Iridium complexes bearing a PNP ligand, favoring facile C(sp^3)–H bond cleavage

Hydrogen iodide is lost upon reaction of PNP with IrI_3, where PNP = 2,6-bis-(di-t-butylphosphinomethyl)pyridine to give crystallographically characterized Ir(PNP)*(I)_2, which reacts with H_2 to give Ir(PNP)(H)(I)_2. Ir(PNP)(Cl)_3 is relatively inert towards the intramolecular C–H activation of the tert-butyl's of the PNP ligand

Comparison of the Fermi-surface topologies of kappa-(BEDT-TTF)_2 Cu(NCS)_2 and its deuterated analogue

We have measured details of the quasi one-dimensional Fermi-surface sections in the organic superconductor kappa-(BEDT-TTF)_2 Cu(NCS)_2 and its deuterated analogue using angle-dependent millimetre-wave techniques. There are significant differences in the corrugations of the Fermi surfaces in the deuterated and undeuterated salts. We suggest that this is important in understanding the inverse isotope effect, where the superconducting transition temperature rises on deuteration. The data support models for superconductivity which invoke electron-electron interactions depending on the topological properties of the Fermi surface

First normal stress difference and crystallization in a dense sheared granular fluid

The first normal stress difference (${\mathcal N}_1$) and the microstructure in a dense sheared granular fluid of smooth inelastic hard-disks are probed using event-driven simulations. While the anisotropy in the second moment of fluctuation velocity, which is a Burnett-order effect, is known to be the progenitor of normal stress differences in {\it dilute} granular fluids, we show here that the collisional anisotropies are responsible for the normal stress behaviour in the {\it dense} limit. As in the elastic hard-sphere fluids, ${\mathcal N}_1$ remains {\it positive} (if the stress is defined in the {\it compressive} sense) for dilute and moderately dense flows, but becomes {\it negative} above a critical density, depending on the restitution coefficient. This sign-reversal of ${\mathcal N}_1$ occurs due to the {\it microstructural} reorganization of the particles, which can be correlated with a preferred value of the {\it average} collision angle $\theta_{av}=\pi/4 \pm \pi/2$ in the direction opposing the shear. We also report on the shear-induced {\it crystal}-formation, signalling the onset of fluid-solid coexistence in dense granular fluids. Different approaches to take into account the normal stress differences are discussed in the framework of the relaxation-type rheological models.Comment: 21 pages, 13 figure

Persistence to high temperatures of interlayer coherence in an organic superconductor

The interlayer magnetoresistance $\rho_{zz}$ of the organic metal \cuscn is studied in fields of up to 45 T and at temperatures $T$ from 0.5 K to 30 K. The peak in $\rho_{zz}$ seen in in-plane fields, a definitive signature of interlayer coherence, remains to $T$s exceeding the Anderson criterion for incoherent transport by a factor $\sim 30$. Angle-dependent magnetoresistance oscillations are modeled using an approach based on field-induced quasiparticle paths on a 3D Fermi surface, to yield the $T$ dependence of the scattering rate $\tau^{-1}$. The results suggest that $\tau^{-1}$ does not vary strongly over the Fermi surface, and that it has a $T^2$ dependence due to electron-electron scattering

Foliation of the Kottler-Schwarzschild-De Sitter Spacetime by Flat Spacelike Hypersurfaces

There exist Kruskal like coordinates for the Reissner-Nordstrom (RN) black hole spacetime which are regular at coordinate singularities. Non existence of such coordinates for the extreme RN black hole spacetime has already been shown. Also the Carter coordinates available for the extreme case are not manifestly regular at the coordinate singularity, therefore, a numerical procedure was developed to obtain free fall geodesics and flat foliation for the extreme RN black hole spacetime. The Kottler-Schwarzschild-de Sitter (KSSdS) spacetime geometry is similar to the RN geometry in the sense that, like the RN case, there exist non-singular coordinates when there are two distinct coordinate singularities. There are no manifestly regular coordinates for the extreme KSSdS case. In this paper foliation of all the cases of the KSSdS spacetime by flat spacelike hypersurfaces is obtained by introducing a non-singular time coordinate.Comment: 12 pages, 4 figure

Angle Dependent Magnetoresistance of the Layered Organic Superconductor \kappa-(ET)2Cu(NCS)2: Simulation and Experiment

The angle-dependences of the magnetoresistance of two different isotopic substitutions (deuterated and undeuterated) of the layered organic superconductor \kappa-(ET)2Cu(NCS)2 are presented. The angle dependent magnetoresistance oscillations (AMRO) arising from the quasi-one-dimensional (Q1D) and quasi-two-dimensional (Q2D) Fermi surfaces in this material are often confused. By using the Boltzman transport equation extensive simulations of the AMRO are made that reveal the subtle differences between the different species of oscillation. No significant differences are observed in the electronic parameters derived from quantum oscillations and AMRO for the two isotopic substitutions. The interlayer transfer integrals are determined for both isotopic substitutions and a slight difference is observed which may account for the negative isotope effect previously reported [1]. The success of the semi-classical simulations suggests that non-Fermi liquid effects are not required to explain the interlayer-transport in this system.Comment: 15 pages, 16 figure

Flows and Duality Symmetries in N=1 Supersymmetric Gauge Theories

We present more examples of dual N=1 SUSY gauge theories. This set of theories is connected by flows to both Seiberg's and Kutasov's dual theories. This provides a unifying picture of the various dual theories. We investigate the dual theories, their flat directions and mass perturbations.Comment: 31 pages, uses harvmac.tex and tables.tex Minor changes - version accepted to Nucl. Phys.

Addition of H_2O and O_2 to Acetone and Dimethylsulfoxide Ligated Uranyl(V) Dioxocations

Gas-phase complexes of the formula [UO_2(lig)]^+ (lig = acetone (aco) or dimethylsulfoxide (dmso)) were generated by electrospray ionization (ESI) and studied by tandem ion-trap mass spectrometry to determine the general effect of ligand charge donation on the reactivity of UO_2^+ with respect to water and dioxygen. The original hypothesis that addition of O_2 is enhanced by strong σ-donor ligands bound to UO_2^+ is supported by results from competitive collision-induced dissociation (CID) experiments, which show near exclusive loss of H_2O from [UO_2(dmso)(H_2O)(O_2)]^+, whereas both H_2O and O_2 are eliminated from the corresponding [UO_2(aco)(H_2O)(O_2)]^+ species. Ligand-addition reaction rates were investigated by monitoring precursor and product ion intensities as a function of ion storage time in the ion-trap mass spectrometer: these experiments suggest that the association of dioxygen to the UO_2^+ complex is enhanced when the more basic dmso ligand was coordinated to the metal complex. Conversely, addition of H_2O is favored for the analogous complex ion that contains an aco ligand. Experimental rate measurements are supported by density function theory calculations of relative energies, which show stronger bonds between UO_2^+ and O_2 when dmso is the coordinating ligand, whereas bonds to H_2O are stronger for the aco complex

Interactions of Poly(amidoamine) Dendrimers with Human Serum Albumin: Binding Constants and Mechanisms

The interactions of nanomaterials with plasma proteins have a significant impact on their in vivo transport and fate in biological fluids. This article discusses the binding of human serum albumin (HSA) to poly(amidoamine) [PAMAM] dendrimers. We use protein-coated silica particles to measure the HSA binding constants (K_b) of a homologous series of 19 PAMAM dendrimers in aqueous solutions at physiological pH (7.4) as a function of dendrimer generation, terminal group, and core chemistry. To gain insight into the mechanisms of HSA binding to PAMAM dendrimers, we combined ^1H NMR, saturation transfer difference (STD) NMR, and NMR diffusion ordered spectroscopy (DOSY) of dendrimer−HSA complexes with atomistic molecular dynamics (MD) simulations of dendrimer conformation in aqueous solutions. The binding measurements show that the HSA binding constants (K_b) of PAMAM dendrimers depend on dendrimer size and terminal group chemistry. The NMR ^1H and DOSY experiments indicate that the interactions between HSA and PAMAM dendrimers are relatively weak. The ^1H NMR STD experiments and MD simulations suggest that the inner shell protons of the dendrimers groups interact more strongly with HSA proteins. These interactions, which are consistently observed for different dendrimer generations (G0-NH_2vs G4-NH_2) and terminal groups (G4-NH_2vs G4-OH with amidoethanol groups), suggest that PAMAM dendrimers adopt backfolded configurations as they form weak complexes with HSA proteins in aqueous solutions at physiological pH (7.4)