Spin-polarized electronic structure of the core-shell ZnO/ZnO:Mn nanowires probed by x-ray absorption and emission spectroscopy

The combination of x-ray spectroscopy methods complemented with theoretical analysis unravels the coexistence of paramagnetic and antiferromagnetic phases in the Zn_0.9Mn_0.1O shell deposited onto array of wurtzite ZnO nanowires. The shell is crystalline with orientation toward the ZnO growth axis, as demonstrated by X-ray linear dichroism. EXAFS analysis confirmed that more than 90% of Mn atoms substituted Zn in the shell while fraction of secondary phases was below 10%. The value of manganese spin magnetic moment was estimated from the Mn K{\beta} X-ray emission spectroscopy to be 4.3{\mu}B which is close to the theoretical value for substitutional Mn_Zn. However the analysis of L_2,3 x-ray magnetic circular dichroism data showed paramagnetic behaviour with saturated spin magnetic moment value of 1.95{\mu}B as determined directly from the spin sum rule. After quantitative analysis employing atomic multiplet simulations such difference was explained by a coexistence of paramagnetic phase and local antiferromagnetic coupling of Mn magnetic moments. Finally, spin-polarized electron density of states was probed by the spin-resolved Mn K-edge XANES spectroscopy and consequently analyzed by band structure calculations.Comment: Supplementary information available at http://www.rsc.org/suppdata/ja/c3/c3ja50153a/c3ja50153a.pdf J. Anal. At. Spectrom., 201

Vascular changes in diabetic retinopathy-a longitudinal study in the Nile rat.

Diabetic retinopathy is the most common microvascular complication of diabetes and is a major cause of blindness, but an understanding of the pathogenesis of the disease has been hampered by a lack of accurate animal models. Here, we explore the dynamics of retinal cellular changes in the Nile rat (Arvicanthis niloticus), a carbohydrate-sensitive model for type 2 diabetes. The early retinal changes in diabetic Nile rats included increased acellular capillaries and loss of pericytes that correlated linearly with the duration of diabetes. These vascular changes occurred in the presence of microglial infiltration but in the absence of retinal ganglion cell loss. After a prolonged duration of diabetes, the Nile rat also exhibits a spectrum of retinal lesions commonly seen in the human condition including vascular leakage, capillary non-perfusion, and neovascularization. Our longitudinal study documents a range and progression of retinal lesions in the diabetic Nile rat remarkably similar to those observed in human diabetic retinopathy, and suggests that this model will be valuable in identifying new therapeutic strategies

Luminescent coordination polymers based on Ca²⁺ and octahedral cluster anions [{M₆Clⁱ₈}Clᵃ₆}²⁻ (M = Mo, W) : synthesis and thermal stability studies

Luminescent coordination polymers (CPs) based of inexpensive stable precursors are attractive materials for applications. Here we report the synthesis and evaluation of the stability and photophysical characteristics of the first examples of phosphorescent CPs based on octahedral molybdenum and tungsten cluster anions. Specifically 1D CP trans-[{Ca(OPPh₃)₄}{{M₆Clⁱ₈}Clᵃ₆}]∞ (M = Mo, W) can be obtained either directly at increased temperature or via intermediate phases [cis-Ca(OPPh₃)₄(H₂O)₂][{M₆Clⁱ₈}Clᵃ₆]∙2CH₃CN that are stable at room-temperature, but convert to the titled CP at temperatures above 100 °C

Joint effect of the mycotoxins T-2 toxin, deoxynivalenol and zearalenone on the weaner pigs against a background of the infection load

Currently, among more than 100 000 known species of fungi about 250 species produce mycotoxins, secondary metabolites which are dangerous to human and animal health. Most of these toxins are highly resistant to physical and chemical factors, and are not destroyed even after prolonged heating of feed contaminated with mycotoxins. The aim of the present study was to investigate the joint effects of T-2 toxin, zearalenone, deoxynivalenol and infectious agents on pigs. The study was conducted inthe Federal Center for Toxicological, Radiation and BiologicalSafety. Studies have shown that the jointdietary intake T-2 toxin at a dose of 70 mg/kg, zearalenoneat a dose of 50 mg/kg and deoxynivalenolat a dose of 1000 mg/kg for 30 days against a background of the simulated Clostridium infection load causes symptomatic mycotoxicosis which is accompanied by activation of lipoperoxidation, decrease in hematological, biochemical and immunological parameters: a reduction in the number of T and B lymphocytes, titers of specific protective antibodies and the development of pathological processes in the tissues and organs of weaner pigs, slow weight gain, increase in feed conversion ratio and the development of infectious disease, confirmed with laboratory tests. The result was different in the group of animals with the same infection load but without introducing mycotoxins into the animal diet. The findings provide strong evidence that chronic intake of fuzariotoxins even at the level of permissible concentrations against a background of infection load predisposes to infectious diseases

A process-based model of methane consumption by upland soils

This study combines a literature survey and field observation data in an ad initio attempt to construct a process-based model of methane sink in upland soils including both the biological and physical aspects of the process. Comparison is drawn between the predicted sink rates and chamber measurements in several forest and grassland sites in the southern part of West Siberia. CH4 flux, total respiration, air and soil temperature, soil moisture, pH, organic content, bulk density and solid phase density were measured during a field campaign in summer 2014. Two datasets from literature were also used for model validation. The modeled sink rates were found to be in relatively good correspondence with the values obtained in the field. Introduction of the rhizospheric methanotrophy significantly improves the match between the model and the observations. The Q10 values of methane sink observed in the field were 1.2-1.4, which is in good agreement with the experimental results from the other studies. Based on modeling results, we also conclude that soil oxygen concentration is not a limiting factor for methane sink in upland forest and grassland ecosystems.Peer reviewe

An approach to verification and validation of MHD codes for fusion applications

We propose a new activity on verification and validation (V&V) of MHD codes presently employed by the fusion community as a predictive capability tool for liquid metal cooling applications, such as liquid metal blankets. The important steps in the development of MHD codes starting from the 1970s are outlined first and then basic MHD codes, which are currently in use by designers of liquid breeder blankets, are reviewed. A benchmark database of five problems has been proposed to cover a wide range of MHD flows from laminar fully developed to turbulent flows, which are of interest for fusion applications: (A) 2D fully developed laminar steady MHD flow, (B) 3D laminar, steady developing MHD flow in a non-uniform magnetic field, (C) quasi-two-dimensional MHD turbulent flow, (D) 3D turbulent MHD flow, and (E) MHD flow with heat transfer (buoyant convection). Finally, we introduce important details of the proposed activities, such as basic V&V rules and schedule. The main goal of the present paper is to help in establishing an efficient V&V framework and to initiate benchmarking among interested parties. The comparison results computed by the codes against analytical solutions and trusted experimental and numerical data as well as code-to-code comparisons will be presented and analyzed in companion paper/paper

Spin-state studies with XES and RIXS: From static to ultrafast

We report on extending hard X-ray emission spectroscopy (XES) along with resonant inelastic X-ray scattering (RIXS) to study ultrafast phenomena in a pump-probe scheme at MHz repetition rates. The investigated systems include low-spin (LS) Fe-II complex compounds, where optical pulses induce a spin-state transition to their (sub)nanosecond-lived high-spin (HS) state. Time-resolved XES clearly reflects the spin-state variations with very high signal-to-noise ratio, in agreement with HS-LS difference spectra measured at thermal spin crossover, and reference HS-LS systems in static experiments, next to multiplet calculations. The 1s2p RIXS, measured at the Fe Is pre-edge region, shows variations after laser excitation, which are consistent with the formation of the HS state. Our results demonstrate that X-ray spectroscopy experiments with overall rather weak signals, such as RIXS, can now be reliably exploited to study chemical and physical transformations on ultrafast time scales. (C) 2012 Elsevier B.V. All rights reserved

Quantum chemical calculations of X-ray emission spectroscopy

The calculation of X-ray emission spectroscopy with equation of motion coupled cluster theory (EOM-CCSD), time dependent density functional theory (TDDFT) and resolution of the identity single excitation configuration interaction with second order perturbation theory (RI-CIS(D)) is studied. These methods can be applied to calculate X-ray emission transitions by using a reference determinant with a core-hole, and they provide a convenient approach to compute the X-ray emission spectroscopy of large systems since all of the required states can be obtained within a single calculation removing the need to perform a separate calculation for each state. For all of the methods, basis sets with the inclusion of additional basis functions to describe core orbitals are necessary, particularly when studying transitions involving the 1s or- bitals of heavier nuclei. EOM-CCSD predicts accurate transition energies when compared with experiment, however, its application to larger systems is restricted by its computational cost and difficulty in converging the CCSD equations for a core-hole reference determinant, which become increasing problematic as the size of the system studied increases. While RI-CIS(D) gives accurate transition energies for small molecules containing first row nuclei, its application to larger systems is limited by the CIS states providing a poor zeroth order reference for perturbation theory which leads to very large errors in the computed transition energies for some states. TDDFT with standard exchange-correlation functionals predicts transition energies that are much larger than experiment. Optimization of a hybrid and short-range cor- rected functional to predict the X-ray emission transitions results in much closer agreement with EOM-CCSD. The most accurate exchange-correlation functional identified is a modified B3LYP hybrid functional with 66% Hartree-Fock exchange, denoted B66LYP, which predicts X-ray emission spectra for a range of molecules including fluorobenzene, nitrobenzene, ace- tone, dimethyl sulfoxide and CF3Cl in good agreement with experiment

Treatment of cryptorchidism in pediatric surgical practice: a multicenter study

Introduction. Cryptorchidism is a common disease in pediatric urological and andrological practice since the issues of tactical approaches and its optimal treatment remain extremely relevant. Cryptorchidism makes a significant contribution to the structure of male infertility.Objective. To conduct a retrospective analysis of treatment results in children and adolescents with cryptorchidism.Materials & methods. This study summarises the treatment results of 8308 patients with cryptorchidism aged from 6 months to 17 years who underwent inpatient treatment in the Russian Federation and the Republic of Uzbekistan.Results. It was revealed that from 2015 to 2019, patients were admitted for surgical treatment evenly over the years. The ratio of right-sided / left-sided / bilateral cryptorchidism was 4.6 : 4.4 : 1 The inguinal form prevailed more than 6 times over the abdominal location. At the same time, 26.1% of the patients underwent surgery at the optimal time, and 9.8% were older than 10 years. More often, children are operated from an open inguinal access (95.0%), much less often — laparoscopically and percutaneously. Stage-by-stage treatment was carried out in 6.0% of patients.Conclusion. Thus, the approach presented in the study in the surgical treatment of cryptorchidism provided good treatment results. The number of disease relapses was 1.9% (mainly among children over 7 years old). Most surgeons are very reserved about primary orchidectomies (only 3.8% were performed)