Enumeration of non-labile oxygen atoms in dissolved organic matter by use of 16O/18O exchange and Fourier transform ion-cyclotron resonance mass spectrometry

We report a simple approach for enumeration of non-labile oxygen atoms in individual molecules of dissolved organic matter (DOM), using acid-catalyzed ¹⁶O/¹⁸O exchange and ultrahigh-resolution Fourier-transform ion-cyclotron-resonance mass spectrometry (FTICR-MS). We found that by dissolving DOM in H₂ ¹⁸O at 95 °C for 20 days it is possible to replace all oxygen atoms of DOM molecules (excluding oxygen from ether groups) with ¹⁸O. The number of exchanges in each molecule can be determined using high-resolution FTICR. Using the proposed method we identified the number of non-labile oxygen atoms in 231 molecules composing DOM. Also, using a previously developed hydrogen–deuterium (H/D)-exchange approach we identified the number of labile hydrogen atoms in 450 individual molecular formulas. In addition, we observed that several backbone hydrogen atoms can be exchanged for deuterium under acidic conditions. The method can be used for structural and chemical characterization of individual DOM molecules, comparing different DOM samples, and investigation of biological pathways of DOM in the environment.     

Enhancement of single‑photon emission from nitrogen‑vacancy centers with TiN/(Al,Sc)N hyperbolic metamaterial

The broadband enhancement of single‑photon emission from nitrogen‐vacancy centers in nanodiamonds coupled to a planar multilayer metamaterial with hyperbolic dispersion is studied experimentally. The metamaterial is fabricated as an epitaxial metal/dielectric superlattice consisting of CMOS‐compatible ceramics: titanium nitride (TiN) and aluminum scandium nitride (Al_xSc_1‐xN). It is demonstrated that employing the metamaterial results in significant enhancement of collected single‑photon emission and reduction of the excited‐state lifetime. Our results could have an impact on future CMOS‐compatible integrated quantum sources.

     

Efficient time integration in multiplicative inelasticity

In Shutov et al. (Comput Methods Appl Mech Eng 265:213–225, 2013), the numerical time integration of a famous large strain model of Maxwell fluid type has been considered. The underlying model is based on the multiplicative decomposition of the deformation gradient and includes a Neo-Hookean hyperelasticity relation as well as an incompressible viscous flow rule. Shutov et al. presented a time stepping algorithm for implicit time integration of the inelastic flow rule, which is based on Euler backward time discretisation, prevents error accumulation and is iteration free. In this contribution, the basic idea of the this approach is applied to more general models of multiplicative viscoelasticity. Here, extended hyperelastic relations including general functions of the first principal invariant of deformation tensors are regarded. An efficient time stepping algorithm is derived, where only one scalar equation for one scalar unknown has to be solved within every time step. The approach is applied to a specific viscoelastic model. (© 2015 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

Prandtl Number in Classical Hard-Sphere and One-Component Plasma Fluids

The Prandtl number is evaluated for the three-dimensional hard-sphere and one-component plasma fluids, from the dilute weakly coupled regime up to a dense strongly coupled regime near the fluid-solid phase transition. In both cases, numerical values of order unity are obtained. The Prandtl number increases on approaching the freezing point, where it reaches a quasi-universal value for simple dielectric fluids of about ≃1.7. Relations to two-dimensional fluids are briefly discussed.     

Molecular Structure,Thermodynamic and Spectral Characteristics of Metal-Free and Nickel Complex of Tetrakis(1,2,5-thiadiazolo)porphyrazine

The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H₂TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H₂TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D_2h and D_4h symmetry was obtained for H₂TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state ¹A_1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H₂TTDPz and NiTTDPz were studied experimentally and simulated theoretically.     

Bulk and surface electron transport in topological insulator candidate YbB6–δ

We report the study of transport and magnetic properties of the YbB_6–δsingle crystals grown by inductive zone melting. A strong disparity in the low temperature resistivity, Seebeck and Hall coefficients is established for the samples with the different level of boron deficiency. The effective parameters of the charge transport in YbB_6–δ are shown to depend on the concentration of intrinsic defects, which is estimated to range from 0.09% to 0.6%. The pronounced variation of Hall mobility μ_H found for bulk holes is induced by the decrease of transport relaxation time from τ ≈ 7.7 fs for YbB_5.994 to τ ≈ 2.2 fs for YbB_5.96. An extra contribution to conductivity from electrons with μ_H≈ –1000 cm² V^–1 s^–1 and the very low concentration n /n_Yb≈ 10^–6 discovered below 20 K for all the single crystals under investigation is suggested to arise from the surface electron states appeared in the inversion layer due to the band bending. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Topological transition in coated wire medium

Employing nonlocal homogenization approach, we investigate the properties of a metamaterial consisting of parallel metallic wires with dielectric coating. We demonstrate that manipulation of dielectric contrast between wire dielectric shell and host material at fixed frequency results in dynamic switching of metamaterial dispersion regime from elliptic to the hyperbolic one, i.e. the topological transition takes place. It is proved that such transition can be induced by the variation of the metamaterial temperature. Our findings thus pave a way to the implementation of a tunable ‘elliptic‐hyperbolic’ metamaterial.     

Shocks and cold fronts in galaxy clusters

The currently operating X-ray imaging observatories provide us with an exquisitely detailed view of the Megaparsec-scale plasma atmospheres in nearby galaxy clusters. At z<0.05$z<0.05$, the Chandra  's 1^″$1^{″}$ angular resolution corresponds to linear resolution of less than a kiloparsec, which is smaller than some interesting linear scales in the intracluster plasma. This enables us to study the previously unseen hydrodynamic phenomena in clusters: classic bow shocks driven by the infalling subclusters, and the unanticipated “cold fronts,” or sharp contact discontinuities between regions of gas with different entropies. The ubiquitous cold fronts are found in mergers as well as around the central density peaks in “relaxed” clusters. They are caused by motion of cool, dense gas clouds in the ambient higher-entropy gas. These clouds are either remnants of the infalling subclusters, or the displaced gas from the cluster's own cool cores.     

A High‐Pressure Polymorph of Phosphorus Nitride Imide

Phosphorus nitride imide, PN(NH), is of great scientific importance because it is isosteric with silica (SiO₂). Accordingly, a varied structural diversity could be expected. However, only one polymorph of PN(NH) has been reported thus far. Herein, we report on the synthesis and structural investigation of the first high‐pressure polymorph of phosphorus nitride imide, β‐PN(NH); the compound has been synthesized using the multianvil technique. By adding catalytic amounts of NH₄Cl as a mineralizer, it became possible to grow single crystals of β‐PN(NH), which allowed the first complete structural elucidation of a highly condensed phosphorus nitride from single‐crystal X‐ray diffraction data. The structure was confirmed by FTIR and ³¹P and ¹H solid‐state NMR spectroscopy. We are confident that high‐pressure/high‐temperature reactions could lead to new polymorphs of PN(NH) containing five‐fold‐ or even six‐fold‐coordinated phosphorus atoms and thus rivalling or even surpassing the structural variety of SiO₂.