Two dinuclear iron(II) complexes K[Fe2(L1)(SCN)4]·2(C3H8O) and [Fe2(L1)(SeCN)3(C5H5N)]·H2O are stabilised in the '[HS-LS]' state by a bis-tetradentate pyrazolate-based ligand

Two air-sensitive dinuclear iron(II) complexes, K[Fe(II)(2)(L(1))(SCN)(4)]·2(C(3)H(8)O) (1) and [Fe(II)(2)(L(1))(SeCN)(3)(C(5)H(5)N)]·H(2)O (2), of 3,5-bis[N,N-bis(2-pyridylmethyl)aminomethyl]-1H-pyrazolate [(L(1))(-)] have been prepared. Interestingly, complex 1 is anionic, featuring four coordinated SCN(-) anions and a potassium counterion whereas complex 2 is neutral, containing a coordinated pyridine molecule and only three coordinated SeCN(-) anions. These are the first iron complexes reported for this type of ligand. Magnetic measurements and M?ssbauer spectra show that both 1 and 2 are in a '[HS-LS]' mixed spin state between 300 and 2 K.     

Two-dimensional heisenberg antiferromagnets: syntheses, X-ray structures, and magnetic behavior of [Cu(pz)2](ClO4)2, [Cu(pz)2](BF4)2, and [Cu(pz)2(NO3)](PF6)

We report on the syntheses, crystal structures, and magnetic susceptibilities of a family of copper pyrazine (pz)-based antiferromagnets with moderate in-plane magnetic exchange. These materials fall into two classes: monoclinic complexes [Cu(pz)2]A2 for A = ClO4 (1) or BF4 (2) and the tetragonal complex [Cu(pz)2(NO3)]PF6 (3). Compound 1 and its deuterated version [Cu(pz-d4)2](ClO4)2 (1a) crystallize in the space group C2/m at room temperature with disordered perchlorate anions. For both 1 and 2, the C centering of the Cu(II), S = 1/2, site yields four equivalent nearest neighbors, producing layers of Cu(II) ions bridged by the pz molecules, which map onto a square magnetic lattice. The layers are offset such that Cu(II) ions lie above and below the holes of adjacent layers. Compound 3 crystallizes in the space group I4/mcm with a layer structure similar to those of 1 and 2 but with Cu(II) ions of adjacent layers stacked above each other and bridged by semicoordinate NO3- ions. The variable-temperature susceptibilities in these compounds approximate a two-dimensional Heisenberg antiferromagnet with J values within the layers of 17.5(3) K (1), 15.3(3) K (2), and 10.8(3) K (3). Ordering transitions are observed in the magnetic data at 4.2(3) and 4.3(5) K for 1 and 2, respectively.     

Experimental determination of the H2SO4/(NH4)2SO4/H2O phase diagram

We have experimentally investigated the water and sulfuric acid-rich regions of the H2SO4/(NH4)2SO4/H2O ternary liquid/solid phase diagram using differential scanning calorimetry (DSC) and infrared spectroscopy of thin films. We present the liquid/solid ternary phase diagram for temperatures below 373 K and H2SO4 concentrations below 60 wt %. We have determined two ternary eutectics and two tributary reaction points for this system in the regions studied. It is also seen that sulfuric acid tetrahydrate (SAT) forms as a metastable solid over a large concentration range. Two true binary systems have been identified: ice/letovicite and SAT/ammonium bisulfate. Finally, we have compared our results to the predictions of the aerosol inorganics model and have found significant differences both in the final melting points and in the location of some of the phase boundaries including a significant discrepancy in the invariant points predicted versus those observed.     

An improved gas-kinetic BGK finite-volume method for three-dimensional transonic flow

During the past decade gas-kinetic methods based on the BGK simplification of the Boltzmann equation have been employed to compute fluid flow in a finite-difference or finite-volume context. Among the most successful formulations is the finite-volume scheme proposed by Xu [K. Xu, A gas-kinetic BGK scheme for the Navier–Stokes equations and its connection with artificial dissipation and Godunov method, J. Comput. Phys. 171 (48) (2001) 289–335]. In this paper we build on this theoretical framework mainly with the aim to improve the efficiency and convergence of the scheme, and extend the range of application to three-dimensional complex geometries using general unstructured meshes. To that end we propose a modified BGK finite-volume scheme, which significantly reduces the computational cost, and improves the behavior on stretched unstructured meshes. Furthermore, a modified data reconstruction procedure is presented to remove the known problem that the Chapman–Enskog expansion of the BGK equation fixes the Prandtl number at unity. The new Prandtl number correction operates at the level of the partial differential equations and is also significantly cheaper for general formulations than previously published methods. We address the issue of convergence acceleration by applying multigrid techniques to the kinetic discretization. The proposed modifications and convergence acceleration help make large-scale computations feasible at a cost competitive with conventional discretization techniques, while still exploiting the advantages of the gas-kinetic discretization, such as computing full viscous fluxes for finite volume schemes on a simple two-point stencil.     

On nonlinear preconditioners in Newton–Krylov methods for unsteady flows

The application of nonlinear schemes like dual time stepping as preconditioners in matrix‐free Newton–Krylov‐solvers is considered and analyzed, with a special emphasis on unsteady viscous flows. We provide a novel formulation of the left preconditioned operator that says it is in fact linear in the matrix‐free sense, but changes the Newton scheme. This allows to get some insight in the convergence properties of these schemes, which is demonstrated through numerical results. Copyright © 2009 John Wiley & Sons, Ltd.     

A note on terminology in multigrid methods

We compare terminology used in the literature on multigrid methods for compressible computational fluid dynamics to that used in linear multigrid theory. Several popular iterative and direct smoothers are presented side-by-side using the same terminology. We argue for greater analysis of these methods in order to place them into a more rigorous framework and to identify the most promising candidates for future development. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Structure and Functional Differences of Cysteine and 3-Mercaptopropionate Dioxygenases: A Computational Study

Thiol dioxygenases are important enzymes for human health; they are involved in the detoxification and catabolism of toxic thiol-containing natural products such as cysteine. As such, these enzymes have relevance to the development of Alzheimer's and Parkinson's diseases in the brain. Recent crystal structure coordinates of cysteine and 3-mercaptopropionate dioxygenase (CDO and MDO) showed major differences in the second-coordination spheres of the two enzymes. To understand the difference in activity between these two analogous enzymes, we created large, active-site cluster models. We show that CDO and MDO have different iron(III)-superoxo-bound structures due to differences in ligand coordination. Furthermore, our studies show that the differences in the second-coordination sphere and particularly the position of a positively charged Arg residue results in changes in substrate positioning, mobility and enzymatic turnover. Furthermore, the substrate scope of MDO is explored with cysteinate and 2-mercaptosuccinic acid and their reactivity is predicted.     

Two‐dimensional implicit time‐dependent calculations on adaptive unstructured meshes with time evolving boundaries

An implicit multigrid‐driven algorithm for two‐dimensional incompressible laminar viscous flows has been coupled with a solution adaptation method and a mesh movement method for boundary movement. Time‐dependent calculations are performed implicitly by regarding each time step as a steady‐state problem in pseudo‐time. The method of artificial compressibility is used to solve the flow equations. The solution mesh adaptation method performs local mesh refinement using an incremental Delaunay algorithm and mesh coarsening by means of edge collapse. Mesh movement is achieved by modeling the computational domain as an elastic solid and solving the equilibrium equations for the stress field. The solution adaptation method has been validated by comparison with experimental results and other computational results for low Reynolds number flow over a shedding circular cylinder. Preliminary validation of the mesh movement method has been demonstrated by a comparison with experimental results of an oscillating airfoil and with computational results for an oscillating cylinder. Copyright © 2005 John Wiley & Sons, Ltd.     

Uranium-sulfilimine chemistry. Hydrolysis of Cp*2UCl2 with HNSPh2 · H2O and the crystal structure of Cp*2UCl(OH)(HNSPh2), a metallocene terminal hydroxy complex of tetravalent uranium

The reaction of Cp*₂UCl₂(HNSPh₂) with HNSPh₂ · H₂O in 1:1 stoichiometry, produces Cp*₂UCl(OH)(HNSPh₂) in good yield. This is the first structurally characterized metallocene f-element complex containing a terminal hydroxy ligand. Cp*₂UCl(OH)(HNSPh₂) is an intermediate in the formation of a tetra uranium-oxo-cluster [Cp^*(Cl)(HNSPh₂)U(μ₃-O)(μ₂-O)₂U(Cl)(HNSPh₂)₂]₂, which forms by hydrolysis of Cp*₂UCl₂ with excess HNSPh₂ · H₂O.     

Sequence-specific B-DNA flexibility modulates Z-DNA formation

Conversion of right-handed B-DNA into left-handed Z-DNA is one of the largest structural transitions in biology that plays fundamental roles in gene expression and regulation. Z-DNA segments must form within genomes surrounded by a sea of B-DNA and require creation of energetically costly B/Z junctions. Here, we show using a combination of natural abundance NMR R(1ρ) carbon relaxation measurements and CD spectroscopy that sequence-specific B-DNA flexibility modulates the thermodynamic propensity to form Z-DNA and the location of B/Z junctions. We observe sequence-specific flexibility in B-DNA spanning fast (ps-ns) and slow (μs-ms) time scales localized at the site of B/Z junction formation. Further, our studies show that CG-repeats play an active role tuning this intrinsic B-DNA flexibility. Taken together, our results suggest that sequence-specific B-DNA flexibility may provide a mechanism for defining the length and location of Z-DNA in genomes.