Geometry-selective synthesis of E or Z N-vinyl ureas (N-carbamoyl enamines)

N-Vinyl ureas are emerging as a valuable class of compounds with both nucleophilic and electrophilic reactivity. They may be made by capturing the enamine tautomer of an imine with an isocyanate, a reaction which in general leads to the E isomer of the vinyl urea. Deprotonation of such a vinyl urea, or of an allyl urea, generates a dipole stabilized Z-allyl anion which may be protonated to return the Z-vinyl urea. Isomerization of an allyl urea with a Ru complex provides an alternative route to E-vinyl ureas.     

Panchromatic trichromophoric sensitizer for dye-sensitized solar cells using antenna effect

The first trichromophoric sensitizer, consisting of covalently linked boradiazaindacene (BODIPY), zinc porphyrin (ZnP), and squaraine (SQ) units, has been synthesized by Heck alkynylation to obtain a panchromatic dye, for dye sensitized solar cells (DSSCs). Efficient intramolecular energy transfers (ET) were observed between all chromophoric subunits and enhance the overall conversion efficiency by 25%. The antenna effect is demonstrated by the photoaction spectrum which features all of a chromophore's absorption bands.     

Elimination versus ring opening: a convergent route to alkylidene-cyclobutanes

Functionalized alkylidene-cyclobutanes have been prepared from 2-fluoropyridinyl-6-oxy precursors derived from vinyl cyclobutanols by a radical addition-elimination process. A wide range of functional groups is tolerated, and the alkylidene-cyclobutanes can be further elaborated into cyclopentanones. The limitation of this approach resides in the competition with opening of the cyclobutane ring.     

Quantification of glucuronidated and sulfated steroids in human urine by ultra-high pressure liquid chromatography quadrupole time-of-flight mass spectrometry

The urinary steroid profile is constituted by anabolic androgenic steroids, including testosterone and its relatives, that are extensively metabolized into phase II sulfated or glucuronidated steroids. The use of liquid chromatography coupled to mass spectrometry (LC-MS) is an issue for the direct analysis of conjugated steroids, which can be used as urinary markers of exogenous steroid administration in doping analysis, without hydrolysis of the conjugated moiety. In this study, a sensitive and selective ultra high-pressure liquid chromatography coupled to quadrupole time-of-flight mass spectrometer (UHPLC-QTOF-MS) method was developed to quantify major urinary metabolites simultaneously after testosterone intake. The sample preparation of the urine (1 mL) was performed by solid-phase extraction on Oasis HLB sorbent using a 96-well plate format. The conjugated steroids were analyzed by UHPLC-QTOF-MS^E with a single-gradient elution of 36 min (including re-equilibration time) in the negative electrospray ionization mode. MS^E analysis involved parallel alternating acquisitions of both low- and high-collision energy functions. The method was validated and applied to samples collected from a clinical study performed with a group of healthy human volunteers who had taken testosterone, which were compared with samples from a placebo group. Quantitative results were also compared to GC-MS and LC-MS/MS measurements, and the correlations between data were found appropriate. The acquisition of full mass spectra over the entire mass range with QTOF mass analyzers gives promise of the opportunity to extend the steroid profile to a higher number of conjugated steroids.     

A semi-analytical model for the behavior of saturated viscoplastic materials containing two populations of voids of different sizes

This paper presents a micromechanical model for a porous viscoplastic material containing two populations of pressurized voids of different sizes. Three scales are distinguished: the microscopic scale (corresponding to the size of the small voids), the mesoscopic scale (corresponding to the size of the large voids) and the macroscopic scale. It is assumed that the first homogenization step is performed at the microscopic scale, and, at the mesoscopic scale, the matrix is taken to be homogeneous and compressible. At the mesoscopic scale, the second homogenization step, on which the present study focuses, is based on a simplified representative volume element: a hollow sphere containing a pressurized void surrounded by a nonlinear viscoplastic compressible matrix. The nonlinear behavior of the matrix, which is expressed using the results obtained in the first homogenization step, is approached using a modified secant linearization procedure involving the discretization of the hollow sphere into concentric layers. Each layer has uniform secant moduli. The predictions of the model are compared with the more accurate numerical results obtained using the finite element method. Good agreement is found to exist with all the macroscopic stress triaxialities and all the porosity and nonlinearity values studied.     

A localized Jarník–Besicovitch theorem

Fundamental questions in Diophantine approximation are related to the Hausdorff dimension of sets of the form {x∈R:δx=δ}, where δ?1 and δx is the Diophantine approximation exponent of an irrational number x. We go beyond the classical results by computing the Hausdorff dimension of the sets {x∈R:δx=f(x)}, where f is a continuous function. Our theorem applies to the study of the approximation exponents by various approximation families. It also applies to functions f which are continuous outside a set of prescribed Hausdorff dimension.     

The Kauffman skein algebra of a surface at $${\sqrt{-1}}$$

We study the structure of the Kauffman algebra of a surface with parameter equal to \({\sqrt{-1}}\). We obtain an interpretation of this algebra as an algebra of parallel transport operators acting on sections of a line bundle over the moduli space of flat SU(2)-connections over the surface. We analyse the asymptotics of traces of curve-operators in TQFT in non standard regimes where the root of unity parametrizing the TQFT accumulates to a root of unity. We interpret the case of \({\sqrt{-1}}\) in terms of parallel transport operators.     

New insights in quantum chemical topology studies using numerical grid-based analyses

New insights in Quantum Chemical Topology of one-electron density functions have been proposed here by using a recent grid-based algorithm (Tang et al., J Phys Condens Matter 2009, 21, 084204), initially designed for the decomposition of the electron density. Beyond the charge analysis, we show that this algorithm is suitable for different scalar functions showing a more complex topology, that is, the Laplacian of the electron density, the electron localization function (ELF), and the molecular electrostatic potential (MEP). This algorithm makes use of a robust methodology enabling to numerically assign the data points of three-dimensional grids to basin volumes, and it has the advantage of requiring only the values of the scalar function without details on the wave function used to build the grid. Our implementation is briefly outlined (program named TopChem), its capabilities are examined, and technical aspects in terms of CPU requirement and accuracy of the results are discussed. Illustrative examples for individual molecules and crystalline solids obtained with gaussian and plane-wave-based density functional theory calculations are presented. Special attention was given to the MEP because its topological analysis is complex and scarce.     

Double-hybrid density-functional theory made rigorous

We provide a rigorous derivation of a class of double-hybrid approximations, combining Hartree-Fock exchange and second-order M?ller-Plesset correlation with a semilocal exchange-correlation density functional. These double-hybrid approximations contain only one empirical parameter and use a density-scaled correlation energy functional. Neglecting density scaling leads to a one-parameter version of the standard double-hybrid approximations. We assess the performance of these double-hybrid schemes on representative test sets of atomization energies and reaction barrier heights, and we compare to other hybrid approximations, including range-separated hybrids. Our best one-parameter double-hybrid approximation, called 1DH-BLYP, roughly reproduces the two parameters of the standard B2-PLYP or B2GP-PLYP double-hybrid approximations, which shows that these methods are not only empirically close to an optimum for general chemical applications but are also theoretically supported.