Assignment of complex species by affinity capillary electrophoresis: The case of Th(IV)-desferrioxamine B

The electrophoretic mobility change of desferrioxamine B (DFO) was monitored by UV absorption spectrophotometry upon increasing the thorium(IV) concentration in the background electrolyte at two acidities ([HClO₄]_Tot = 0.0316 and 0.0100 M). These data enabled to assess the speciation model and to determine the equilibrium constant of [Th(DFO)H₂]³⁺ at fixed ionic strength (I = 0.1 M (H,Na)ClO₄). Affinity capillary electrophoresis (ACE) turned out to be most helpful in identifying the complexed species by ascertaining its charge and protonation state. The assignment of the correct stoichiometry relied on the reliable estimation of the electrophoretic mobility by assuming similar hydrodynamic radii for (DFO)H₄⁺ and the chelate. The value of the apparent equilibrium constant (log β₁₁₂ = 38.7 ± 0.4) obtained by ACE compares favorably well with those reported in the literature for thorium and a range of other metal ions, according to a linear free-energy relationship. This method is useful for studying metal-ligand binding equilibria and provides valuable information for further modelling the behavior of tetravalent actinides under environmental conditions. Structural information about the prevalent solution species in acidic conditions was gained by DFT calculations, confirming the bishydroxamato coordination mode of Th⁴⁺ by the diprotonated ligand.     

Approximation by an iterative method of a low‐Mach model with temperature dependent viscosity

In this work, we prove the existence and the uniqueness of the strong solution of a low‐Mach model, for which the dynamic viscosity of the fluid is a given function of its temperature. The method is based on the convergence study of a sequence towards the solution, for which the rates are also given. The originality of the approach is to consider the system in terms of the temperature and the velocity, leading to a nonlinear temperature equation and the development of some specific tools and results.     

One-Pot Synthesis of Metastable 2,5-Dihydrooxepines through Retro-Claisen Rearrangements: Method and Applications

A one-pot methodology to synthesize metastable bicyclic 2,5-dihydrooxepines from cyclic 1,3-diketones and 1,4-dibromo-2-butenes through the retro-Claisen rearrangement of syn-2-vinylcyclopropyl diketone intermediates is reported. DFT calculations were performed to understand the reaction selectivity and mechanisms towards [1,3]- or [3,3]-sigmatropic rearrangements, highlighting the crucial influence of the temperature. The reaction was successfully applied to a short protecting group-free total synthesis of radulanin A, a natural 2,5-dihydrobenzoxepine. Moreover, the strong herbicidal potential of this natural product is demonstrated for the first time.     

A brittle material with tunable elasticity: Crêpe paper

We study the mechanical response, and tearing features of crêpe paper, a two-dimensional, very anisotropic material, with one direction much less stiff than the other one. Depending on how the soft direction has been pre-stretched or not, the apparent Young modulus of the material can be varied over a broad range, while its fracture energy remains unaltered. The classical tearing concertina problem shows that a macroscopic measurement (the shape of the teared region) provides a direct access to the fracture properties of the material (effective Young's modulus, and fracture energy). The overall discussion is conducted in the frame of Griffith's theory of fracture.     

Determination of fexofenadine in Hank's balanced salt solution by high‐performance liquid chromatography with ultraviolet detection: application to Caco‐2 cell permeability studies

The drug‐transporting proteins can affect the pharmacokinetics and pharmacodymanics of many drugs, resulting in an erratic and unpredictable pharmacological response. The Caco‐2 monolayer is routinely applied to investigate the carrier‐mediated transport of drugs. Therefore, the selection of a marker compound able to characterize the activity of such transporters is crucial. Fexofenadine (FEX), a P‐gp/OATP substrate, can be considered a suitable probe. However, in order to use be used as a marker compound, it is mandatory to develop an analytical method able to quantify this drug during the in vitro permeability assay. An HPLC method with ultraviolet detection was developed; the mobile phase consisted of phosphate buffer (pH 3.2) containing 10 m m of sodium octanosulphonate and acetonitrile (60:40) and the flow rate was set at 1.2 mL/min. Fexofenadine was eluted at 40°C, the retention time was about 4.6 min. The LOD and LOQ values were 1.9 and 6.2 ng/mL, respectively. Verapamil and ketoconazole, the most common P‐gp inhibitors, were eluted as distinct peaks of that corresponding to fexofenadine The method was successfully applied to quantify the amount of FEX transported across the Caco‐2 monolayer and could be an additional tool for those investigating the role of membrane transporters on drug absorption. Copyright © 2014 John Wiley & Sons, Ltd.     

CoI-Catalyzed Barbier Reactions of Aromatic Halides with Aromatic Aldehydes and Imines

The reductive Barbier coupling of aromatic halides and electrophiles has been achieved using a CoBr₂/1,10-phenanthroline catalytic system and over stoichiometric amounts of zinc. The reaction displayed a broad scope of substrates, including (hetero)aryl chlorides as pro-nucleophiles and aldehydes or imines as electrophiles, leading to diarylmethanols and diarylmethylamines in moderate to excellent yields, respectively.     

Potent Anticancer Efficacy of First-In-Class CuII and AuIII Metaled Phosphorus Dendrons with Distinct Cell Death Pathways

First-in-class Cu^II and Au^III metaled phosphorus dendrons were synthesized and showed significant antiproliferative activity against several aggressive breast cancer cell lines. The data suggest that the cytotoxicity increases with reducing length of the alkyl chains, whereas the replacement of Cu^II with Au^III considerably increases the antiproliferative activity of metaled phosphorus dendrons. Very interestingly, we found that the cell death pathway is related to the nature of the metal complexed by the plain dendrons. Cu^II metaled dendrons showed a potent caspase-independent cell death pathway, whereas Au^III metaled dendrons displayed a caspase-dependent apoptotic pathway. The complexation of plain dendrons with Au^III increased the cellular lethality versus dendrons with Cu^II and promoted the translocation of Bax into the mitochondria and the release of Cytochrome C (Cyto C).     

A new class of conformable spectral observers for signal reconstruction

In this work, the design of spectral observers for signal reconstruction based on Kalman filters is performed and evaluated. The conformable derivative and the beta‐derivative were used to design the Kalman filters. Both derivatives satisfy the same formulas of the classical derivation, eg, the chain rule. The derivative order, the Ricatti equation parameters, and the observers tuning parameters were optimized using an optimization algorithm based on the bat's echolocation behavior (Bat algorithm). The simulation results showed the advantages of using the proposed observers for the signal reconstruction.