Mass-spectrometric study of molecular and ionic sublimation of gadolinium and terbium tribromides in Knudsen and Langmuir modes

Molecular and ionic sublimation of gadolinium and terbium tribromides in Knudsen and Langmuire modes was studied by the method of high-temperature mass-spectrometry. On the basis of obtained enthalpies of sublimation and ion-molecule reactions the enthalpies of formation of LnBr3 and Ln2Br6 molecules and LnBr4− and Ln2Br7− negative ions were determined. For the first time the electron work function for crystals of the studied tribromides was calculate

Features of ultrasound and dopplerometric endometry examination in autoimmune thyroiditis patients with abnormal uterine bleeding

Abnormal uterine bleeding  occurs in 10–30% of reproductive age women. Ultrasound examination is one of the most effective methods of diagnosing lesions of the pelvic organs while it has high sensitivity (96%), but low specificity (13.8%) in relation to endometrial lesions, the informativeness of ultrasound in the diagnosis of abnormal uterine bleeding ranges from 60 to 93.3%. It had been revealed revealed that the imbalance of thyroid hormones can have a direct effect on the endometrium. Thus, the analysis of ultrasound examinations data  together with dopplerometric assessment of the blood flow of the internal genital organs in autoimmune thyroiditis patients with abnormal uterine bleeding is an urgent task of modern gynecology. The purpose is to determine the features of ultrasound exanimation with Doppler assessment of the endometrium  in autoimmune thyroiditis patients with abnormal uterine bleeding. Materials and methods.  The patients’ examinations were carried out from 2019 to 2022 We examined 120 patients, of whom 90 (75%) suffered from abnormal uterine bleeding and 30 (25%) did not have signs of gynecological and somatic pathology (control group). Abnormal bleeding patients average age was 36.3±3.2 years. The average age of bleeding and thyroid pathology women was 34.8±2.6 years, the control group average age was 30.7±2.9 years. Results. Echographic signs of endometrium structural changes were detected in 83 (92.2%) of abnormal nautoimmune bleeding women and in 7 (7.8%) women ultrasound signs of pathology were not detected. Significant differences were found when analyzing the results of ultrasonographic examination of patients with bleeding and bleeding + thyroid pathology. Conclusion. Ultrasound is an important method that contributes to a significant improvement in the diagnosis of isolated or combined benign uterine diseases in women with abnormal autoimmune bleeding at the background of thyroid pathology, and in most cases corresponds to the histological diagnosis

Aspects of blockchain reliability considering its consensus algorithms

The reliability of blockchain as an information system is discussed in this article. There were considered two types of models for blockchain systems. One assumes an almost ideal decentralized network with the probability of a software crush on an independent nodes, other adds to this approach a probability of the communication channels corruption. We study consensus algorithms used in blockchain and make assumptions about their reliability and functioning in practice

Implementation of analytical Hartree-Fock gradients for periodic systems

We describe the implementation of analytical Hartree-Fock gradients for periodic systems in the code CRYSTAL, emphasizing the technical aspects of this task. The code is now capable of calculating analytical derivatives with respect to nuclear coordinates for systems periodic in 0, 1, 2 and 3 dimensions (i.e. molecules, polymers, slabs and solids). Both closed-shell restricted and unrestricted Hartree-Fock gradients have been implemented. A comparison with numerical derivatives shows that the forces are highly accurate.Comment: accepted by Comp. Phys. Com

Electronic Structures and Bonding of Oxygen on Plutonium Layers

Oxygen adsorption on delta-Pu (100) and (111) surfaces have been studied at both non-spin-polarized and spin-polarized levels using the generalized gradient approximation of density functional theory (GGA-DFT)with Perdew and Wang functionals. The center position of the (100) surface is found to be the most favorable site with chemisorption energies of 7.386 eV and 7.080 eV at the two levels of theory. The distances of the oxygen adatom from the Pu surface are found to be 0.92A and 1.02A, respectively. For the (111) surface non-spin-polarized calculations, the center position is also the preferred site with a chemisorption energy of 7.070 eV and the distance of the adatom being 1.31A, but for spin-polarized calculations the bridge and the center sites are found to be basically degenerate, the difference in chemisorption energies being only 0.021 eV. In general, due to the adsorption of oxygen, plutonium 5f orbitals are pushed further below the Fermi energy, compared to the bare plutonium layers. The work function, in general, increases due to oxygen adsorption on plutonium surfaces.Comment: Spin-polarization is considered, and the paper is revised accordingl

Probing the 5f Electrons in Am-I by Hybrid Density Functional Theory

The ground states of the actinides and their compounds continue to be matters of considerable controversies. Experimentally, Americium-I (Am-I) is a non-magnetic dhcp metal whereas theoretically an anti-ferromagnetic ground state is predicted. We show that hybrid density functional theory, which admixes a fraction of exact Hartree-Fock (HF) exchange with approximate DFT exchange, can correctly reproduce the ground state properties of Am. In particular, for a 0.40 fraction of HF exchange we obtain a non-magnetic ground state with equilibrium atomic volume, bulk modulus, 5f electron population, and the density of electronic states all in good agreement with experimental data. We argue that the exact HF exchange corrects the overestimation of the approximate DFT exchange interaction.Comment: 1 table, 4 figures. Chemical Physics Letters, in press (2009

Determination of the Bending Rigidity of Graphene via Electrostatic Actuation of Buckled Membranes

The small mass and atomic-scale thickness of graphene membranes make them highly suitable for nanoelectromechanical devices such as e.g. mass sensors, high frequency resonators or memory elements. Although only atomically thick, many of the mechanical properties of graphene membranes can be described by classical continuum mechanics. An important parameter for predicting the performance and linearity of graphene nanoelectromechanical devices as well as for describing ripple formation and other properties such as electron scattering mechanisms, is the bending rigidity, {\kappa}. In spite of the importance of this parameter it has so far only been estimated indirectly for monolayer graphene from the phonon spectrum of graphite, estimated from AFM measurements or predicted from ab initio calculations or bond-order potential models. Here, we employ a new approach to the experimental determination of {\kappa} by exploiting the snap-through instability in pre-buckled graphene membranes. We demonstrate the reproducible fabrication of convex buckled graphene membranes by controlling the thermal stress during the fabrication procedure and show the abrupt switching from convex to concave geometry that occurs when electrostatic pressure is applied via an underlying gate electrode. The bending rigidity of bilayer graphene membranes under ambient conditions was determined to be $35.5^{+20}_{-15}$ eV. Monolayers have significantly lower {\kappa} than bilayers

Topological mechanochemistry of graphene

In view of a formal topology, two common terms, namely, connectivity and adjacency, determine the quality of C-C bonds of sp2 nanocarbons. The feature is the most sensitive point of the inherent topology of the species so that such external action as mechanical deformation should obviously change it and result in particular topological effects. The current paper describes the effects caused by uniaxial tension of a graphene molecule in due course of a mechanochemical reaction. Basing on the molecular theory of graphene, the effects are attributed to both mechanical loading and chemical modification of edge atoms of the molecule. The mechanical behavior is shown to be not only highly anisotropic with respect to the direction of the load application, but greatly dependent on the chemical modification of the molecule edge atoms thus revealing topological character of the graphene deformation.Comment: 9 pages, 10 figures, 1 table. arXiv admin note: text overlap with arXiv:1301.094

Structure-Sensitive Mechanism of Nanographene Failure

The response of a nanographene sheet to external stresses is considered in terms of a mechanochemical reaction. The quantum chemical realization of the approach is based on a coordinate-of-reaction concept for the purpose of introducing a mechanochemical internal coordinate (MIC) that specifies a deformational mode. The related force of response is calculated as the energy gradient along the MIC, while the atomic configuration is optimized over all of the other coordinates under the MIC constant-pitch elongation. The approach is applied to the benzene molecule and (5, 5) nanographene. A drastic anisotropy in the microscopic behavior of both objects under elongation along a MIC has been observed when the MIC is oriented either along or normally to the C-C bonds chain. Both the anisotropy and high stiffness of the nanographene originate at the response of the benzenoid unit to stress.Comment: 19 pages, 7 figures 1 tabl

The fate of oxidative strand breaks in mitochondrial DNA

Mitochondrial DNA (mtDNA) is particularly vulnerable to somatic mutagenesis. Potential mechanisms include DNA polymerase γ (POLG) errors and the effects of mutagens, such as reactive oxygen species. Here, we studied the effects of transient hydrogen peroxide (H(2)O(2) pulse) on mtDNA integrity in cultured HEK 293 cells, applying Southern blotting, ultra-deep short-read and long-read sequencing. In wild-type cells, 30 min after the H(2)O(2) pulse, linear mtDNA fragments appear, representing double-strand breaks (DSB) with ends characterized by short GC stretches. Intact supercoiled mtDNA species reappear within 2–6 h after treatment and are almost completely recovered after 24 h. BrdU incorporation is lower in H(2)O(2)-treated cells compared to non-treated cells, suggesting that fast recovery is not associated with mtDNA replication, but is driven by rapid repair of single-strand breaks (SSBs) and degradation of DSB-generated linear fragments. Genetic inactivation of mtDNA degradation in exonuclease deficient POLG p.D274A mutant cells results in the persistence of linear mtDNA fragments with no impact on the repair of SSBs. In conclusion, our data highlight the interplay between the rapid processes of SSB repair and DSB degradation and the much slower mtDNA re-synthesis after oxidative damage, which has important implications for mtDNA quality control and the potential generation of somatic mtDNA deletions