[H3tren] templated iron fluorides; synthesis, crystal structures and Mössbauer studies

The hydrothermal synthesis, using tris-(2-ethylamino)amine (tren) as a template, and the crystal structures of three new hybrid iron fluorides, (H₃O)₂·[H₃tren]₂·(FeF₆)₂·(FeF₅(H₂O))·2H₂O (I), [H₃tren]₂·(FeF₆)₂·(FeF₂(H₂O)₄)·8H₂O (II) and [H₃tren]₂·(FeF₆)·(F)₃·H₂O (III), are reported. I, II, and III are triclinic (P-1), monoclinic (P2₁/c) and orthorhombic (I222), respectively. The structure of I is built up from isolated FeF₆ and FeF₅(H₂O) distorted octahedra separated by triprotonated [H₃tren]³⁺ cations, disordered H₃O⁺ cations and H₂O molecules. In II, Fe^IIIF₆ and neutral [Fe^IIF₂(H₂O)₄] octahedra form, together with [H₃tren]³⁺ cations, infinite (100) layers separated by extra water molecules. The structure of III consists of isolated and disordered FeF₆ octahedra, fluoride anions F⁻ connected to [H₃tren]³⁺ cations and extra fluoride anions F⁻ disordered with H₂O molecules. All [H₃tren]³⁺ cations have a “spider” type conformation. ⁵⁷Fe Mössbauer characterization shows that +III valence state can only be considered for iron cations in I and III and preliminary Mössbauer results are consistent with the presence of both +II and +III valences for iron cations in II, in agreement with the crystallographic results.     

Air‐Stable {(C5H5)Co} Catalysts for [2+2+2] Cycloadditions

Cobalt cyclopentadienyl complexes incorporating a fumarate and a CO ligand (see picture) efficiently catalyze inter‐ and intramolecular [2+2+2] cycloadditions of alkynes, nitriles, and/or alkenes to give benzenes, pyridines, or 1,3‐cyclohexadienes. Unlike catalysts such as [CpCo(CO)₂] or [CpCo(C₂H₄)₂] (Cp=C₅H₅), they are air‐stable, easy to handle, compatible with microwave conditions, and do not necessarily require irradiation to be active.

     

Progress in Scanning Electrochemical Microscopy by Coupling with Electrochemical Impedance and Quartz Crystal Microbalance

Scanning electrochemical microscopy (SECM) is a powerful technique for performing quantitative measurements at a local scale. This paper covers the development of combinations of SECM with electrochemical impedance spectroscopy (EIS) and electrochemical quartz crystal microbalance (EQCM). Basic aspects are described and potential applications reported by several research groups are covered. The unique advantages of the coupled techniques—with additional information being obtained from each coupling—are also discussed.     

Thermodynamic prediction of bulk metallic glass forming alloys in ternary Zr–Cu–X (X = Ag,Al, Ti,Ga) systems

Prediction of bulk metallic glass (BMG) forming compositions has always been a challenge due to thermodynamic and kinetic constraints. In the present investigation, a parameter based on the enthalpy of chemical mixing (?H_chem) and the mismatch entropy (?S_σ/k_B) has been used to correlate with glass forming ability in some Zr based BMGs. The new thermodynamic parameter, P_HS = ?H_chem × ?S_σ/k_B, is found to have strong correlation with glass forming ability in the configurational entropy (?S_config/R) range of 0.9–1.0. P_HS has been calculated for compositions in Zr–Cu–Ag, Zr–Cu–Al, Zr–Cu–Ti and Zr–Cu–Ga ternary systems. It is observed that in all the systems studied, the best BMG composition (highest critical diameter (Z_c) of glass formation) is the one that corresponds to the highest negative P_HS value. Present approach using P_HS could be road map to design new BMG forming compositions.     

Weak solutions to a stationary heat equation with nonlocal radiation boundary condition and right‐hand side in Lp (p⩾1)

Accurate modelling of heat transfer in high‐temperature situations requires accounting for the effect of heat radiation. In complex industrial applications involving dissipative heating, we hardly can expect from the mathematical theory that the heat sources will be in a better space than L¹. In this paper, we focus on a stationary heat equation with nonlocal boundary conditions and L^p right‐hand side, with p?1 being arbitrary. Thanks to new coercivity results, we are able to produce energy estimates that involve only the L^p norm of the heat sources and to prove the existence of weak solutions. Copyright © 2008 John Wiley & Sons, Ltd.     

Navier–Stokes equations with nonhomogeneous boundary conditions in a convex bi-dimensional domain

We prove the existence of a weak solution to Navier–Stokes equations describing the isentropic flow of a gas in a convex and bounded region, ΩR², with nonhomogeneous Dirichlet boundary conditions on ∂Ω. These results are also extended to flow domain surrounding an obstacle.     

Right-handed vector fields & the Lorenz attractor

The main purpose of this paper is to introduce a class of vector fields on the 3-sphere that we call “right-handed”. Roughly speaking, they are characterized by the fact that any two orbits link positively. We give various natural examples and provide some kind of homological characterization. We then describe some of the main dynamical properties of these flows. This article is based on the 5th Takagi Lectures that the author delivered at the University of Tokyo on October 4 and 5, 2008.     

MULTISPECIES AND SINGLE‐SPECIES MODELS OF FISH POPULATION DYNAMICS: COMPARING PARAMETER ESTIMATES

Abstract Population features inferred from single‐species, age‐structured models are compared to those inferred from a multispecies, age‐structured model that includes predator‐prey interactions among three commercially harvested fish species—walleye pollock, Atka mackerel, and Pacific cod—on the Aleutian Shelf, Alaska. The multispecies framework treats the single‐species models and data as a special case of the multispecies model and data. The same data from fisheries and surveys are used to estimate model parameters for both single‐species and multispecies configurations of the model. Additionally, data from stomach samples and predator rations are used to estimate the parameters of the multispecies model. One form of the feeding functional response, predator pre‐emption, was selected using AIC from seven alternative models for how the predation rate changes with the densities of prey and possibly other predators. Differences in estimated population dynamics and productivity between the multispecies and single‐species models were observed. The multispecies model estimated lower mackerel population sizes from 1964–2003 than the single‐species model, while the spawning biomass of pollock was estimated to have declined more than three times faster since 1964 by the multispecies model. The variances around the estimates of spawning biomass were smaller for mackerel and larger for pollock in the multispecies model compared to the single‐species model.     

Projected iterative algorithms for complex symmetric systems arising in magnetized multicomponent transport

We investigate iterative algorithms for solving complex symmetric constrained singular systems arising in magnetized multicomponent transport. The matrices of the corresponding linear systems are symmetric with a positive semi-definite real part and an imaginary part with a compatible nullspace. We discuss well posedness, the symmetry of generalized inverses and Cholesky methods. We investigate projected stationary iterative methods as well as projected orthogonal residuals algorithms generalizing previous results on real systems. As an application, we consider the linear systems arising from the kinetic theory of gases and providing transport coefficients of partially ionized gas mixtures subjected to a magnetic field.