Electron-Stimulated Hydrogen Desorption from Nickel and Palladium

New experimental data are presented on the radiation-stimulated diffusion of hydrogen in metals, in particular, nickel and palladium, under the action of a 30-keV accelerated electron beam. Hydrogen desorption rates from nickel and palladium are determined for thermal and electron beam heating; a substantial shift of the thermal gas-desorption peaks to the low-temperature range is detected upon radiationinduced heating. The presence of an internal hydrogen atmosphere is shown to create favorable conditions for the vibrational-translational exchange (V–T exchange), non-equilibrium redistribution, and desorption of hydrogen from a solid upon irradiation. Accelerated hydrogen migration stimulated by electrons with an energy below the defect-formation threshold is explained at a qualitative level. First-principles calculations of the electronic structure of the metal–hydrogen system reveal that plasmons are also an efficient mechanism for radiation-energy dissipation over the whole crystal.     

Electron Spin Polarization of Photo-Excited Copper Coproporphyrin I: From Monomers to Dimers

The results of the electron paramagnetic resonance (EPR) and transient EPR (TREPR) of copper complexes of coproporphyrin I in different solvents before and after the laser pulse photo-excitation have been presented. Continuous-wave EPR spectra of the CuCPP-1 complex in o-terphenyl indicate the presence of only monomer fragments, while in the solution of the chloroform and isopropanol mixture, the complexes dimerize and the amount of dimers is five times larger than that of monomer complexes. Parameters describing EPR spectra of monomer and dimer CuCPP-1 complexes have been determined. It was established that the fine structure tensor of the dimer complex is rotated with respect to the g-tensor, which coincides with the tensor of monomer complexes. TREPR spectra of CuCPP-1 complexes in o-terphenyl and in the chloroform and isopropanol mixture after the laser photo-excitation are mainly due to spin-polarized ground states of monomer and dimer complexes, respectively. The TREPR spectra of the monomer CuCPP-1 show the emissive spin-polarized signal of the ground state. For dimer fragments, the net polarization is observed in the form of absorption and there is a small contribution from the multiplet polarization, which decays fast in time. The time dependence of TREPR of CuCPP-1 complexes in the chloroform and isopropanol mixture is described with allowance for these contributions from the ground state of the dimer and the contribution from the ground state of the monomer, which is manifested at larger times. Differences in the spin polarization of ground states and their possible origin are discussed.     

Studying the effects of temperature and radiation on the Al x O1 − x /TiNC system

The penetration of hydrogen through protective layers of aluminum oxide fixed on the surface of nanocrystalline (NC) titanium is studied. A film 400 nm thick is prepared by the magnetron sputtering. Radiation- and thermally-induced gas release are employed. It is found that the Al _x O_1?x film prevents the release of hydrogen from a sample under both radiation and thermal effects. The temperature of hydrogen extraction from metal hydride accumulators can be reduced by 200–250°C, provided that heating is performed under conditions of surface irradiation by electrons with energies of ～30 keV and current densities of 2 to 3 μA cm^?2.     

Cre-lox66/lox71-Based Elimination of Phosphotransacetylase or Acetaldehyde Dehydrogenase Shifted Carbon Flux in Acetogen Rendering Selective Overproduction of Ethanol or Acetate

Acetogen strain Clostridium sp. MT1121 produced 300?mM acetate (p?<?0.005) and 321?mM ethanol (p?<?0.005) from synthesis gas (syngas) blend 60?% CO and 40?%?H₂. Clostridium sp. MT1121 was metabolically engineered to eliminate production of either acetate or acetaldehyde during syngas fermentation. We used Cre-lox66/lox71-based gene removal system to eliminate either phosphotransacetylase (pta), or acetaldehyde dehydrogenase (aldh). The resulted biocatalyst with eliminated pta increased ethanol yield to 610?mM (p?<?0.005). Inactivation of pta rendered only 502?mM of ethanol (p?<?0.005). The acetogen biocatalyst with eliminated aldh produced 450?mM acetate (p?<?0.005). The role of cell energy pool preservation for re-directed carbon flux is discussed. This is the first report on time- and cost-efficient gene elimination in acetogens using lox66/lox71 gene elimination system.     

Properties and structure of oxidized coatings deposited onto Al-Cu and Al-Mg alloys

The results of new studies of creating protective oxide coatings based on Al₂O₃ (Si, Mn) and deposited onto aluminum alloys using electrolyte-plasma oxidation are presented. An analysis is performed by scanning electron microscopy (SEM) with energy dispersive spectroscopy (EDS), X-ray diffraction, Rutherford backscattering of ⁴He⁺ and protons, nanoindentation, scratching, friction coefficient measurements, and acoustic emission measurements. The results demonstrate that the deposited coatings have a high quality, hardness, and wear resistance and a low thermal diffusivity. Apart from Al₂O₃, the coatings are found to have Si, Mn, C, and Ca. The stoichiometry of the coatings is determined. The density and hardness of the coatings are close to those of ??-Al₂O₃ in the coating on an Al-Cu (D-16) substrate, and these values of the coating on an Al-Mg (S006) are lower by a factor of 1.5.     

Excitation of the hydrogen subsystem in metals and alloys by ionizing radiation

Models of nonequilibrium-stimulated diffusion and the release of hydrogen and its isotopes from metals by the action of ionizing radiation are considered. It is suggested that the acceleration of the release of hydrogen from metals by the action of radiation is due to the excitation of nonequilibrium vibrational states in the hydrogen subsystem of the metals and a reduction in the surface potential barrier by the desorbing molecules. It is shown, in particular, that the diffusion coefficient of deuterium in Pd is increased by a factor of 30 by the action of radiation compared with a nonirradiated sample. Tomsk Polytechnical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 3–10, November, 1998.     

Effect of Organotin Compounds and Their Complexes with Phosphatidylcholine on Peroxide Oxidation of Lipid Structural Fragments

Oxidation of a lipid structural fragment, oleic acid, in the presence of a series of organotin compounds and their complexes with phosphatidylcholine was studied at 25, 37, 65, and 95°C. At a nearly physiological temperature, acceleration of hydroperoxide accumulation in the presence of these complexes was observed. At 65°C, addition of organotin derivatives leads to increase in the initial rate of hydroperoxide accumulation, but the kinetic curves acquire an S-like character as the reaction progresses. These data indicate that the rate of decomposition of hydroperoxides exceeds the rate of their accumulation. In the presence of 2,6-di-tert-butylphenol as antioxidant, the promoting effect of organotin compounds disappears. A possible reaction mechanism and the role of radical species arising from dissociation of the CÄSn bond are discussed.     

A physical model of the action of low-intensity laser radiation on biological objects

A new model of the action of low-intensity laser radiation (LILR) on biological objects on the cellular level is proposed. The model implies that, because the laser radiation is coherent, the illumination in the bulk of a biological object can acquire a spatially periodic character (in the form of an interference pattern or speckle structure), with the period of alternating dark and light regions being comparable with the size of cells or cell organelles. Under these conditions of high-gradient illumination, an electrical field can arise (the Dember effect) that can change the character of photostimulated reactions and the membrane charge state not only in the cell itself but also in its organelles, which leads to shifts in the life cycle of cells (and/or bacteria).     

Excitation of the hydrogen subsystem in metals and alloys by ionizing radiation

The results of research on the nonequilibrium liberation of deuterium from niobium, palladium, and stainless steel under electron-beam bombardment are reported. The maximum on the deuterium gas liberation curve in the low-temperature region is shown to shift under linear heating with simultaneous electron-beam bombardment in comparison with linear heating without such bombardment. The shift reaches 130° in Nb, 100° in stainless steel, and 65° in Pd. The rate of radiation-stimulated gas liberation increases nonlinearly with the concentration of deuterium introduced and the electron-beam current. Tomsk Polytechnical University. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, p. 41–46. July, 1998.