Resonance Assisted Chalcogen Bonding as a New Synthon in the Design of Dyes

Intramolecular chalcogen bonding in arylhydrazones of sulfamethizole is strengthened by conjugation in the π-system of a noncovalent five-membered ring. The S⋅⋅⋅O distance in the sulfamethizole moiety of these compounds ranges from 2.698(3) to 2.806(15) Å, which indicates its strong dependence on the attached arylhydrazone fragments. Information on the nature of the intramolecular chalcogen bond was afforded by DFT calculations.     

Stochastic modeling of quality of systems operating in a heterogeneous environment

We consider systems that are subject to an external mixed Poisson shock process. Each shock can result in a failure of a system with a given probability and is survived with the complementary probability. Each shock additionally decreases the quality function that describes the performance of a system, thus forming the corresponding stochastic process. Expectations (unconditional and conditional on survival) and relevant variability characteristics for the stochastic quality function are derived. Some monotonicity properties of the conditional quality function are investigated and the future values of this function are derived.     

Pulsed EPR Dipolar Spectroscopy under the Breakdown of the High-Field Approximation: The High-Spin Iron(III) Case

Pulsed EPR dipolar spectroscopy (PDS) offers several methods for measuring dipolar coupling and thus the distance between electron-spin centers. To date, PDS measurements to metal centers were limited to ions that adhere to the high-field approximation. Here, the PDS methodology is extended to cases where the high-field approximation breaks down on the example of the high-spin Fe³⁺/nitroxide spin-pair. First, the theory developed by Maryasov et al. (Appl. Magn. Reson. 2006 , 30, 683–702) was adapted to derive equations for the dipolar coupling constant, which revealed that the dipolar spectrum does not only depend on the length and orientation of the interspin distance vector with respect to the applied magnetic field but also on its orientation to the effective g-tensor of the Fe³⁺ ion. Then, it is shown on a model system and a heme protein that a PDS method called relaxation-induced dipolar modulation enhancement (RIDME) is well-suited to measuring such spectra and that the experimentally obtained dipolar spectra are in full agreement with the derived equations. Finally, a RIDME data analysis procedure was developed, which facilitates the determination of distance and angular distributions from the RIDME data. Thus, this study enables the application of PDS to for example, the highly relevant class of high-spin Fe³⁺ heme proteins.     

Cyclometallated 1,2,3-triazol-5-ylidene iridium(III) complexes: synthesis,structure, and photoluminescence properties

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Synthesis,X-ray and DFT Studies of 6-halo-3-(hydroxymethyl)cinnolin-4(1H)-ones

Chemistry of Heterocyclic Compounds - The Richter cyclization was used for the synthesis of 6-halo-3-(hydroxymethyl)cinnolin-4(1H)-ones. X-ray analysis revealed that these compounds exist as dimers...     

On a single discrete scale for preventive maintenance with two shock processes affecting a complex system

A new approach to optimal maintenance of systems (networks) is suggested. It is applied to systems subject to two external independent shock processes. A system ‘consists’ of two parts, and each shock process affects only its own part. A new notion of bivariate signature is suggested and used for obtaining survival characteristics of a system and further optimization of the preventive maintenance actions. The preventive maintenance optimization is considered in the univariate discrete scale that counts the overall numbers of shocks of both types. An example of a transportation network is considered. Copyright © 2016 John Wiley & Sons, Ltd.     

Spectral Photoluminescent Parameters of Barley Seeds (Hordéum vulgáre) Infected with Fusarium ssp

We needed effective and sustainable technologies for better microbiological control of crops, including Fusarium. However, photoluminescent UV–Vis methods are potential for diagnosing plant diseases with Fusarium. It has not been sufficiently studied despite the application of these methods for other biological researches. The excitation spectrum of the seeds during infection shifts to the shorter wavelength and a new maximum appears in the region λ ≈ 232 nm. The photoluminescence of infected seeds increases with excitation by radiation of wavelengths λ_e,1 = 232 nm, λ_e,2 = 362 nm and λ_e,3 = 424 nm by 1.33–3.14 times, and λ_e,3 = 424 nm—decreases by 1.1 times. Statistical moments μ₃ and μ₄, asymmetry and kurtosis change only with short-wave excitation. When analyzing the decomposition of the frequency spectrum into Gaussian curves, the most informative ratio is the ratio of right-handed and left-handed Gaussians under excitation λ_e,2 = 362 nm and λ_e,3 = 424 nm. The ratios of their maxima change during infection by 1.36–3.2 times, and for excitation by radiation λ_e,2, the frequency boundaries of Gaussians change. The results of measurements and calculations provide a basis for the development of a method and device for photoluminescence diagnostics of fusarium seeds in UV–Vis ranges.