An approach to the synthesis of furanoheliangolides through Diels-Alder reactions

The core structure of the natural sesquiterpene lactones furanoheliangolides, an 11-oxabicyclo[6.2.1]undecane system, was synthesized through a pathway involving two Diels-Alder reactions.     

Nafion/tetraruthenated porphyrin glassy carbon-modified electrode: characterization and voltammetric studies of sulfite oxidation in water–ethanol solutions

In this work, the modification of a glassy carbon electrode with tetraruthenated porphyrins electrostatically assembled onto a Nafion film, previously adsorbed on the electrode surface, is reported. This modified electrode was characterized by scanning electron microscopy–energy-dispersive X-ray, Raman spectroscopy, UV-Vis spectroelectrochemistry, and cyclic voltammetry. The Nafion film onto the glassy carbon electrode shows a smooth disposition; when the tetraruthenated porphyrin is incorporated on the Nafion film, the complex is adsorbed in a homogeneous way. The modified electrode catalyzes HSO₃⁻ oxidation in water–ethanol solutions and shows an enhanced stability compared with the electrode modified with the dip coating method. Rotating disk electrode experiments showed a kinetic limitation to the electron transfer controlled by charge propagation in the film. I/E curves show a Tafel slope of 120 mV/decade corresponding to a first electron-transfer reaction, depending on the potential, as the determining step. Spectroelectrochemical experiments demonstrated that Ru(II) is the active site for the electrocatalysis.     

A nonlocal nonlinear diffusion equation in higher space dimensions

We study the initial-value problem for a nonlocal nonlinear diffusion operator which is analogous to the porous medium equation, in the whole RN, N?1, or in a bounded smooth domain with Neumann or Dirichlet boundary conditions. First, we prove the existence, uniqueness and the validity of a comparison principle for solutions of these problems. In RN we show that if initial data is bounded and compactly supported, then the solutions is compactly supported for all positive time t, this implies the existence of a free boundary. Concerning the Neumann problem, we prove that the asymptotic behavior of the solutions as t→∞, they converge to the mean value of the initial data. For the Dirichlet problem we prove that the asymptotic behavior of the solutions as t→∞, they converge to zero.     

Determination of eight fatty acid ethyl esters in meconium samples by headspace solid‐phase microextraction and gas chromatography–mass spectrometry

A number of fatty acid ethyl esters (FAEEs) have recently been detected in meconium samples. Several of these FAEEs have been evaluated as possible biomarkers for in utero ethanol exposure. In the present study, a method was optimized and validated for the simultaneous determination of eight FAEEs (ethyl laurate, ethyl myristate, ethyl palmitate, ethyl palmitoleate, ethyl stearate, ethyl oleate, ethyl linoleate and ethyl arachidonate) in meconium samples. FAEEs were extracted by headspace solid‐phase microextraction. Analyte detection and quantification were carried out using GC‐MS operated in chemical ionization mode. The corresponding D5‐ethyl esters were synthesized and used as internal standards. The LOQ and LOD for each analyte were <150 and <100 ng/g, respectively. The method showed good linearity (r²>0.98) in the concentration range studied (LOQ – 2000 ng/g). The intra‐ and interday imprecision, given by the RSD of the method, was lower than 15% for all FAEEs studied. The validated method was applied to 63 authentic specimens. FAEEs could be detected in alcohol‐exposed newborns (>600 ng/g cumulative concentration). Interestingly, FAEEs could also be detected in some non‐exposed newborns, although the concentrations were much lower than those measured in exposed cases.     

A Validated LC Method for the Quantitation of Cefotaxime in pH-Sensitive Nanoparticles

A sensitive and rapid routine LC method was validated for measuring cefotaxime incorporated in three different pH-sensitive nanoparticles. The drug was chromatographed on a C18 reversed-phase column; the mobile phase used was 0.05 M aqueous ammonium acetate, acetonitrile and tetrahydrofuran (87:11:2, v/v) adjusted to pH 5.5 with acetic acid. The flow rate was 1 mL min^?1 and cefotaxime was quantified at 254 nm, with a sensitivity range of 0.005 AUFS. The validated method was specific, linear (R ² ≥ 0.999), precise and accurate in a concentration range of 0.2–50.0 μg mL^?1. The method was rapid, selective and suitable for evaluation of cefotaxime in pH-sensitive Eudragit nanoparticles.     

Transient dynamics around unstable periodic orbits in the generalized repressilator model

We study the temporal dynamics of the generalized repressilator, a network of coupled repressing genes arranged in a directed ring topology, and give analytical conditions for the emergence of a finite sequence of unstable periodic orbits that lead to reachable long-lived oscillating transients. Such transients dominate the finite time horizon dynamics that is relevant in confined, noisy environments such as bacterial cells (see our previous work [Strelkowa and Barahona, J. R. Soc. Interface 7, 1071 (2010)]), and are therefore of interest for bioengineering and synthetic biology. We show that the family of unstable orbits possesses spatial symmetries and can also be understood in terms of traveling wave solutions of kink-like topological defects. The long-lived oscillatory transients correspond to the propagation of quasistable two-kink configurations that unravel over a long time. We also assess the similarities between the generalized repressilator model and other unidirectionally coupled electronic systems, such as magnetic flux gates, which have been implemented experimentally.     

Restart strategies for GRASP with path-relinking heuristics

GRASP with path-relinking is a hybrid metaheuristic, or stochastic local search (Monte Carlo) method, for combinatorial optimization. A restart strategy in GRASP with path-relinking heuristics is a set of iterations {i ₁, i ₂, …} on which the heuristic is restarted from scratch using a new seed for the random number generator. Restart strategies have been shown to speed up stochastic local search algorithms. In this paper, we propose a new restart strategy for GRASP with path-relinking heuristics. We illustrate the speedup obtained with our restart strategy on GRASP with path-relinking heuristics for the maximum cut problem, the maximum weighted satisfiability problem, and the private virtual circuit routing problem.