Copper(II)–lanthanide(III) 15-metallacrown-5 complexes based on pyrazinohydroxamic acid as new multiple-binding pentagonal platforms with Lewis amphoteric nature

Reaction of copper(II) acetate, lanthanium(III) or gadolinium(III) nitrate (1/5 equiv.) with pyrazinohydroxamic acid (H₂Pyzha) in DMF led to a series of new heterobimetallic 15-metallacrown-5 complexes. In a MeOH/H₂O solution the complexes exist as molecular unassociated metallacrowns. In solid state their structures are more complicated as it has been confirmed by X-ray analysis: discrete molecular metallacrowns [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(NO₃)] · 0.5C₆H₆ · H₂O (1), [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅](NO₃) · 1.5DMF · 0.5H₂O (2), [La(NO₃)₂{Cu(pyzha)}₅(DMF)₅]NO₃ · 1.5DMF · 2C₆H₆ (3) are solvates, whereas compound [{La(NO₃)₂{Cu(pyzha)}₅(DMF)₅}₂(μ²-NO₃)](NO₃) · 3DMF (4) is a dimer, where μ-bridged nitrate links two copper centres of the adjacent metallamacrocycles. Complex [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₂(H₂O)(NO₃)] · CH₂Cl₂ · DMF (5) self-associates into a polymer chain by means of one pyrazine moiety and the copper ring atom. Reaction of the molecular metallacrowns with excess of inorganic salts CdBr₂ or Cu(OAc)₂ proceeds as anion methathesis process affording heteroanionic metallacrowns: molecular [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₅] [Gd(NO₃)₂{Cu(pyzha)}₅(DMF)₄(H₂O)][CdBr₄] · 1.5DMF (6), and 3D hydrogen bonded polymer [La(μ²-OAc)(H₂O)₃{Cu(pyzha)}₅ (H₂O)₄(NO₃)](NO₃) · 4H₂O (7).     

Two‐Step Oxidation Synthesis of Sulfur with a Red Aggregation‐Induced Emission

Sulfur is not normally considered a light‐emitting material, even though there have been reports of a dim luminescence of this compound in the blue‐to‐green spectral region. Now, it is shown how to make red‐emissive sulfur by a two‐step oxidation approach using elemental sulfur and Na₂S as starting materials, with a high photoluminescence quantum yield of 7.2 %. Polysulfide is formed first and is partially transformed into Na₂S₂O₃ in the first step, and then turns back to elemental S in the second step. The elevated temperature and relatively oxygen‐deficient environment during the second step transforms Na₂S₂O₃ into Na₂SO₃ incorporated with oxygen vacancies, thus resulting in the formation of a solid‐state powder consisting of elemental S embedded in Na₂SO₃. It shows aggregation‐induced emission properties, attributed to the influence of oxygen vacancies on the emission dynamics of sulfur by providing additional lower energy states that facilitate the radiative relaxation of excitons.     

Revealing Phosphorus Nitrides up to the Megabar Regime: Synthesis of α′-P3N5, δ-P3N5 and PN2

Non-metal nitrides are an exciting field of chemistry, featuring a significant number of compounds that can possess outstanding material properties. These properties mainly rely on maximizing the number of strong covalent bonds, with crosslinked XN₆ octahedra frameworks being particularly attractive. In this study, the phosphorus–nitrogen system was studied up to 137 GPa in laser-heated diamond anvil cells, and three previously unobserved phases were synthesized and characterized by single-crystal X-ray diffraction, Raman spectroscopy measurements and density functional theory calculations. δ-P₃N₅ and PN₂ were found to form at 72 and 134 GPa, respectively, and both feature dense 3D networks of the so far elusive PN₆ units. The two compounds are ultra-incompressible, having a bulk modulus of K₀=322 GPa for δ-P₃N₅ and 339 GPa for PN₂. Upon decompression below 7 GPa, δ-P₃N₅ undergoes a transformation into a novel α′-P₃N₅ solid, stable at ambient conditions, that has a unique structure type based on PN₄ tetrahedra. The formation of α′-P₃N₅ underlines that a phase space otherwise inaccessible can be explored through materials formed under high pressure.     

New Blood Coagulation Factor XIIa Inhibitors: Molecular Modeling,Synthesis, and Experimental Confirmation

In the modern world, complications caused by disorders in the blood coagulation system are found in almost all areas of medicine. Thus, the development of new, more advanced drugs that can prevent pathological conditions without disrupting normal hemostasis is an urgent task. The blood coagulation factor XIIa is one of the most promising therapeutic targets for the development of anticoagulants based on its inhibitors. The initial stage of drug development is directly related to computational methods of searching for a lead compound. In this study, docking followed by quantum chemical calculations was used to search for noncovalent low-molecular-weight factor XIIa inhibitors in a focused library of druglike compounds. As a result of the study, four low-molecular-weight compounds were experimentally confirmed as factor XIIa inhibitors. Selectivity testing revealed that two of the identified factor XIIa inhibitors were selective over the coagulation factors Xa and XIa.     

Panel‐based stratified cluster sampling and analysis for photovoltaic outdoor measurements

We study a stratified multisite cluster‐sampling panel time series approach in order to analyse and evaluate the quality and reliability of produced items, motivated by the problem to sample and analyse multisite outdoor measurements from photovoltaic systems. The specific stratified sampling in spatial clusters reduces sampling costs and allows for heterogeneity as well as for the analysis of spatial correlations due to defects and damages that tend to occur in clusters. The analysis is based on weighted least squares using data‐dependent weights. We show that this does not affect consistency and asymptotic normality of the least squares estimator under the proposed sampling design under general conditions. The estimation of the relevant variance–covariance matrices is discussed in detail for various models including nested designs and random effects. The strata corresponding to damages or manufacturers are modelled via a quality feature by means of a threshold approach. The analysis of outdoor electroluminescence images shows that spatial correlations and local clusters may arise in such photovoltaic data. Further, relevant statistics such as the mean pixel intensity cannot be assumed to follow a Gaussian law. We investigate the proposed inferential tools in detail by simulations in order to assess the influence of spatial cluster correlations and serial correlations on the test's size and power. ©2016 The Authors. Applied Stochastic Models in Business and Industry published by John Wiley & Sons, Ltd.     

Electric-field-induced symmetry breaking of angular momentum distribution in atoms

We report the experimental observation of alignment to orientation conversion in the 7D3/2 and 9D3/2 states of Cs in the presence of an external dc electric field and without the influence of magnetic fields or atomic collisions. Initial alignment of angular momentum states was created by two-step excitation with linearly polarized laser radiation. The appearance of transverse orientation of angular momentum was confirmed by the observation of circularly polarized light. We present experimentally measured signals and compare them with the results of a detailed theoretical model based on the optical Bloch equations. The effect is odd under time reversal and should be taken into account in ever more sensitive searches for an electron electric dipole moment.     

Multicanonical Monte Carlo modelling of BER penalty in transmission systems with optical regeneration

A quantitative analysis of the BER penalty due to deviations from the optimal decision level in systems employing optical regeneration is presented. Applying extensive Multicanonical Monte Carlo modelling we study the accumulation of BER with propagation and compare different analytical approximations of the regenerator nonlinear transfer function.     

On the nuclear modification factor at RHIC and LHC

We show that pQCD factorization incorporated with pre-hadronization energy-loss effect naturally leads to flatness of the nuclear modification factor RAA$R_{\mathit{AA}}$ for produced hadrons at high transverse momentum pT$p_T$. We consider two possible scenarios for the pre-hadronization: In scenario 1, the produced gluon propagates through dense QCD medium and loses energy. In scenario 2, all gluons first decay to quark–antiquark pairs and then each pair loses energy as propagating through the medium. We show that the estimates of the energy-loss in these two different models lead to very close values and is able to explain the suppression of high-pT$p_T$ hadrons in nucleus–nucleus collisions at RHIC. We show that the onset of the flatness of RAA$R_{\mathit{AA}}$ for the produced hadron in central collisions at midrapidity is about pT≈15$p_T\approx 15$ and 25 GeV at RHIC and the LHC energies, respectively. We show that the smallness (RAA<0.5$R_{\mathit{AA}}<0.5$ ) and the high-pT$p_T$ flatness of RAA$R_{\mathit{AA}}$ obtained from the kT$k_T$ factorization supplemented with the Balitsky–Kovchegov (BK) equation is rather generic and it does not strongly depend on the details of the BK solutions. We show that energy-loss effect reduces the nuclear modification factor obtained from the kT$k_T$ factorization about 30–50% at moderate pT$p_T$.     

Complete band gaps in one-dimensional left-handed periodic structures

Artificially fabricated structures with periodically modulated parameters such as photonic crystals offer novel ways of controlling the flow of light due to the existence of a range of forbidden frequencies associated with a photonic band gap. It is believed that modulation of the refractive index in all three spatial dimensions is required to open a complete band gap and prevent the propagation of electromagnetic waves in all directions. Here we reveal that, in sharp contrast to what was known before and contrary to the accepted physical intuition, a one-dimensional periodic structure containing the layers of transparent left-handed (or negative-index) metamaterial can trap light in three-dimensional space due to the existence of a complete band gap.     

Uniform integral representation for the fluctuating field propagating through the multi-scale media

A uniform integral representation for the wave field propagating through the statistically homogeneous multi-scale medium was obtained. It is shown that the considered expression for the field contains the limiting cases for both the Born’s approximation for the single-scattered field and a phase approximation of geometric optics method. Hybrid method formulae for calculation of the fluctuation field, taking into account the effect of backscattering enhancement can be obtained from the investigated integral representation, provided that the spectrum of inhomogeneities can be represented as a sum of two uncorrelated components: small-scale and large-scale. The paper contains the numerical simulation results of the effect of average intensity enhancement of the backscattered field in the medium containing both large- and small-scale irregularities. Unlike the hybrid method of calculation, the proposed approach does not require explicit separation of the inhomogeneities spectrum into two uncorrelated components and allows investigating the effect of the average intensity enhancement of the backscattered field in a more general situation. In particular, numerical calculations have shown that the effect of enhancement of the backscattered signal may occur in the study of the high-latitude ionosphere by method of incoherent scattering of radio waves.