Catalytic Hydroetherification of Unactivated Alkenes Enabled by Proton-Coupled Electron Transfer

We report a catalytic, light-driven method for the intramolecular hydroetherification of unactivated alkenols to furnish cyclic ether products. These reactions occur under visible-light irradiation in the presence of an Ir^III-based photoredox catalyst, a Brønsted base catalyst, and a hydrogen-atom transfer (HAT) co-catalyst. Reactive alkoxy radicals are proposed as key intermediates, generated by direct homolytic activation of alcohol O−H bonds through a proton-coupled electron-transfer mechanism. This method exhibits a broad substrate scope and high functional-group tolerance, and it accommodates a diverse range of alkene substitution patterns. Results demonstrating the extension of this catalytic system to carboetherification reactions are also presented.     

Continuous‐Flow Microwave Synthesis of Metal–Organic Frameworks: A Highly Efficient Method for Large‐Scale Production

Metal–organic frameworks are having a tremendous impact on novel strategic applications, with prospective employment in industrially relevant processes. The development of such processes is strictly dependent on the ability to generate materials with high yield efficiency and production rate. We report a versatile and highly efficient method for synthesis of metal–organic frameworks in large quantities using continuous flow processing under microwave irradiation. Benchmark materials such as UiO‐66, MIL‐53(Al), and HKUST‐1 were obtained with remarkable mass, space–time yields, and often using stoichiometric amounts of reactants. In the case of UiO‐66 and MIL‐53(Al), we attained unprecedented space–time yields far greater than those reported previously. All of the syntheses were successfully extended to multi‐gram high quality products in a matter of minutes, proving the effectiveness of continuous flow microwave technology for the large scale production of metal–organic frameworks.     

Local Semicircle Law for Random Regular Graphs

We consider random d‐regular graphs on N vertices, with degree d at least (log N)⁴. We prove that the Green's function of the adjacency matrix and the Stieltjes transform of its empirical spectral measure are well approximated by Wigner's semicircle law, down to the optimal scale given by the typical eigenvalue spacing (up to a logarithmic correction). Aside from well‐known consequences for the local eigenvalue distribution, this result implies the complete (isotropic) delocalization of all eigenvectors and a probabilistic version of quantum unique ergodicity.© 2017 Wiley Periodicals, Inc.     

A Comprehensive Study on the Full Series of Alkali-Metal Selenocyanates AI[SeCN] (AI=Li−Cs)

The full series of quasibinary alkali-metal selenocyanates was synthesized either by oxidation of the respective cyanides (A=Li−Rb) or by metathesis (A=Cs). For Li[SeCN] only ball-milling and subsequent annealing led to the isolation of the quasibinary selenocyanate. Their structures were refined from single-crystal and powder X-ray data. The respective solid-state IR and Raman spectra were interpreted with the aid of solid-state quantum-mechanical calculations and DSC-TGA measurements allowed for extraction of melting points. Only for Li[SeCN] a possible phase transition was observed that is discussed on the basis of VT-PXRD experiments. It is also the only quasibinary selenocyanate to form a hydrate (Li[SeCN] ⋅ 2H₂O).     

Hydrophobic modification of nanocellulose and all-cellulose composite films using deep eutectic solvent as a reaction medium

Cellulose - In this work, deep eutectic solvent (DES) based on imidazole and triethylmethylammonium chloride was used as a reaction medium for the esterification of cellulose nanofiber (CNF) and...     

Sudden tensile loading of a rubberlike bar

In uniaxial tension, the stress–strain curve for rubber changes curvature from concave to convex as the strain increases. For sudden tensile loading of a bar, a one-dimensional model that reflects this behavior leads to an under-determined problem reminiscent of that arising in materials capable of undergoing phase transitions. In the latter setting, adding the kinetic relation underlying the phase change to the conventional statement of the problem removes the indeterminacy; the same is true when such a relation is used in a formal way in the problem for rubber. This presents a physical question: What is the evolutionary process at the microscale whose kinetics are needed in the dynamics of rubber?     

On Saint-Venant's principle in the two-dimensional linear theory of elasticity

Archive for Rational Mechanics and Analysis -