Oxone® Promoted Nef Reaction. Simple Conversion of Nitro Group Into Carbonyl

A mild and convenient oxidative Nef reaction using Oxone^® (potassium hydrogen persulfate) is described. Following our procedure primary and secondary nitroalkanes generate carboxylic acids and ketones, respectively, both in good yields.

     

Synthesis of New Macrocyclic Aryl Phosphonates. X-Ray Structure and Clathration Properties

Williamson condensation of bis-o-hydroxy aryl phosphonates with dihaloalkylaryl derivatives yields the title compounds. They show interesting stereochemical aspects and some of them can be used in chiral recognitions and separations.     

Study of Ground State Interactions of Enantiopure Chiral Quaternary Ammonium Salts and Amides,Nitroalkanes, Nitroalkenes,Esters, Heterocycles,Ketones and Fluoroamides

Chiral phase-transfer catalysis provides high level of enantiocontrol, however no experimental data showed the interaction of catalysts and substrates. ¹H NMR titration was carried out on Cinchona and Maruoka ammonium bromides vs. nitro, carbonyl, heterocycles, and N−F containing compounds. It was found that neutral organic species and quaternary ammonium salts interacted via an ensemble of catalyst ⁺N−C−H and (sp²)C−H, specific for each substrate studied. The correspondent BArF salts interacted with carbonyls via a diverse set of ⁺N−C−H and (sp²)C−H compared to bromides. This data suggests that BArF ammonium salts may display a different enantioselectivity profile. Although not providing quantitative data for the affinity constants, the data reported proofs that chiral ammonium salts coordinate with substrates, prior to transition state, through specific C−H positions in their structures, providing a new rational to rationalize the origin of enantioselectivity in their catalyses.     

The Chemistry of Nucleation: In Situ Pair Distribution Function Analysis of Secondary Building Units During UiO-66 MOF Formation

The concept of secondary building units (SBUs) is central to all science on metal-organic frameworks (MOFs), and they are widely used to design new MOF materials. However, the presence of SBUs during MOF formation remains controversial, and the formation mechanism of MOFs remains unclear, due to limited information about the evolution of prenucleation cluster structures. Here in situ pair distribution function (PDF) analysis was used to probe UiO-66 formation under solvothermal conditions. The expected SBU—a hexanuclear zirconium cluster—is present in the metal salt precursor solution. Addition of organic ligands results in a disordered structure with correlations up to 23 Å, resembling crystalline UiO-66. Heating leads to fast cluster aggregation, and further growth and ordering results in the crystalline product. Thus, SBUs are present already at room temperature and act as building blocks for MOF formation. The proposed formation steps provide insight for further development of MOF synthesis.     

Measuring bank contagion in Europe using binary spatial regression models

The recent European sovereign debt crisis clearly illustrates the importance of measuring the contagion effects of bank failures. Indeed, to better understand and monitor contagion risk, the European Central Bank has assumed the supervision of the largest banks in each of the member states. We propose a measure of contagion risk based on the spatial autocorrelation parameter of a binary spatial autoregressive model. Using different specifications of the interbank connectivity matrix, we estimate the contagion parameter for banks within the Eurozone, between 1996 and 2012. We provide evidence of high levels of systemic risk due to contagion during the European sovereign debt crisis.     

Bile enterogastric reflux sensor using plastic optical fibers

Abstract

A portable optical-fiber sensor for ambulatory assessment of the enterogastric reflux, based on the optical properties of the bile, was developed. It makes use of two light-emitting diodes and of an appropriate electronic circuit that processes the signals and provides the readout on a display. A suitable probe for in vivo measurements was designed. Plastic fiber bundles are used in order to obtain probe flexibility and low price. In vivo measurements performed on different patients show the superiority of this technique over existing methods.