the lever – arm rule. The Merchuck equation was satisfactorily used to correlate the solubility curve.     

Fibrations of Genus Two on Complex Surfaces

This work is devoted to the study of fibrations of genus 2 by using as its main tool the theory of singular holomorphic foliations. In particular we obtain a sharp differentiable version of Matsumoto–Montesinos theory. In the case of isotrivial fibrations, these methods are powerful enough to provide a detailed global picture of the both the ambient surface and of the structure of the fibrations itself.     

A hybrid collocation method for a nonlinear Volterra integral equation with weakly singular kernel

This work is concerned with the numerical solution of a nonlinear weakly singular Volterra integral equation. Owing to the singular behavior of the solution near the origin, the global convergence order of product integration and collocation methods is not optimal. In order to recover the optimal orders a hybrid collocation method is used which combines a non-polynomial approximation on the first subinterval followed by piecewise polynomial collocation on a graded mesh. Some numerical examples are presented which illustrate the theoretical results and the performance of the method. A comparison is made with the standard graded collocation method.     

On the approximate solution to an initial boundary valued problem for the Cahn–Hilliard equation

The particular approximate solution of the initial boundary valued problem to the Cahn–Hilliard equation is provided. The Fourier Method is combined with the Adomian’s decomposition method in order to provide an approximate solution that satisfy the initial and the boundary conditions. The approximate solution also satisfies the mass conservation principle.     

A pointwise constrained version of the Liapunov convexity theorem for single integrals

Given any AC solution ${\overline{x} : [a,b] \rightarrow \mathbb{R}^{n}}$ to the convex ordinary differential inclusion $$x^{\prime} ( t) \in co\{v^{1} ( t), \ldots, v^{m} ( t)\} \qquad a.e. on [ a,b], \qquad \qquad (^{*})$$ we aim at solving the associated nonconvex inclusion $$x^{\prime} ( t) \in \{v^{1} ( t), \ldots, v^{m} ( t)\} \qquad a.e.,x( a) = \overline{x} ( a), x( b) = \overline{x} ( b), \qquad \qquad (^{**})$$ under an extra pointwise constraint (e.g. on the first coordinate): $$x_{1} ( t) \leq \overline{x}_{1} ( t) \qquad \forall t \in [ a,b]. \qquad \qquad \qquad (^{***})$$ While the unconstrained inclusion (**) had been solved already in 1940 by Liapunov, its constrained version, with (***), was solved in 1994 by Amar and Cellina in the scalar n = 1 case. In this paper we add an extra geometrical hypothesis which is necessary and sufficient, in the vector n > 1 case, for it existence of solution to the constrained inclusion (**) and (***). We also present many examples and counterexamples to the 2 × 2 case.     

FTIR Spectroscopy as a Tool to Study Age-Related Changes in Cardiac and Skeletal Muscle of Female C57BL/6J Mice

Studying aging is important to further understand the molecular mechanisms underlying this physiological process and, ideally, to identify a panel of aging biomarkers. Animals, in particular mice, are often used in aging studies, since they mimic important features of human aging, age quickly, and are easy to manipulate. The present work describes the use of Fourier Transform Infrared (FTIR) spectroscopy to identify an age-related spectroscopic profile of the cardiac and skeletal muscle tissues of C57BL/6J female mice. We acquired ATR-FTIR spectra of cardiac and skeletal muscle at four different ages: 6; 12; 17 and 24 months (10 samples at each age) and analyzed the data using multivariate statistical tools (PCA and PLS) and peak intensity analyses. The results suggest deep changes in protein secondary structure in 24-month-old mice compared to both tissues in 6-month-old mice. Oligomeric structures decreased with age in both tissues, while intermolecular β-sheet structures increased with aging in cardiac muscle but not in skeletal muscle. Despite FTIR spectroscopy being unable to identify the proteins responsible for these conformational changes, this study gives insights into the potential of FTIR to monitor the aging process and identify an age-specific spectroscopic signature.     

Enhancement of Antibiotic Activity by 1,8-Naphthyridine Derivatives against Multi-Resistant Bacterial Strains

The search for new antibacterial agents has become urgent due to the exponential growth of bacterial resistance to antibiotics. Nitrogen-containing heterocycles such as 1,8-naphthyridine derivatives have been shown to have excellent antimicrobial properties. Therefore, the purpose of this study was to evaluate the antibacterial and antibiotic-modulating activities of 1,8-naphthyridine derivatives against multi-resistant bacterial strains. The broth microdilution method was used to determine the minimum inhibitory concentration (MIC) of the following compounds: 7-acetamido-1,8-naphthyridin-4(1H)-one and 3-trifluoromethyl-N-(5-chloro-1,8-naphthyridin-2-yl)-benzenesulfonamide. The antibiotic-modulating activity was analyzed using subinhibitory concentrations (MIC/8) of these compounds in combination with norfloxacin, ofloxacin, and lomefloxacin. Multi-resistant strains of Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus were used in both tests. Although the compounds had no direct antibacterial activity (MIC ≥ 1.024 µg/mL), they could decrease the MIC of these fluoroquinolones, indicating synergism was obtained from the association of the compounds. These results suggest the existence of a structure–activity relationship in this group of compounds with regard to the modulation of antibiotic activity. Therefore, we conclude that 1,8-naphthyridine derivatives potentiate the activity of fluoroquinolone antibiotics against multi-resistant bacterial strains, and thereby interesting candidates for the development of drugs against bacterial infections caused by multidrug resistant strains.