15 research outputs found

    The Semantic and Etymological Peculiarities of the Verbs of Blame

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    The article deals with the semantic analysis of the verbs of blame (brawl, castigate, condemn, curse, damn, lecture, rate, rebuke, reprehend, reprimand, reproach, reprobate, reprove, row, strafe, swear, trounce) in the perspective of semantics, as well as etymology. In accordance with the dominant cross-disciplinary approach to the linguistic research, the semantics of the verbs under study is analyzed in correlation with the relevant extra-linguistic data. It reveals the necessity of using some data of cognitive linguistics together with etymological methods of semantic analysis. The complex of cognitive and etymological methods helps to determine the functioning of the verbs in different kinds of discourse, and to find the closest equivalent in the Russian language

    Redox Regulation of Calcium Signaling in Cancer Cells by Ascorbic Acid Involving the Mitochondrial Electron Transport Chain

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    Previously, we have reported that ascorbic acid regulates calcium signaling in human larynx carcinoma HEp-2 cells. To evaluate the precise mechanism of Ca2+ release by ascorbic acid, the effects of specific inhibitors of the electron transport chain components on mitochondrial reactive oxygen species (ROS) production and Ca2+ mobilization in HEp-2 cells were investigated. It was revealed that the mitochondrial complex III inhibitor (antimycin A) amplifies ascorbate-induced Ca2+ release from intracellular stores. The mitochondrial complex I inhibitor (rotenone) decreases Ca2+ release from intracellular stores in HEp-2 cells caused by ascorbic acid and antimycin A. In the presence of rotenone, antimycin A stimulates ROS production by mitochondria. Ascorbate-induced Ca2+ release in HEp-2 cells is shown to be unaffected by catalase. The results obtained suggest that Ca2+ release in HEp-2 cells caused by ascorbic acid is associated with induced mitochondrial ROS production. The data obtained are in line with the concept of redox signaling that explains oxidant action by compartmentalization of ROS production and oxidant targets

    Two Mechanisms of Chlorocuprate Reactions with Alkyl Radicals: Dramatic Role of Nuclearity

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    Interaction of copper chlorides with radicals is a key step of single electron transfer reactions and is responsible for high selectivity of copper-catalyzed radical processes. In the present article reactions of binuclear copper­(II) chlorides with methyl radical were studied in the scope of density functional theory. The results of quantum-chemical calculations of potential energy surfaces allow proposing that there are at least two reasons for the lower activity of binuclear complexes Cu<sub>2</sub>Cl<sub>6</sub><sup>2–</sup> in comparison with CuCl<sub>4</sub><sup>2–</sup>. First, the radicals react with binuclear chlorocuprates via an atom transfer mechanism through an activation barrier, in contrast to the barrierless character of such reactions with partition of CuCl<sub>4</sub><sup>2–</sup>. Second, only in the systems with binuclear copper chloro complexes may an alternative path of spontaneous formation of chloroorganocuprates be realized. These intermediates may be dormant species in radical reactions

    Inhomogeneities in PNIPAM Aqueous Solutions: The Inside View by Spin Probe EPR Spectroscopy

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    Coil to globule transition in poly(N-isopropylacrylamide) aqueous solutions was studied using spin probe continuous-wave electronic paramagnetic resonance (CW EPR) spectroscopy with an amphiphilic TEMPO radical as a guest molecule. Using Cu(II) ions as the “quencher” for fast-moving radicals in the liquid phase allowed obtaining the individual spectra of TEMPO radicals in polymer globule and observing inhomogeneities in solutions before globule collapsing. EPR spectra simulations confirm the formation of molten globules at the first step with further collapsing and water molecules coming out of the globule, making it denser

    Structure and Dynamics of Inhomogeneities in Aqueous Solutions of Graft Copolymers of N-Isopropylacrylamide with Lactide (P(NIPAM-<i>graft</i>-PLA)) by Spin Probe EPR Spectroscopy

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    Coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers of NIPAM with different content of oligolactide groups were studied using spin probe continuous wave EPR spectroscopy. The technique of the suppressing of TEMPO as spin probe by spin exchange with Cu2+ ions was applied. This approach allowed us to detect individual EPR spectra of the probe in collapsed globules and estimate its magnetic and dynamic parameters reliably. The formation of inhomogeneities at temperatures lower than the volume phase transition temperature measured via transmission, and differential scanning calorimetry was fixed. An increase in oligolactide content in copolymers leads to the formation of looser globules, allowing for the exchange of the probe molecules between the globules and the external solution

    New Insight into the Mechanism of Drug Release from Poly(d,l-lactide) Film by Electron Paramagnetic Resonance

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    A novel approach based on convolution of the electron paramagnetic resonance (EPR) spectra was used for quantitative study of the release kinetics of paramagnetic dopants from poly(d,l-lactide) films. A non-monotonic dependence of the release rate on time was reliably recorded. The release regularities were compared with the dynamics of polymer structure changes determined by EPR, SEM, and optic microscopy. The data obtained allow for the conclusion that the main factor governing dopant release is the formation of pores connected with the surface. In contrast, the contribution of the dopant diffusion through the polymer matrix is negligible. The dopant release can be divided into two phases: release through surface pores, which are partially closed with time, and release through pores initially formed inside the polymer matrix due to autocatalytic hydrolysis of the polymer and gradually connected to the surface of the sample. For some time, these processes co-occur. The mathematical model of the release kinetics based on pore formation is presented, describing the kinetics of release of various dopants from the polymer films of different thicknesses

    Effect of graphene grains size on the microwave electromagnetic shielding effectiveness of graphene/polymer multilayers

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    The influence of CVD graphene grain size on the electromagnetic (EM) shielding performance of graphene/polymethyl methacrylate (PMMA) multilayers in Ka-band was studied both experimentally and theoreti- cally. We found that increasing the average graphene grain size from 20 to 400 microns does not change the EM properties of heterostructures consisting of graphene layers sandwiched between sub-micron thick PMMA spacers. The independence of EM interference shielding effectiveness on the graphene grain size between 20 to 400 microns allows one to use cheaper (or more convenient regimes of CVD) graphene samples with low crystallinity and small grain size in the development of new graphene-based passive electromagnetic devices operated at high frequencies

    Solute Diffusion into Polymer Swollen by Supercritical CO2 by High-Pressure Electron Paramagnetic Resonance Spectroscopy and Chromatography

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    High-pressure electron paramagnetic resonance (EPR) was used to measure translational diffusion coefficients (Dtr) of a TEMPONE spin probe in poly(D,L-lactide) (PDLLA) and swollen in supercritical CO2. Dtr was measured on two scales: macroscopic scale (&gt;1 μm), by measuring spin probe uptake by the sample; and microscopic scale (&lt;10 nm), by using concentration-dependent spectrum broadening. Both methods yield similar translational diffusion coefficients (in the range 5–10 × 10−12 m2/s at 40–60 °C and 8–10 MPa). Swollen PDLLA was found to be homogeneous on the nanometer scale, although the TEMPONE spin probe in the polymer exhibited higher rotational mobility (τcorr = 6 × 10−11 s) than expected, based on its Dtr. To measure distribution coefficients of the solute between the swollen polymer and the supercritical medium, supercritical chromatography with sampling directly from the high-pressure vessel was used. A distinct difference between powder and bulk polymer samples was only observed at the start of the impregnation process

    New Allosteric Modulators of AMPA Receptors: Synthesis and Study of Their Functional Activity by Radioligand-Receptor Binding Analysis

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    The synthetic approaches to three new AMPA receptor modulators—derivatives of 1,11-dimethyl-3,6,9-triazatricyclo[7.3.1.13,11]tetradecane-4,8,12-trione—had been developed and all steps of synthesis were optimized. The structures of the compounds contain tricyclic cage and indane fragments necessary for binding with the target receptor. Their physiological activity was studied by radioligand-receptor binding analysis using [3H]PAM-43 as a reference ligand, which is a highly potent positive allosteric modulator of AMPA receptors. The results of radioligand-binding studies indicated the high potency of two synthesized compounds to bind with the same targets as positive allosteric modulator PAM-43 (at least on AMPA receptors). We suggest that the Glu-dependent specific binding site of [3H]PAM-43 or the receptor containing this site may be one of the targets of the new compounds. We also suggest that enhanced radioligand binding may indicate the existence of synergistic effects of compounds 11b and 11c with respect to PAM-43 binding to the targets. At the same time, these compounds may not compete directly with PAM-43 for its specific binding sites but bind to other specific sites of this biotarget, changing its conformation and thereby causing a synergistic effect of cooperative interaction. It can be expected that the newly synthesized compounds will also have pronounced effects on the glutamatergic system of the mammalian brain
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