X-ray crystallographic structure of the 9,10-dihydro-11,12bis[(1,3,3-trimethylureido)methyl]-9,10ethanoanthracene dihydrate

As a part of studies on MDR reversal agents, structure of the 9,10-dihydro-11,12-bis[(1,3,3-trimethylureido)methyl]-9,10-ethanoanthracene dihydrate is reported. Crystal data: C₂₆H₃₄N₄O₂ × 2 H₂O; mol. mass 470.60; monoclinic; space group: C2/c, a = 15.7492(6) Å; b = 7.2245(3) Å; c = 24.3442(10) Å; β = 106.795(2)^∘; V = 2651.73(22) ų; z = 4; dx = 1.179 mg/m³; μ = 0.64 mm⁻¹; F(000) = 1016; final R = 0.061 for 2501 reflections [I > 4 σ (I)]. Only half of the molecule is unique. The two nonplanar rings from the independent part of 9,10-dihydro-9,10-ethanoanthracene adopt a boat conformation. Crystallographic data demonstrate the “syn-syn” conformation of urea substituents in the molecule. In the crystal, water molecules are linked to the main species by H-bonds: O3′⋅sH12w—O1—H11w⋅sO3′(1.5 − x, 0.5 − y, 1 − z).     

Chelate-Controlled Asymmetric Synthesis of 2-Substituted 2,3-Dihydropyridin-4(1H)-ones: Synthesis of D- and L-aminodeoxyaltrose derivatives

Asymmetric methylation and phenylation of the chiral pyridinium salt 7 , as well as methylation of chiral pyridinium salt 18 , with Grignard reagents occurred in good yield and with good-to-excellent diastereoselectivities (Schemes 2 and 3, resp.). These results are best explained by assuming chelate control to govern the asymmetric alkylation/arylation process. The minimum-energy conformations of the out-of-plane twisted pyridinium salts 7 and 18 , as determined by the ‘Molecular Simulations Cerius-Dreiding II’ program, are in good agreement with the postulated asymmetric chelate-control mechanism.     

Geometries with dual affine planes and symplectic quadrics

Farmer and Hale [3] prove that every copolar space fully embedded in a finite projective space PG(n, q), with q>, is the copolar space arising from a symplectic polarity. We show that this result is still valid in arbitrary projective spaces; this provides a different and shorter proof of [3] in the finite case.     

Size-fractionated characterization and quantification of nanoparticle release rates from a consumer spray product containing engineered nanoparticles

This study describes methods developed for reliable quantification of size- and element-specific release of engineered nanoparticles (ENP) from consumer spray products. A modified glove box setup was designed to allow controlled spray experiments in a particle-minimized environment. Time dependence of the particle size distribution in a size range of 10–500 nm and ENP release rates were studied using a scanning mobility particle sizer (SMPS). In parallel, the aerosol was transferred to a size-calibrated electrostatic TEM sampler. The deposited particles were investigated using electron microscopy techniques in combination with image processing software. This approach enables the chemical and morphological characterization as well as quantification of released nanoparticles from a spray product. The differentiation of solid ENP from the released nano-sized droplets was achieved by applying a thermo-desorbing unit. After optimization, the setup was applied to investigate different spray situations using both pump and gas propellant spray dispensers for a commercially available water-based nano-silver spray. The pump spray situation showed no measurable nanoparticle release, whereas in the case of the gas spray, a significant release was observed. From the results it can be assumed that the homogeneously distributed ENP from the original dispersion grow in size and change morphology during and after the spray process but still exist as nanometer particles of size <100 nm. Furthermore, it seems that the release of ENP correlates with the generated aerosol droplet size distribution produced by the spray vessel type used. This is the first study presenting results concerning the release of ENP from spray products.     

Electronic spectra of uranyl chloride complexes in acetone: a CASSCF/CASPT2 investigation

A theoretical study is presented of the electronic spectra of the complexes UO(2)Cl(2)ac(4), UO(2)Cl(2)ac(3), [UO(2)Cl(3)ac(2)](-) and [UO(2)Cl(3)ac](-) (ac = acetone) using perturbation theory based on a complete-active-space type wavefunction (CASSCF/CASPT2). Both scalar relativistic effects and spin-orbit coupling were included in the calculations. The calculated excitation energies and oscillator strength values have been compared to the experimental absorption spectrum for uranyl chloride complexes in acetone solution, for chloride-to-uranyl ratios between two and three. The main purpose of this work was to investigate the origin of the remarkable intensity increase observed in the lower part of the experimental absorption spectra, upon addition of chloride to uranyl complexes in acetone. The calculated excitation energies for the different complexes are similar and closely correspond to the experimental data. However, in none of the theoretical spectra, the high intensities observed in the lower part of the experimental spectrum are reproduced.     

Universal additive effect of temperature on the rheology of amorphous solids

Extensive measurements of macroscopic stress in a 2D Lennard-Jones glass, over a broad range of temperatures (T) and strain rates (γ), demonstrate a very significant decrease of the flowing stress with T, even much below the glass transition. A detailed analysis of the interplay between loading, thermal activation, and mechanical noise leads us to propose that over a broad (γ, T) region, the effect of temperature amounts to a mere lowering of the strains at which plastic events occur, while the athermal avalanche dynamics remains essentially unperturbed. Up to the vicinity of the glass transition, temperature is then shown to correct the athermal stress by a (negative) additive contribution which presents a universal form, thus bringing support to and extending an expression proposed by Johnson and Samwer [Phys. Rev. Lett. 95, 195501 (2005)].     

Bifurcation analysis of a generalized Gause model with prey harvesting and a generalized Holling response function of type III

In this paper we study a generalized Gause model with prey harvesting and a generalized Holling response function of type III: . The goal of our study is to give the bifurcation diagram of the model. For this we need to study saddle-node bifurcations, Hopf bifurcation of codimension 1 and 2, heteroclinic bifurcation, and nilpotent saddle bifurcation of codimension 2 and 3. The nilpotent saddle of codimension 3 is the organizing center for the bifurcation diagram. The Hopf bifurcation is studied by means of a generalized Liénard system, and for b=0 we discuss the potential integrability of the system. The nilpotent point of multiplicity 3 occurs with an invariant line and can have a codimension up to 4. But because it occurs with an invariant line, the effective highest codimension is 3. We develop normal forms (in which the invariant line is preserved) for studying of the nilpotent saddle bifurcation. For b=0, the reversibility of the nilpotent saddle is discussed. We study the type of the heteroclinic loop and its cyclicity. The phase portraits of the bifurcations diagram (partially conjectured via the results obtained) allow us to give a biological interpretation of the behavior of the two species.     

Synthesis of functionalized diarylmethanes via a copper-catalyzed cross-coupling of arylmagnesium reagents with benzylic phosphates

A combination of copper chloride, triethyl phosphite, and tetrabutylammonium iodide is a very efficient catalytic system for the synthesis of polyfunctionalized diarylmethanes, using the cross-coupling reaction of arylmagnesium halides with benzylic phosphates. The antibiotic Trimethoprim has been prepared using this Cu(I)-catalyzed cross-coupling in 52% overall yield (four steps).