Influence of different O2/H2O ratios on He atmospheric pressure plasma jet impinging on a dielectric surface

A two dimensional (2D) axisymmetric fluid model is built to investigate the effect of different O2 and H2O admixture on the plasma dynamics and the distribution of reactive species in He atmospheric pressure plasma jet (APPJ). The increase of O2: H2O ratio slows down both the intensity and the propagation speed of ionization wave. Due to the decrease of both H2O ionization rate and H2O Penning ionization as well as the stronger electronegativity of O2, the increase of O2: H2O ratio results in a significant reduction of electron density in the APPJ, which restricts the occurrence of electron collision ionization reactions and inhibits the propagation of plasma. The excitation energy loss of O2 is not the reason for the weakening of the plasma ionization wave. The densities of O2+, O- and O2- increase with the rise of O2 admixture while H2O+ decreases due to the decrease of electron density and H2O concentration. OH- density is affected by both the increase of O- and the decrease of H2O so it shows peak in the case of O2: H2O=7:3. O is mainly produced by the excitation reactions and the electron recombination reaction (e + O2+ → 2O), which is directly related to the O2 concentration. OH is mainly produced by e + H2O → e + H + OH so the OH density decreases due to the decrease of electron density and H2O concentration with the increase of O2: H2O ratio. On the dielectric surface when the propagation of streamer extinguishes, O flux shows an upward trend while the OH flux decreases, and the propagation distance of O and OH decreases with the increase of O2: H2O ratio.

Mathematical modeling of the influence of non-catalytic dissociation / recombination of water molecules in the desalination channel on electric convection

The article formulates a two-dimensional mathematical model of non-stationary transport of 1: 1 electrolyte in a potentiodynamic mode, taking into account electroconvection and non-catalytic dissociation / recombination reaction of water molecules in electromembrane systems, which are considered as the desalting channel of an electrodialysis device. The model is described by a system of coupled Navier-Stokes and Nernst-Planck-Poisson equations taking into account the electric force and physically justified boundary conditions. The article establishes the basic laws of mass transport, taking into account the dissociation / recombination of water molecules. It was shown for the first time that a double electric layer of hydrogen and hydroxyl ions arises in the recombination region. It is shown that between the region of recombination and quasi-equilibrium regions of space charge there are regions of electroneutrality and equilibrium with an almost linear distribution of concentrations. It was found that even under prelimiting, but close enough to the limiting current, modes, non-catalytic dissociation of water molecules in the quasi-equilibrium region of space charge occurs so intensely that the concentration of hydrogen and hydroxyl ions becomes comparable to the concentration of potassium and chlorine ions. At overlimiting current densities, due to the appearance of an extended space charge region and intense dissociation of water molecules in this region, as well as an increase in the electric double layer in the recombination region, the space charge and the dissociation / recombination reaction of water molecules significantly affect each other. In turn, this has a decisive effect on electroconvection and, accordingly, on the transport of salt ions.

Chemically Induced Spin Hyperpolarization: Coherence Formation in Reaction Products

Chemically induced dynamic nuclear polarization (CIDNP) has emerged as a highly informative method to study spin-dependent radical reactions by analyzing enhanced NMR (nuclear magnetic resonance) signals of their diamagnetic reaction products. In this way, one can probe the structure of elusive radical intermediates and determine their magnetic parameters. A careful examination of experimental CIDNP data at variable magnetic fields shows that formation of hyperpolarized molecules in a coherent state is a ubiquitous though rarely discussed phenomenon. The presence of nuclear spin coherences commonly leads to subsequent polarization transfer among coupled spins in the diamagnetic products of radical recombination reaction that must be taken into account when analyzing the results of CIDNP experiments at low magnetic field. Moreover, such coherent polarization transfer can be efficiently exploited to polarize spins, which do not acquire CIDNP directly. Here we explain under what conditions such coherences can be generated, focusing on the key role of level anti-crossings in coherent polarization transfer, and provide experimental approaches to probing nuclear spin coherences and their time evolution. We illustrate the theoretical consideration of the outlined coherent spin phenomena in CIDNP by examples, obtained for the dipeptide tryptophan–tryptophan.

Mec1/Tel1-independent role of protein phosphatase 4 in Hop1 assembly to promote meiotic chromosome axis formation in budding yeast

Dynamic changes in chromosomal structure that occur during meiotic prophase play an important role in the progression of meiosis. Among them, meiosis-specific chromosomal axis-loop structures are important as a scaffold for integrated control between the meiotic recombination reaction and the associated checkpoint system to ensure accurate chromosome segregation. However, the molecular mechanism of the initial step of chromosome axis-loop construction is not well understood. Here, we showed that, in budding yeast, a Tel1/Mec1-related protein phosphatase 4 (PP4) is required to promote the assembly of a chromosomal axis components Hop1 and Red1 onto meiotic chromatin via interaction with Hop1. PP4 did not affect Rec8 assembly. Notably, unlike the previously known function of PP4, this novel function was independent of Tel1/Mec1 kinase functions. The defect in Hop1/Red1 assembly in the absence of PP4 function was not suppressed by Pch2 dysfunction. Since Pch2 is a conserved AAA+ ATPase and facilitates eviction of Hop1 protein from the chromosome axis, suggesting that PP4 is required for the initial step of chromatin loading of Hop1 rather than stabilizing Hop1 on the chromosome axis. These results indicate phosphorylation/dephosphorylation-mediated regulation of Hop1 recruitment onto chromatin during chromosome axis construction before meiotic double-strand break formation.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in a Plasma Using a Mid-Infrared Dual-Comb Spectrometer

Conventional mechanical Fourier Transform Spectrometers (FTS) can simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz (0.18 nm at a wavelength of 3333 nm), a temporal resolution of 20 μs, a total wavelength coverage over 300 cm−1 and a total measurement time of ~70 s. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring the fast dynamics of chemical reactions over a broad wavelength range, which can be interesting for chemical kinetic research, particularly for the combustion and plasma analysis community.

Theoretical Analysis of the Stationary Transport of 1:1 Salt Ions in a Cross-Section of a Desalination Channel, Taking into Account the Non-Catalytic Dissociation/Recombination Reaction of Water Molecules

In electromembrane systems, the theoretical study of salt ion transport usually uses mathematical models of salt ion transport in the depleted diffusion layer of ion-exchange membranes. This study uses a one-dimensional mathematical model of salt ion transport in a cross-section of a desalination channel formed by anion-exchange and cation-exchange membranes, taking into account an effect of a dissociation/recombination reaction of water molecules. The reaction on the one hand leads to an overlimiting mass transfer due to the effect of exaltation of the limiting current. On the other hand, an appearance of new electric charge carriers (hydrogen and hydroxyl ions) can reduce the space charge that occurs in membranes and suppress an electroconvective mechanism of overlimiting transport. Thus, there is a problem of studying these phenomena together, taking into account their mutual influence, and this article is devoted to the solution of this problem. Theoretically, using a method of mathematical modeling and numerical research, main regularities are established; in particular, it is shown that the dissociation/recombination reaction of water molecules does not lead to the destruction of the double electric layer at the membranes, but also creates a new double electric layer in the middle of the desalination channel. Thus, the space charge and the dissociation/recombination reaction significantly affect each other and simultaneously the transport of salt ions.

Visible-Light Sensitive Photocatalytic Activity of FeOx- and P-Modified TiO2 with Rutile Structure

Nanocrystalline rutile TiO2 particles were prepared via hydrothermal treatment of Ti-containing precursors obtained by low-temperature aging for a transparent diluted HCl solution of amorphous TiO2. The products were modified with FeOx and phosphoric acid, and the photocatalytic activities of the obtained catalysts under visible-light irradiation were examined. By the addition of FeOx or phosphoric acid, the photocatalytic activity of the rutile TiO2 was slightly increased. On the contrary, by the FeOx loading and subsequent addition of phosphoric acid, significant increases in the photocatalytic activity were attained. Results of UV-vis suggest that the iron oxides formed on the surface of rutile TiO2 were changed into highly dispersed iron phosphate species by the addition of phosphoric acid. It was presumed that these species effectively suppress the recombination reaction between the photogenerated electrons and holes and contribute to the high photocatalytic activity of the rutile TiO2 photocatalysts modified with FeOx and phosphoric acid.

Broadband Time-Resolved Absorption and Dispersion Spectroscopy of Methane and Ethane in A Plasma Using a Mid-Infrared Dual-Comb Spectrometer

Conventional mechanical Fourier Transform Spectrometers (FTS) are able to simultaneously measure absorption and dispersion spectra of gas-phase samples. However, they usually need very long measurement times to achieve time-resolved spectra with a good spectral and temporal resolution. Here, we present a mid-infrared dual-comb-based FTS in an asymmetric configuration, providing broadband absorption and dispersion spectra with a spectral resolution of 5 GHz, a temporal resolution of 20 μs, and a total measurement time of a few minutes. We used the dual-comb spectrometer to monitor the reaction dynamics of methane and ethane in an electrical plasma discharge. We observed ethane/methane formation as a recombination reaction of hydrocarbon radicals in the discharge in various static and dynamic conditions. The results demonstrate a new analytical approach for measuring fast molecular absorption and dispersion changes and monitoring fast dynamics of chemical reactions, which can be interesting for chemical kinetic research and particularly for the combustion and plasma analysis community.

Functional Analysis of the Acinetobacter baumannii XerC and XerD Site-Specific Recombinases: Potential Role in Dissemination of Resistance Genes

Modules composed of a resistance gene flanked by Xer site-specific recombination sites, the vast majority of which were found in Acinetobacter baumannii, are thought to behave as elements that facilitate horizontal dissemination. The A. baumannii xerC and xerD genes were cloned, and the recombinant clones used to complement the cognate Escherichia coli mutants. The complemented strains supported the resolution of plasmid dimers, and, as is the case with E. coli and Klebsiella pneumoniae plasmids, the activity was enhanced when the cells were grown in a low osmolarity growth medium. Binding experiments showed that the partially purified A. baumannii XerC and XerD proteins (XerCAb and XerDAb) bound synthetic Xer site-specific recombination sites, some of them with a nucleotide sequence deduced from existing A. baumannii plasmids. Incubation with suicide substrates resulted in the covalent attachment of DNA to a recombinase, probably XerCAb, indicating that the first step in the recombination reaction took place. The results described show that XerCAb and XerDAb are functional proteins and support the hypothesis that they participate in horizontal dissemination of resistant genes among bacteria.