Sterically Hindered o‐Quinone Annulated with Dithiete: A Molecule Comprising Diolate and Dithiolate Coordination Sites

A new stable sterically hindered o‐quinone annelated with a 1,2‐dithiete ring was prepared by using mild conditions. The skeleton of the compound comprises diolate and dithiolate functions that have the potential to bind metals leading to the corresponding complexes. The reactivity of this compound as a ligand with respect to both coordination sites was studied. Reactions with metals indicate that the o‐quinone function is reduced in the first stage to give semiquinonate and catecholate complexes. The dithiolate coordination site was involved in the reaction in a few cases only after diolate was bound. A trinuclear manganese complex with coordination on both sites was obtained and characterized by EPR spectroscopy. The electrochemical study of this quinone fused with dithiete is reported.     

A model of imperfect interface with damage

In this paper two models of damaged materials are presented. The first one describes a structure composed by two adherents and an adhesive which is micro-cracked and subject to two different regimes, one in traction and one in compression. The second model is a model of interface derived from the first one through an asymptotic analysis, and it can be interpreted as a model for contact with adhesion and unilateral constraint. Simple numerical examples are presented.     

Combined use of three forms of chiroptical spectroscopies in the study of the absolute configuration and conformational properties of 3-phenylcyclopentanone, 3-phenylcyclohexanone,and 3-phenylcycloheptanone

Three forms of chiroptical spectroscopies, electronic circular dichroism (ECD), vibrational circular dichroism (VCD), and optical rotatory dispersion (ORD) have been employed to study the configuration and conformational properties of the three molecules: (S)-3-phenylcyclopentanone, (S)-3-phenylcyclohexanone, and (S)-3-phenylcycloheptanone (including (S)-3-phenylcyclopentanone-2,2,5,5-d₄ and (S)-3-phenylcyclohexanone-2,2,6,6-d₄). ECD and VCD spectra in the mid-IR for the three molecular systems are marginally dependent on fine conformational details, as interpreted in terms of standard DFT computational methods, with common spectroscopic features to the three systems clearly identified. Accounting for vibronic coupling mechanisms reproduces the structuring of ECD n→π^∗ band. The ORD curves are quite similar for the three types of molecules, but their interpretation highlights a crucial role played by conformations of the cycloalkanone ring in the case of (S)-3-phenylcycloheptanone. The same conclusions are reached by considering the VCD spectra in the CH-stretching region.     

Superelectrophilic activation of N-aryl amides of 3-arylpropynoic acids: synthesis of quinolin-2(1H)-one derivatives

The superelectrophilic activation of N-aryl amides of 3-arylpropynoic acids by Bronsted superacids (CF₃SO₃H, HSO₃F) or strong Lewis acids AlX₃ (X=Cl, Br) results in the formation of 4-aryl quinolin-2(1H)-ones in quantitative yields. The vinyl triflates or vinyl chlorides may be formed as additional reaction products. The investigated amides in reactions with benzene give 4,4-diaryl 3,4-dihydroquinolin-2-(1H)-ones under the superelectrophilic activation. 4-Aryl quinolin-2(1H)-ones in POCl₃ are converted into 4-aryl 2-chloroquinolines. 4-Fluorophenyl-4-phenyl 3,4-dihydroquinolin-2-(1H)-one give N-formylation products in a yield of 79% under the Vilsmeier–Haack reaction conditions.     

A projection approach to optimal control of elastic beam dynamics

Controlled lateral motions of an elastic beam – extended body with a cuboid shape – are studied. A generalized statement of the initial-boundary value problem is given in the frame of 3D linear elasticity based on the integral formulation of constitutive relations. A numerical approach relying on the Fourier method and semi-discretization technique is proposed to design the optimal boundary control that moves the beam to a given final state and minimizes a quadratic cost function. Some results of numerical simulation and quality analysis are presented and discussed. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure,Electrochemical Properties,and Antiradical Activity

A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh₃, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph₃SbBr₂ in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 1–3 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical.     

Slit Holomorphic Stochastic Flows and Gaussian Free Field

It was realized recently that the chordal, radial and dipolar Schramm–Löwner evolution (SLEs) are special cases of a general slit holomorphic stochastic flow. We characterize those slit holomorphic stochastic flows which generate level lines of the Gaussian free field. In particular, we describe the modifications of the Gaussian free field (GFF) corresponding to the chordal and dipolar SLE with drifts. Finally, we develop a version of conformal field theory based on the background charge and Dirichlet boundary condition modifications of GFF and present martingale-observables for these types of SLEs.     

Application of Fast Grey RA to the spectrophotometric determination of copper in liver of Egyptian camels

The ortho-orthohydroxyazo dye 15690-Solochromate Fast Grey RA, CI mordant Black 19 (reddish navy-blue black) has been used as a reagent for the spectrophotometric determination of copper in liver of Egyptian camels. To determine copper digest, 1-g dry liver samples with 5 ml of each of 50% v/v sulfuric and concentrated nitric followed by 3 ml hydrogen peroxide, get rid of excess acid by repeated evaporation and washing, transfer quantitatively to 100 ml flask, make with water up to volume, to 1 ml add 2 ml 0.05 N nitric, 2 ml 0.2 M ascorbic acid, 3 ml 0.005% FG make up with water to 10 ml. Measure extinction at 555 mμ. Such a procedure gave satisfactory results as compared to the DEDTC procedure and a recovery of 98.8%.     

A General Variational Criterion for Chemically Active Continuous Media

A variational criterion describing the nonstationary flow of a mixture of chemically active compressible fluid components is presented. The problem considered constitutes a generalization of previous works [1, 2] of the authors. It is shown that the Euler-Lagrange equations corresponding to arbitrary variations of the chemical potentials, the velocity components, and the temperature are identical to the laws of conservation of mass of each component, of momentum, and of entropy, respectively.