On confined McKean Langevin processes satisfying the mean no-permeability boundary condition

We construct a confined Langevin type process aimed to satisfy a mean no-permeability condition at the boundary. This Langevin process lies in the class of conditional McKean Lagrangian stochastic models studied by Bossy, Jabir and Talay (2010) [5]. The confined process considered here is a first construction of solutions to the class of Lagrangian stochastic equations with boundary condition issued by the so-called PDF methods for Computational Fluid Dynamics. We prove the well-posedness of the confined system when the state space of the Langevin process is a half-space.     

Two-dimensional curved fronts in a periodic shear flow

This paper is devoted to the study of traveling fronts of reaction-diffusion equations with periodic advection in the whole plane R². We are interested in curved fronts satisfying some “conical” conditions at infinity. We prove that there is a minimal speed c^∗ such that curved fronts with speed c exist if and only if c≥c^∗. Moreover, we show that such curved fronts are decreasing in the direction of propagation, that is, they are increasing in time. We also give some results about the asymptotic behaviors of the speed with respect to the advection, diffusion and reaction coefficients.     

On constructing total orders and solving vector optimization problems with total orders

In this paper, we introduce a construction method of total ordering cone on \mathbbRⁿ{\mathbb{R}^n} . It is shown that any total ordering cone on \mathbbRⁿ{\mathbb{R}^n} is isomorphic to the cone \mathbbRⁿ_lex{\mathbb{R}^n_{lex}} . Existence of a total ordering cone that contain given cone with a compact base is shown. By using this cone, a solving method of vector and set valued optimization problems is presented.     

Synthesis, structure, and properties of a T-shaped 14-electron stiboranyl-gold complex

A cyclic stiboranyl-gold complex (1) supported by two 1,8-naphthalenediyl linkers has been synthesized and structurally characterized. The gold atom of this complex adopts a T-shaped geometry and is separated from the antimony center by only 2.76 ?. Surprisingly, the trivalent gold atom of this complex is involved in an aurophilic interaction, a phenomenon typically only observed for monovalent gold complexes. This phenomenon indicates that the stiboranyl ligand possesses strong σ-donating properties making the trivalent gold atom of 1 electron rich. This view is supported by DFT calculations as well as Au L(3)- and Sb K-edge XANES spectra which reveal that 1 may also be described as an aurate-stibonium derivative. In agreement with this view, complex 1 shows no reactivity toward the halides Cl(-), Br(-), and I(-). It does, however, rapidly react with F(-) to form an unprecedented anionic aurate fluorostiborane complex ([2](-)) which has been isolated as the tetra-n-butylammonium salt. The increased coordination number of the antimony center in this anionic complex ([2](-)) does not notably affect the Au-Sb separation (2.77 ?) or the geometry at the gold atom which remains T-shaped.     

Copper‐Catalyzed Bis(methoxycarbonyl)carbene Reactions of α,β‐Unsaturated Carboxamides

The [Cu(acac)₂]‐catalyzed reactions of α,β‐unsaturated carboxamides with dimethyl diazomalonate yielded dihydrofuran derivatives by a 1,5‐electrocyclic reaction at C(β), and butadiene derivatives by carbene addition reaction at C(α) (Schemes 4 and 5; Table). Phenyl substituents at the N‐atom of the amides seem to be effective on the reaction pathways (Table).     

Separation and characterization of gold nanoparticle mixtures by flow-field-flow fractionation

We show that using asymmetric flow-field-flow fractionation and UV-vis detector it is possible to separate, characterize, and quantify the correct number size distribution of gold nanoparticle (AuNP) mixtures of various sizes in the 5-60 nm range for which simple dynamic light scattering measurements give misleading information. The size of the collected nanoparticles fractions can be determined both in solution and in the solid state, and their surface chemistry characterized by NMR. This method will find widespread applications both in the process of "size purification" after the synthesis of AuNP and in the identification and characterization of gold-based nanomaterials in consumer products.     

Bio-dissolution of colloidal-size clay minerals entrapped in microporous silica gels

Four colloidal-size fractions of strongly anisotropic particles of nontronite (NAu-2) having different ratios of basal to edge surfaces were incubated in the presence of heterotrophic soil bacteria to evaluate how changes in mineral surface reactivity influence microbial dissolution rate of minerals. To avoid any particle aggregation, which could change the reactive surface area available for dissolution, NAu-2 particles were immobilized in a biocompatible TEOS-derived silica matrix. The resulting hybrid silica gels support bacterial growth with NAu-2 as the sole source of Fe and Mg. Upon incubation of the hybrid material with bacteria, between 0.3% and 7.5% of the total Fe included in the mineral lattice was released with a concomitant pH decrease. For a given pH value, the amount of released Fe varied between strains and was two to twelve-fold higher than under abiotic conditions. This indicates that complexing agents produced by bacteria play an important role in the dissolution process. However, in contrast with proton-promoted NAu-2 dissolution (abiotic incubations) that was negatively correlated with particle size, bacterial-enhanced dissolution was constant for all size fractions used. We conclude that bio-dissolution of nontronite particles under acidic conditions seems to be controlled by bacterial metabolism rather than by the surface reactivity of mineral.     

Comparison of epithelial and fibroblastic cell behavior on nano/micro-topographic PCL membranes produced by crystallinity control

In this study, the relationship between the cellular morphology and the material surface topography was investigated. Poly(ε-caprolactone) (PCL) membranes were prepared in a wide range of surface wettabilities by means of crystallinity-controlled solvent casting process. Membrane surfaces were characterized by atomic force microscope (AFM), scanning electron microscope (SEM), and static/dynamic water contact angle measurements. It was found that solvent evaporation and non-solvent (methanol) addition to the solvent (THF) are the most decisive parameters to change the surface topography. The non-solvent addition and the decrease in solvent evaporation temperature from room temperature to -20 °C caused increased polymeric chain mobility and crystallization time. Such changes in crystallization parameters led to the formation of micro/nano-sized features on the membrane. Cell culture studies indicated that in contrast to Madin Darby kidney (MDBK) epithelial cells, L929 mouse fibroblast preferred rough and porous surfaces.     

Synthesis, magnetic properties, and magnetic structure of a natrochalcite structural variant, KM(II)2D3O2(MoO4)2 (M = Mn, Fe, or Co)

We report the syntheses, crystal structures, and magnetic properties of KMn(2)(H(3)O(2))(MoO(4))(2) (MnH), KMn(2)(D(3)O(2))(MoO(4))(2) (MnD), KFe(2)(H(3)O(2))(MoO(4))(2) (FeH), KFe(2)(D(3)O(2))(MoO(4))(2) (FeD), KCo(2)(H(3)O(2))(MoO(4))(2) (CoH), and KCo(2)(D(3)O(2))(MoO(4))(2) (CoD), and the magnetic structures of MnD and FeD. They belong to the structural variant (space group I2/m) of the mineral natrochalcite NaCu(2)(H(3)O(2))(SO(4))(2) (space group C2/m) where the diagonal within the ac-plane of the latter become one axis of the former. The structure of MnD, obtained from Rietveld refinement of a high-resolution neutron pattern taken at 300 K, consists of chains of edge-sharing octahedra bridged by MoO(4) and D(3)O(2) to form layers, which are connected to K through the oxygen atoms to form the three-dimensional (3D)-network. The X-ray powder diffraction patterns of the other two compounds were found to belong to the same space group with similar parameters. The magnetic susceptibilities of MnH and FeH exhibit long-range ordering of the moments at a Ne?el temperature of 8 and 11 K, respectively, which are accompanied by additional strong Bragg reflections in the neutron diffraction in the ordered state, consistent with antiferromagnetism. Analyses of the neutron data for MnD and FeD reveal the presence of both long- and short-range orderings and commensurate magnetic structures with a propagation vector of (?, 0, ?). The moments are antiferromagnetically ordered within the chains with alternation between chains to generate four nonequivalent nuclear unit cells. For MnD the moments are perpendicular to the chain axis (b-axis) while for FeD they are parallel to the b-axis. The overall total is a fully compensated magnetic structure with zero moment in each case. Surprisingly, for KCo(2)(D(3)O(2))(MoO(4))(2) neither additional peaks nor increase of the nuclear peaks' intensities were observed in the neutron diffraction patterns below the magnetic anomaly at 12 K which was identified to originate from a small quantity of a ferromagnetic compound, Co(2)(OH)(2)MoO(4).     

3,5-Bis(ethynyl)pyridine and 2,6-bis(ethynyl)pyridine spanning two Fe(Cp*)(dppe) units: role of the nitrogen atom on the electronic and magnetic couplings

The role of the nitrogen atom on the electronic and magnetic couplings of the mono-oxidized and bi-oxidized pyridine-containing complex models [2,6-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) and [3,5-{Cp(dpe)Fe-C≡C-}(2)(NC(5)H(3))](n+) is theoretically tackled with the aid of density-functional theory (DFT) and multireference configuration interaction (MR-CI) calculations. Results are analyzed and compared to those obtained for the reference complex [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+). The mono-oxidized species show an interesting behavior at the borderline between spin localization and delocalization and one through-bond communication path among the two involving the central ring, is favored. Investigation of the spin state of the dicationic complexes indicates ferromagnetic coupling, which can differ in magnitude from one complex to the other. Very importantly, electronic and magnetic properties of these species strongly depend not only upon the location of the nitrogen atom in the ring versus that of the organometallic end-groups but also upon the architectural arrangement of one terminus, with respect to the other and/or vis-à-vis the central ring. To help validate the theoretical results, the related families of compounds [1,3-{Cp*(dppe)Fe-C≡C-)}(2)(C(6)H(4))](n+), [2,6-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+), [3,5-{Cp*(dppe)Fe-C≡C-}(2)(NC(5)H(3))](n+) (n = 0-2) were experimentally synthesized and characterized. Electrochemical, spectroscopic (infrared (IR), M?ssbauer), electronic (near-infrared (NIR)), and magnetic properties (electron paramagnetic resonance (EPR), superconducting quantum interference device (SQUID)) are discussed and interpreted in the light of the theoretical data. The set of data obtained allows for many strong conclusions to be drawn. A N atom in the long branch increases the ferromagnetic interaction between the two Fe(III) spin carriers (J > 500 cm(-1)), whereas, when placed in the short branch, it dramatically reduces the magnetic exchange in the di-oxidized species (J = 2.14(5) cm(-1)). In the mixed-valence compounds, when the N atom is positioned on the long branch, the intermediate excited state is higher in energy than the different ground-state conformers and the relaxation process provides exclusively the Fe(II)/Fe(III) localized system (H(ab) ≠ 0). Positioning the N atom on the short branch modifies the energy profile and the diabatic mediating state lies just above the reactant and product diabatic states. Consequently, the LMCT transition becomes less energetic than the MMCT transition. Here, the direct coupling does not occur (H(ab) = 0) and only the coupling through the bridge (c) and the reactant (a) and product (b) diabatic states is operating (H(ac) = H(bc) ≠ 0).