Nano palladium supported on high‐surface‐area metal–organic framework MIL‐101: an efficient catalyst for Sonogashira coupling of aryl and heteroaryl bromides with alkynes

Palladium nanoparticle‐incorporated metal–organic framework MIL‐101 (Pd/MIL‐101) was successfully synthesized and characterized using X‐ray diffraction, nitrogen physisorption, X‐ray photoelectron, UV–visible and infrared spectroscopies, and transmission electron microscopy. The characterization techniques confirmed high porosity and high surface area of MIL‐101 and high stability of nano‐size palladium particles. Pd/MIL‐101 nanocomposite was investigated for the Sonogashira cross‐coupling reaction of aryl and heteroaryl bromides with various alkynes under copper‐free conditions. The reusability of the catalyst was tested for up to four cycles without any significant loss in catalytic activity. Copyright © 2015 John Wiley & Sons, Ltd.     

Full counting statistics of transport electrons through a two-level quantum dot with spin–orbit coupling

We study the full counting statistics of transport electrons through a semiconductor two-level quantum dot with Rashba spin–orbit (SO) coupling, which acts as a nonabelian gauge field and thus induces the electron transition between two levels along with the spin flip. By means of the quantum master equation approach, shot noise and skewness are obtained at finite temperature with two-body Coulomb interaction. We particularly demonstrate the crucial effect of SO coupling on the super-Poissonian fluctuation of transport electrons, in terms of which the SO coupling can be probed by the zero-frequency cumulants. While the charge currents are not sensitive to the SO coupling.     

Synthesis of Highly Substituted γ‐Butyrolactones by a Gold‐Catalyzed Cascade Reaction of Benzyl Esters

Easily accessible benzylic esters of 3‐butynoic acids in a gold‐catalyzed cyclization/rearrangement cascade reaction provided 3‐propargyl γ‐butyrolactones with the alkene and the carbonyl group not being conjugated. Crossover experiments showed that the formation of the new C?C bond is an intermolecular process. Initially propargylic–benzylic esters were used, but alkyl‐substituted benzylic esters worked equally well. In the case of the propargylic–benzylic products, a simple treatment of the products with aluminum oxide initiated a twofold tautomerization to the allenyl‐substituted γ‐butyrolactones with conjugation of the carbonyl group, the olefin, and the allene. The synthetic sequence can be conducted stepwise or as a one‐pot cascade reaction with similar yields. Even in the presence of the gold catalyst the new allene remains intact.     

New Effects in the Poly-N-Vinylcaprolactam/Titanium(IV) Oxides Nanocomposite System and Their Nature

Nanocomposites based on poly-N-vinylcaprolactam (PVC), characterized by different drying temperatures of aqueous PVC solution at 25°С (PVC25) and 40°С (PVC40), with titanium(IV) oxide nanoparticles (TONs) (η-phase (TP: TiO_{2 – x} · mH₂O) with a superstructure to the anatase structure and ordered solid solution with partial replacement of oxygen atoms in the η-phase with peroxo group O ₂ ^2– (PP: TiO _x (O₂)_{2 – x} · nH₂O)) have been obtained for the first time and characterized by X-ray diffraction and IR spectroscopy. It is found that a common feature of TP/PVC and PP/PVC obtained by dry mixing and grinding is the decrease in the number of water molecules for TP and PP in the interlayer space of the structure and their attachment to the PVC amide groups; the differences are related to the specificity of PVC behavior in these systems: mechanodestruction of PVC in PP/PVC40 and different numbers of water molecules in PVC25 and PVC40.