A 93Nb Solid‐State NMR and Density Functional Theory Study of Four‐ and Six‐Coordinate Niobate Systems

A variable B₀ field static (broadline) NMR study of a large suite of niobate materials has enabled the elucidation of high‐precision measurement of ⁹³Nb NMR interaction parameters such as the isotropic chemical shift (δ_iso), quadrupole coupling constant and asymmetry parameter (C_Q and η_Q), chemical shift span/anisotropy and skew/asymmetry (Ω/Δδ and κ/η_δ) and Euler angles (α, β, γ) describing the relative orientation of the quadrupolar and chemical shift tensorial frames. These measurements have been augmented with ab initio DFT calculations by using WIEN2k and NMR‐CASTEP codes, which corroborate these reported values. Unlike previous assertions made about the inability to detect CSA (chemical shift anisotropy) contributions from Nb^V in most oxo environments, this study emphasises that a thorough variable B₀ approach coupled with the VOCS (variable offset cumulative spectroscopy) technique for the acquisition of undistorted broad (?1/2?+1/2) central transition resonances facilitates the unambiguous observation of both quadrupolar and CSA contributions within these ⁹³Nb broadline data. These measurements reveal that the ⁹³Nb electric field gradient tensor is a particularly sensitive measure of the immediate and extended environments of the Nb^V positions, with C_Q values in the 0 to >80 MHz range being measured; similarly, the δ_iso (covering an approximately 250 ppm range) and Ω values (covering a 0 to approximately 800 ppm range) characteristic of these niobate systems are also sensitive to structural disposition. However, their systematic rationalisation in terms of the Nb? O bond angles and distances defining the immediate Nb^V oxo environment is complicated by longer‐range influences that usually involve other heavy elements comprising the structure. It has also been established in this study that the best computational method(s) of analysis for the ⁹³Nb NMR interaction parameters generated here are the all‐electron WIEN2k and the gauge included projector augmented wave (GIPAW) NMR‐CASTEP DFT approaches, which account for the short‐ and long‐range symmetries, periodicities and interaction‐potential characteristics for all elements (and particularly the heavy elements) in comparison with Gaussian 03 methods, which focus on terminated portions of the total structure.     

Sugawara-Type Constraints in Hyperbolic Coset Models

In the conjectured correspondence between supergravity and geodesic models on infinite-dimensional hyperbolic coset spaces, and E ₁₀/K(E ₁₀) in particular, the constraints play a central role. We present a Sugawara-type construction in terms of the E ₁₀ Noether charges that extends these constraints infinitely into the hyperbolic algebra, in contrast to the truncated expressions obtained in Damour et al. (Class. Quant. Grav. 24:6097, 2007) that involved only finitely many generators. Our extended constraints are associated to an infinite set of roots which are all imaginary, and in fact fill the closed past light-cone of the Lorentzian root lattice. The construction makes crucial use of the E ₁₀ Weyl group and of the fact that the E ₁₀ model contains both D = 11 supergravity and D = 10 IIB supergravity. Our extended constraints appear to unite in a remarkable manner the different canonical constraints of these two theories. This construction may also shed new light on the issue of ‘open constraint algebras’ in traditional canonical approaches to gravity.     

A Bioinspired Molybdenum Complex as a Catalyst for the Photo‐ and Electroreduction of Protons

A molybdenum–dithiolene–oxo complex was prepared as a model of some active sites of Mo/W‐dependent enzymes. The ligand, a quinoxaline–pyran‐fused dithiolene, mimics molybdopterin present in these active sites. For the first time, this type of complex was shown to be active as a catalyst for the photoreduction of protons with excellent turnover numbers (500) and good stability in aqueous/organic media and for the electroreduction of protons in acetonitrile with remarkable rate constants (1030 s^?1 at ?1.3 V versus Ag/AgCl). DFT calculations provided insight into the catalytic cycle of the reaction, suggesting that the oxo ligand plays a key role in proton exchange. These results provide a basis to optimize this new class of H₂‐evolving catalysts.     

Mining for bioactive scaffolds with scaffold networks: improved compound set enrichment from primary screening data

Identification of meaningful chemical patterns in the increasing amounts of high-throughput-generated bioactivity data available today is an increasingly important challenge for successful drug discovery. Herein, we present the scaffold network as a novel approach for mapping and navigation of chemical and biological space. A scaffold network represents the chemical space of a library of molecules consisting of all molecular scaffolds and smaller "parent" scaffolds generated therefrom by the pruning of rings, effectively leading to a network of common scaffold substructure relationships. This algorithm provides an extension of the scaffold tree algorithm that, instead of a network, generates a tree relationship between a heuristically rule-based selected subset of parent scaffolds. The approach was evaluated for the identification of statistically significantly active scaffolds from primary screening data for which the scaffold tree approach has already been shown to be successful. Because of the exhaustive enumeration of smaller scaffolds and the full enumeration of relationships between them, about twice as many statistically significantly active scaffolds were identified compared to the scaffold-tree-based approach. We suggest visualizing scaffold networks as islands of active scaffolds.     

Forensic examination of ink by high-performance thin layer chromatography--the United States Secret Service Digital Ink Library

Forensic examinations of ink have been performed since the beginning of the 20th century. Since the 1960s, the International Ink Library, maintained by the United States Secret Service, has supported those analyses. Until 2009, the search and identification of inks were essentially performed manually. This paper describes the results of a project designed to improve ink samples' analytical and search processes. The project focused on the development of improved standardization procedures to ensure the best possible reproducibility between analyses run on different HPTLC plates. The successful implementation of this new calibration method enabled the development of mathematical algorithms and of a software package to complement the existing ink library.     

Characterisation of martian soil simulants for the ExoMars rover testbed

The European Space Agency (ESA) ExoMars mission involves landing a rover on the surface of Mars on an exobiology mission to extend the search for life. The locomotion capabilities of the ExoMars rover will enable it to use its scientific instruments in a wide variety of locations. Before it is sent to Mars, this locomotion system must be tested and its performance limitations understood. To test the locomotion performance of the ExoMars rover, three martian regolith simulants were selected: a fine dust analogue, a fine Aeolian sand analogue, and a coarse sand analogue. To predict the performance of the ExoMars rover locomotion system in these three regolith simulants, it is necessary to measure some fundamental macroscopic properties of the materials: cohesion, friction angle, and various bearing capacity constants. This paper presents the tests conducted to determine these properties. During these tests, emphasis was placed on preparing the regolith simulants at different levels of density in order to evaluate its impact on the value of the parameters in particular. It was shown that compaction can influence the Bekker coefficients of pressure-sinkage. The shear properties are consistent with the critical state model at normal stresses similar to those of the ExoMars rover in all but one of the simulants, which showed behaviour more consistent with transitional soil behaviour. It is necessary to give due consideration to these variations to ensure a robust test regime is developed when testing the tractive ability of the ExoMars mobility system.     

Turbulent forced convection heat transfer of non-Newtonian nanofluids

Forced convection heat transfer of non-Newtonian nanofluids in a circular tube with constant wall temperature under turbulent flow conditions was investigated experimentally. Three types of nanofluids were prepared by dispersing homogeneously γ-Al₂O₃, TiO₂ and CuO nanoparticles into the base fluid. An aqueous solution of carboxymethyl cellulose (CMC) was used as the base fluid. Nanofluids as well as the base fluid show shear-thinning (pseudoplastic) rheological behavior. Results indicate that the convective heat transfer coefficient of nanofluids is higher than that of the base fluid. The enhancement of the convective heat transfer coefficient increases with an increase in the Peclet number and the nanoparticle concentration. The increase in the convective heat transfer coefficient of nanofluids is greater than the increase that would be observed considering strictly the increase in the effective thermal conductivity of nanofluids. Experimental data were compared to heat transfer coefficients predicted using available correlations for purely viscous non-Newtonian fluids. Results show poor agreement between experimental and predicted values. New correlation was proposed to predict successfully Nusselt numbers of non-Newtonian nanofluids as a function of Reynolds and Prandtl numbers.     

Constraints on the time scale of nuclear breakup from thermal hard-photon emission

Measured hard-photon multiplicities from second-chance nucleon-nucleon collisions are used in combination with a kinetic thermal model to estimate the breakup times of excited nuclear systems produced in nucleus-nucleus reactions at intermediate energies. The obtained nuclear breakup time for the ¹²⁹Xe + ^natSn reaction at 50 A MeV is Δτ ≈ 100-300 fm/c for all reaction centralities. The lifetime of the radiating sources produced in seven other different heavy-ion reactions studied by the TAPS experiment is consistent with Δτ ≈ 100 fm/c, such relatively long thermal photon emission times do not seemingly support the interpretation of nuclear breakup as due to a fast spinodal process for the heavy nuclear systems studied.     

Dicke-narrowed spectral line shapes of CO in Ar: Experimental results and a revised interpretation

The shapes of Dicke-narrowed spectral lines in the fundamental P-branch of CO in Ar are studied by comparing high-resolution measurements and theoretical calculations. The measured spectra were recorded at temperatures between 214 and 324 K, and at pressures between 0.025 and 1 atm. The calculations are based on solving a transport/relaxation equation for the appropriate off-diagonal element of the density matrix; they use a realistic intermolecular potential to determine the speed-dependent collisional broadening, and a rigid sphere potential to determine the Dicke narrowing. It is found that the calculations can reproduce the measured spectra within the experimental noise under all conditions, but that the magnitude of the Dicke narrowing in the measured spectra is 70-90% less than predicted from the mass diffusion constant. A revised view of the collision operator resolves the discrepancy in principle, and leads to a better understanding of the line shape problem in general.