Pyrrolothieno[1,4]diazepines: Synthesis of alkoxy derivatives

Reactivity of 2-(2-formyl-1H-pyrrol-1-yl)-3-thiophenecarbonitrile and of 2-(2-formyl-1H-pyrrol-1-yl)-3-thiophenecarboxamide was evaluated against various alkoxides. The synthetic pathways involved in these reactions which led to new 4- and 6-alkoxypyrrolothieno[1,4]diazepines are described.     

Behaviour at the non-positive integers of Dirichlet series associated to polynomials of several variables

In this paper, we relate the special values at a non-positive integer \({\underline{\mathbf{s}}=(s_{1},\ldots, s_{r})= -\underline{\mathbf{N}}= (-N_{1},\ldots, -N_{r})}\) obtained by meromorphic continuation of the multiple Dirichlet series \({{Z(\underline{\mathbf{P}}, \underline{\mathbf{s}})=\sum_{\underline{m}\in {\mathbb{N}}^{*n}}{\frac{1}{\prod_{i=1}^{r}{P_{i}^{ s_{i}}(\underline{m})}}}}}\) to special values of the function \({Y(\underline{\mathbf{P}}, \underline{\mathbf{s}})=\int_{[1, +\infty[^{n}} {\prod_{i=1}^{r}{P_{i}^{- s_{i}}(\underline{\mathbf{x}})}\; d{\underline{\mathbf{x}}}}}\) where \({\underline{\mathbf{P}}=(P_{1},..., P_{r}),\; (r\geq 1)}\) are elliptic polynomials in “\({n}\) ” variables. We prove a simple relation between \({Z(\underline{\mathbf{P}}_{\underline{\mathbf{a}}}, -\underline{\mathbf{N}})}\) and \({Y(\underline{\mathbf{P}}_{\underline{\mathbf{a}}}, -\underline{\mathbf{N}})}\), such that for all \({\underline{\mathbf{a}} \in {\mathbb{R}}^{n}_{+}}\), we denote \({\underline{\mathbf{P}}_{\underline{\mathbf{a}}}:=(P_{1 \underline{\mathbf{a}}},\ldots, P_{r \underline{\mathbf{a}}})}\), where \({P_{i\;\underline{\mathbf{a}}}(\underline{\mathbf{x}}):= P_i(\underline{\mathbf{x}}+ \underline{\mathbf{a}})\; (1\leq i\leq r)}\) is the shifted polynomial.     

A new LQP alternating direction method for solving variational inequality problems with separable structure

We presented a new logarithmic-quadratic proximal alternating direction scheme for the separable constrained convex programming problem. The predictor is obtained by solving series of related systems of non-linear equations in a parallel wise. The new iterate is obtained by searching the optimal step size along a new descent direction. The new direction is obtained by the linear combination of two descent directions. Global convergence of the proposed method is proved under certain assumptions. We show the O(1 / t) convergence rate for the parallel LQP alternating direction method.     

Hinge Distortion in Platinum(II) Dimers with a Pt(2)S(2) Ring. An ab Initio Molecular Orbital Study

Ab initio calculations have been carried out for Pt(II) dimers with S(2)(-) and/or RS(-) bridging ligands in order to elucidate the factors governing the structural preference, planar or hinged, of these complexes. Calculations have been performed for systems which model all structurally characterized Pt(II) binuclear complexes. All possible determinants of the hinge angle have been taken into account in the ab initio calculations. These show that electronic rather than steric effects govern the geometry of the central Pt(2)S(2) ring. Only one minimum of energy has been found for each complex, but the energetic cost of the hinge motion is low. Complexes with two S(2)(-), or with one S(2)(-) and one RS(-), bridging ligands are hinged; the decrease of the through-ring antibonding interaction between the in-plane sulfur p orbitals with folding appears to be the determinant for hinging. Complexes with two RS(-) bridging ligands can be planar or hinged depending on the relative orientation, syn or anti, of the R groups, on the nature, L(4) or L(2)L(2)', of the terminal ligands, and in the latter case on their disposition, cis or trans. However, the aromatic or aliphatic nature of bridging thiolates does not influence the geometry of the Pt(2)S(2) ring significantly. Conclusions drawn from platinum dimers can be extended to the palladium analogs.     

Microporous membranes obtained from polypropylene blend films by stretching

Blends of two linear polypropylenes (PP, having different molecular weights) were prepared to develop microporous membranes through melt extrusion followed by stretching. The role of high molecular weight chains on the row-nucleated lamellar crystallization was investigated. The orientation of crystalline and amorphous phases was measured by wide angle X-ray diffraction (WAXD) and Fourier transform infrared (FTIR). Long period spacing was obtained using small angle X-ray scattering (SAXS). The effects of annealing temperature and applied elongation during annealing on the crystallinity of the films were studied using differential scanning calorimetry (DSC). It was found that annealing at 140 °C contributed significantly to the perfection of the crystalline phase. Scanning electron microscopy (SEM) images of the membrane surface showed more pore density and uniform pore size as the amount of high molecular weight component increased. The addition of the high M_w PP improved the water vapor transmission rate (WVTR) of the membranes, indicating increased interconnectivity of the pores, which was also confirmed from cross-section SEM micrographs of the membranes. The surface area and pore dimensions of the microporous membranes were measured using the BET nitrogen absorption technique and mercury porosimetry, respectively. The influences of temperature and amount of stretching during cold and hot stretching on WVTR were also explored. Tensile properties in the machine and transverse directions (MD and TD, respectively) as well as puncture resistance in the normal direction (ND) were evaluated. As the high M_w PP was added, a slight reduction in the mechanical properties along MD and TD and no changes in ND were observed.     

Polymer ferroelectret based on polypropylene foam: piezoelectric properties prediction using dynamic mechanical analysis

Thin polypropylene (PP) foam films were produced by continuous extrusion using supercritical nitrogen (N₂) and then charged via corona discharge. The samples were characterized by dynamic mechanical analysis as a simple method to predict the piezoelectric properties of the cellular PP obtained. The results were then related to morphological analysis based on scanning electron microscopy and mechanical properties in tension. The results showed that the presence of a nucleating agent (CaCO₃) substantially improved the morphology (in terms of cell size and cell density) of the produced foam. Also, an optimization of the extrusion (screw design, temperature profile, blowing agent, and nucleating agent content) and post‐extrusion (calendering temperature and speed) conditions led to the development of a stretched eye‐like cellular structure with uniform cell size distribution. This morphology produced higher storage and loss moduli in the machine (longitudinal) direction than for the transverse direction, as well as higher piezoelectric properties. The morphological and mechanical results showed that higher cell aspect ratio led to lower Young's modulus, which is suitable to achieve higher piezoelectric properties. Finally, the best quasi‐static piezoelectric d₃₃ coefficient was 550 pC/N for a cellular PP ferroelectret having a uniform eye‐like cellular structure using N₂ as the ionizing gas inside the cells, while the highest value was only 250 pC/N when air was used. Hence, the value of d₃₃ can be improved by more than 100% just by replacing air with N₂ as the ionizing gas. Copyright © 2016 John Wiley & Sons, Ltd.     

Influence of Internal Structure and Medium Length on Transport and Deposition of Suspended Particles: A Laboratory Study

A laboratory study was undertaken on the transport and the deposition of suspended particles (silt of modal diametre 6 μm) in three columns of different length, filled with glass beads or gravel. Tracer tests were carried out at various flow velocities by short pulses of a mixture of suspended particles/dissolved tracer. The breakthrough curves were competently described with the analytical solution of a convection dispersion equation with a first-order deposition rate and the hydro-dispersive parameters were deduced. For the same experimental conditions, the results showed a difference in the behaviour of the suspended particles transport and deposition rates within the two porous media tested. The internal structure of both media governs the particle-grain collision frequency as well as the particles trapping. The scale effect was highlighted and affects the dispersivity, the size exclusion effect, the recovery rates and the deposition rates. Longitudinal dispersion increases with mean pore velocity and is described with a nonlinear relationship. The dispersivity increases with the column length. The size exclusion effect is more important in the short column. The recovery rate increases with flow velocity and decreases while increasing column length. The deposition rates increases until a critical flow velocity then decreases. This critical velocity is also sensitive to the scale effect, and increases with the column length.     

Biaxial orientation characterization on-line and off-line and structure properties correlations in films

In this paper, biaxial orientation characterization techniques are briefly reviewed. Results obtained using birefringence and Fourier Transform Infrared Spectroscopy (FTIR) techniques are presented for different applications: On-line monitoring of birefringence for an amorphous polymer (polystyrene); On-line and off-line determination of orientation (birefringence) of polyethylene terephthalate (PET) and finally off-line measurement of orientation on polyethylene (LDPE) films using FTIR. Some typical morphologies of blown LDPE films are reported and discussed. Finally, correlations between orientation on one hand and shrinkage and tear strength on the other are attempted.     

Nanoparticles of [Fe(NH2‐trz)3]Br2⋅3 H2O (NH2‐trz=2‐Amino‐1,2,4‐triazole) Prepared by the Reverse Micelle Technique: Influence of Particle and Coherent Domain Sizes on Spin‐Crossover Properties

By changing the surfactant/water ratio , nanoparticles of the iron(II) spin crossover material, [Fe(NH₂‐trz)₃]Br₂ ? 3 H₂O (with NH₂‐trz=4‐amino‐1,2,4‐triazole), have been synthesised from 1 μm down to 30 nm (see figure). Magnetic and reflectivity experiments indicate that the critical size for observing a thermal hysteresis in this 1D polymer family is around 50 nm, and powder X‐ray diffraction shows that particles of about 30 nm are constituted by about one coherent domain.