Palladium-catalyzed direct (hetero)arylation of ethyl oxazole-4-carboxylate: an efficient access to (hetero)aryloxazoles

A straightforward route toward 2-(hetero)arylated and 2,5-di(hetero)arylated oxazoles through regiocontrolled palladium-catalyzed direct (hetero)arylation of ethyl oxazole-4-carboxylate with iodo-, bromo-, and chloro(hetero)aromatics followed by a two-step hydrolysis/decarboxylation sequence was described. The method was applied here to a neat synthesis of two 2,5-di(hetero)aryloxazole natural products, balsoxin and texaline.     

Cancellation of Raman pulse walk-off by slow light

We theoretically demonstrate in a nonlinear optical fiber system with a narrowband Raman gain that pulse walk-off between the pump and the Raman Stokes waves can be fully compensated for by Raman slow light, leading to group-velocity matching between the interacting waves, greater useful interaction length, and thereby enhanced Raman amplification efficiency. Limitations due to Kerr effect are further discussed.     

Electron polarizability of crystalline solids in quantizing magnetic fields and topological gap numbers

A theory of the static electron polarizability of crystals whose energy spectrum is modified by quantizing magnetic fields is presented. The polarizability is strongly affected by nondissipative Hall currents induced by the presence of crossed electric and magnetic fields: these can even change its sign. Results are illustrated in detail for a two-dimensional square lattice. The polarizability and the Hall conductivity are, respectively, linked to the two topological quantum numbers entering the so-called Diophantine equation. These numbers could in principle be detected in actual experiments.     

Molecular Determinant of DIDS Analogs Targeting RAD51 Activity

RAD51 is the central protein in DNA repair by homologous recombination (HR), involved in several steps of this process. It is shown that overexpression of the RAD51 protein is correlated with increased survival of cancer cells to cancer treatments. For the past decade, RAD51 overexpression-mediated resistance has justified the development of targeted inhibitors. One of the first molecules described to inhibit RAD51 was the 4,4′-diisothiocyanato-stilbene-2,2′-disulfonic acid (DIDS) molecule. This small molecule is effective in inhibiting different functions of RAD51, however its mode of action and the chemical functions involved in this inhibition have not been identified. In this work, we used several commercial molecules derived from DIDS to characterize the structural determinants involved in modulating the activity of RAD51. By combining biochemical and biophysical approaches, we have shown that DIDS and two analogs were able to inhibit the binding of RAD51 to ssDNA and prevent the formation of D-loop by RAD51. Both isothiocyanate substituents of DIDS appear to be essential in the inhibition of RAD51. These results open the way to the synthesis of new molecules derived from DIDS that should be greater modulators of RAD51 and more efficient for HR inhibition.     

A Fused Hexacyclic Ring System: Diastereoselective Polycyclization of 2,4‐Dienals through an Interrupted iso‐Nazarov Reaction

We report an unprecedented domino polycyclization from readily available 2,4‐dienals and cyclic α,β‐unsaturated imines that is initiated by an iso‐Nazarov reaction. This Brønsted acid promoted reaction enables the concomitant formation of four bonds, three cycles, and four contiguous stereogenic centers to yield elaborated structures in a single operation. A range of fused hexacyclic molecules is obtained in a highly diastereoselective manner.     

Application of a micro/macro‐homogenization procedure to the investigation of the mechanical behavior of ionomer membranes for fuel cells

A microhomogenization/macrohomogenization procedure is proposed to compute the mechanical and swelling behavior of ionomer (Nafion) membranes for fuel cells under external compression loads. The membrane is viewed as a periodic porous media composed of a charged solid phase saturated by an aqueous electrolyte solution. We establish the equation of state in a single membrane pore based on a rigorous treatment of thermodynamic, electrostatic (Poisson–Boltzmann equation) and of mechanical equilibrium. The homogenization technique is then applied to propagate the information available in the pore‐scale model to the macroscale. Numerical experiments are performed to illustrate the results in a cylindrical pore geometry. The results show that the swelling pressure can be approximated by the osmotic pressure, which depends on the charge density at the pore walls and the pore radius. The model predicts the water content of liquid equilibrated membrane under various compression loads and the results are consistent with literature data. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 1496–1509     

General and Practical Formation of Thiocyanates from Thiols

A new method for the cyanation of thiols and disulfides using cyanobenziodoxol(on)e hypervalent iodine reagents is described. Both aliphatic and aromatic thiocyanates can be accessed in good yields in a few minutes at room temperature starting from a broad range of thiols with high chemioselectivity. The complete conversion of disulfides to thiocyanates was also possible. Preliminary computational studies indicated a low energy concerted transition state for the cyanation of the thiolate anion or radical. The developed thiocyanate synthesis has broad potential for various applications in synthetic chemistry, chemical biology and materials science.