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

Nitrous oxide emissions from the Arabian Sea: A synthesis

We computed high-resolution (1º latitude x 1º longitude) seasonal and annual nitrous oxide (N2O) concentration fields for the Arabian Sea surface layer using a database containing more than 2400 values measured between December 1977 and July 1997. N2O concentrations are highest during the southwest (SW) monsoon along the southern Indian continental shelf. Annual emissions range from 0.33 to 0.70 Tg N2O and are dominated by fluxes from coastal regions during the SW and northeast monsoons. Our revised estimate for the annual N2O flux from the Arabian Sea is much more tightly constrained than the previous consensus derived using averaged in-situ data from a smaller number of studies. However, the tendency to focus on measurements in locally restricted features in combination with insufficient seasonal data coverage leads to considerable uncertainties of the concentration fields and thus in the flux estimates, especially in the coastal zones of the northern and eastern Arabian Sea. The overall mean relative error of the annual N2O emissions from the Arabian Sea was estimated to be at least 65%

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

Modular Palladium Bipyrazoles for the Isomerization of Allylbenzenes - Mechanistic Considerations and Insights into Catalyst Design and Activity, Role of Solvent, and Additive Effects

The catalytic activity of novel bidentate N,N-chelated palladium complexes derived from electron excessive, backbone fused 3,3′-bipyrazoles in the selective isomerization of terminal arylpropenoids and 1-alkenes is described. The catalysts are easily modified by appropriate wing tip substitution, while maintaining the same bulky, rigid unreactive aliphatic backbone. Eleven novel palladium complexes with different electronic and steric properties were investigated. Their performance in the palladium(II)-catalyzed isomerization of a series of substituted allylbenzenes was evaluated in terms of electronic as well as steric effects. Besides the clear finding of a general trend towards higher catalyst activity with more electron-donating properties of the coordinated N,N-bidentate ligands, we found that the catalytic process strongly depends on the choice of solvents and additives. Extensive solvent screening revealed that reactions run best in a 2:1 toluene-methanol mixture, with the alcohol employed being a crucial factor in terms of electronic and steric factors. A reaction mechanism involving a hydride addition–elimination mechanism starting with a palladium hydride species generated in situ in alcoholic solutions, as corroborated by experiments using deuterium labeled allylbenzene, seems to be most likely. The proposed mechanism is also supported by the observed reaction rate orders of κobs[cat.]≈1 (0.94), κobs [substrate]=0.20→1.0 (t→∞) and κobs [methanol]=−0.51 for the isomerization of allylbenzene. Furthermore, the influence of acid and base, as well as the role of the halide coordinated to the catalyst, are discussed. The system catalyzes the isomerization of allylbenzenes very efficiently yielding high E:Z selectivities under very mild conditions (room temperature) and at low catalyst loadings of 1 mol% palladium even in unpurified solvents. The integrity and stability of the catalyst system were confirmed by multiple addition reaction cycles, successive filtration and isolation experiments, and the lack of palladium black formation

Strategy for allocating the MSD magnets and vacuum chambers

An analogous strategy as applied for the MSI septum magnets allows an optimisation of the installation of the MSD septa regarding magnet and chamber allocation. Even if the gain in aperture is small, of the order of half a millimetre, it is not negligible and- being essentially for free - should nevertheless be implemented

Quantum entanglement of charges in bound states with finite-size dyons

We show that the presence of finite-size monopoles can lead to a number of interesting physical processes involving quantum entanglement of charges. Taking as a model the classical solution of the N=2 SU(2) Yang-Mills theory, we study interaction between dyons and scalar particles in the adjoint and fundamental representation. We find that there are bound states of scalars and dyons, which, remarkably, are always an entangled configuration of the form |\psi > =|dyon+> |scalar-> +/- |dyon->|scalar+>. We determine the energy levels and the wave functions and also discuss their stability.Comment: 29 pages, 3 figures. Minor correction in references (to appear in JHEP04 (2002) 010

Reclassification of ICD-9 Codes into Meaningful Categories for Oncology Survivorship Research

Background. The International Classification of Disease, ninth revision (ICD-9) is designed to code disease into categories which are placed into administrative databases. These databases have been used for epidemiological studies. However, the categories used in the ICD9-codes are not always the most effective for evaluating specific diseases or their outcomes, such as the outcomes of cancer treatment. Therefore a re-classification of the ICD-9 codes into new categories specific to cancer outcomes is needed. Methods. An expert panel comprised of two physicians created broad categories that would be most useful to researchers investigating outcomes and morbidities associated with the treatment of cancer. A Senior Data Coordinator with expertise in ICD-9 coding, then joined this panel and each code was re-classified into the new categories. Results. Consensus was achieved for the categories to go from the 17 categories in ICD-9 to 39 categories. The ICD-9 Codes were placed into new categories, and subcategories were also created for more specific outcomes. The results of this re-classification is available in tabular form. Conclusions. ICD-9 codes were re-classified by group consensus into categories that are designed for oncology survivorship research. The novel re-classification system can be used by those involved in cancer survivorship research

Rhodium complexes bearing tetradentate diamine-bis(phenolate) ligands

Using tetradentate, dianionic ligands, several new rhodium complexes have been prepared. Some of these diamine-bis(phenolate) compounds, are active for C–H activation of benzene. These complexes are air and thermally stable. All four complexes were characterized by X-ray diffraction

BPS String Solutions in Non-Abelian Yang-Mills Theories and Confinement

Starting from the bosonic part of N=2 Super QCD with a 'Seiberg-Witten' N=2 breaking mass term, we obtain string BPS conditions for arbitrary semi-simple gauge groups. We show that the vacuum structure is compatible with a symmetry breaking scheme which allows the existence of Z_k-strings and which has Spin(10) -> SU(5) x Z_2 as a particular case. We obtain BPS Z_k-string solutions and show that they satisfy the same first order differential equations as the BPS string for the U(1) case. We also show that the string tension is constant, which may cause a confining potential between monopoles increasing linearly with their distance.Comment: 11 pages, Latex. Minor changes to the text. Final version to appear in Phys. Rev.