Anharmonic force constants of GaSb from the measured third order elastic constants at 300°K

The third-order elastic constants of single crystal GaSb are determined using ultrasonic pulse interferometer at 10 MHz. The constants at 300°K, in units of 10¹¹ N.m.⁻², are C_l11 = ™ 4 ·75 ± 0·06 C₁₄₄ = + 0·50 ± 0·25 C₁₁₃ = ™ 3 ·08 ± 0·02 C₁₆₆ = ™ 2·16 ± 0·13 C₁₂₃ = ™ 0 ·44 ± 0·29 C₄₅₆ = ™ 0·25 ± 0·15 These constants are used to evaluate the three anharmonic first and second neighbour force constants based on modified Keating’s model. The constants are (in units of 10¹¹ N.m⁻²)γ=− 2·406;δ=0·407;ε=−0·222.     

Kinetics of formation of O2(1Σ) molecules in reactions involving excited O2(1Δ) oxygen molecules and I(2P1/2) iodine atoms

The results of our experimental study of the kinetics of formation of O₂(¹Σ) molecules in energy-exchange reactions O₂(¹Δ) + I(⁵ p,² P _1/2) and O₂(a,¹Δ) + O₂(a,¹Δ) are presented. The ratio of rate constants was obtained for these reactions (4800 ± 300). Setting the rate constant of the deactivation of O₂(¹Σ) molecules on CO₂ molecules at 4.1 · 10^–13 cm³/s, we evaluated the rate constants for these reactions at a temperature of approximately 330 K: (1.7 ± 0.2) · 10⁻¹³ and (3.6 ± 0.5) · 10⁻¹⁷ cm³/s, respectively.     

Synthesis, Characterization, DNA-Binding and Antiproliferative Activity of Nd(III) Complexes With N-(Nitrogen Heterocyclic) Norcantharidin Acylamide Acid

Three novel complexes [Nd(L)(NO₃)(H₂O)₂]·NO₃·2H₂O (HL¹ = N-pyrimidine norcantharidin acylamide acid, C₁₂H₁₃N₃O₄; HL² = N-pyridine norcantharidin acylamide acid, C₁₃H₁₄N₂O₄; HL³ = N-phenyl norcantharidin acylamide acid, C₁₄H₁₅NO₄) were synthesized. HL¹, HL² and HL³ are the ligand of complex(1), complex(2) and complex(3), respectively. Their structures were characterized by elemental analysis, conductivity measurement, infrared spectra and thermogravimetric analysis. The DNA-binding properties of the complexes have been investigated by fluorescence spectroscopy and viscosity measurements. The results suggest that the complexes can bind to DNA by partial intercalation. The liner Stern-Volmer quenching constant K_sq values are 3.3(±0.21)(1), 1.7(±0.19)(2) and 0.9(±0.04)(3), respectively. Complex (1) and (2) have been found to cleave pBR322 plasmid DNA at physiological pH and temperature. The test of antiproliferation activity indicates that complex(1) has strong antiproliferative ability against the SMMC7721 (IC₅₀ = 131.7 ± 23.4 μmol·L⁻¹) and A549 (IC₅₀ = 128.4 ± 19.9 μmol·L⁻¹) cell lines. The inhibition rates of complex(2) (IC₅₀ = 86.3 ± 11.3 μmol·L⁻¹) are much higher than that of NCTD (IC₅₀ = 115.5 ± 9.5 μmol·L⁻¹) and HL² (111.0 ± 5.7 μmol·L⁻¹) against SMMC7721 cell lines.     

Electrical conductivity of BaCe0.9Nd0.1O3−α in H2+H2O+Ar gas mixture

Electroconductivity of BaCe_0.9Nd_0.1O_3−α was studied as a function of the composition of the H₂+H₂O+Ar mixture and temperature in the interval from 873 to 1173 K. It was shown that the electroconductivity was independent of P_H2 (0.97 to 0.10 atm) and P_O2 (10⁻²¹ to 10⁻²⁶ atm), but depended on P_H2O (0.08 to 0.005 atm). A mathematical processing of the P_H2O dependencies of the electroconductivity, which was performed in terms of a classical model of defect formation in high-temperature proton-conducting solid electrolytes, yielded equilibrium constants of the reaction of water dissolution in BaCe_0.9Nd_0.1O_3−α and mobilities of protons and oxygen ions. The temperature dependencies of these quantities were used to determine the mobility activation energies of protons (E_a=34±7 kJ/mole) and oxygen ions (E_a=72±8 kJ/mole), and also the enthalpy (ΔH=−150±25 kJ/mole) and the entropy (ΔS=153±26 kJ/mole·K) of the reaction of water dissolution in BaCe_0.9Nd_0.1O_3−α.     

Complexation of heterocyclic ligands with DNA in aqueous solution

We have used spectrophotometry to study self-association and complexation with DNA by organic heterocyclic compounds in the acridine and phenothiazine series: proflavin, thionine, and methylene blue. Based on the experimental concentration dependences of the molar absorption coefficient of the molecules in an aqueous buffer solution (0.01 M NaCl, 0.01 M Na₂EDTA, 0.01 M Tris, pH 7.4, T = 298 K), we have determined the equilibrium dimerization constants for the dyes and the DNA complexation parameters using the Scatchard and McGhee-von Hippel models. The observed increase in the cooperativity parameters as the dimerization constants of the ligands increase allowed us to hypothesize that the same interactions occur between dye molecules adsorbed on DNA as in their self-association. The equilibrium DNA-binding constants for the ligands, obtained using the McGhee-von Hippel cooperative model, are (20.9 ± 2.7)·10³ M⁻¹ for proflavin and (33.8 ± 4.1)·10³ M⁻¹ for thionine. Using the Scatchard model, taking into account intercalation and “external” binding of ligands with DNA, we determined the DNA complexation constants for methylene blue: (26.4 ± 4.6)·10³ and (96 ± 17)·10³ M⁻¹ respectively. Based on analysis of the data obtained, we hypothesized that the predominant type of binding with DNA is intercalation binding in the case of proflavin and thionine, and “external” binding with the DNA surface in the case of methylene blue. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 2, pp. 242–249, March–April, 2008.     

Effect of the humidity on the uptake of NO<Subscript>3</Subscript> on coatings composed of MgCl<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and MgBr<Subscript>2</Subscript> · 6H<Subscript>2</Subscript>O and mixtures thereof with NaCl

The reactive uptake of NO₃ radicals on the surface of wetted individual X salts and of wetted X-NaCl salts (X = MgCl₂ · 6H₂O and MgBr₂ · 6H₂O) at [H₂O] = 2 × 10¹²−2 × 10¹⁵ cm⁻³ and NO₃ (4.8 × 10¹² cm⁻³) was studied using a reactor with a movable insert covered with a salt coating in combination with a mass spectrometer for monitoring the initial reactant and products. The probabilities of NO₃ uptake γ on X-NaCl binary salts as functions of the content of doping salt were determined. A parametric approximation of the experimental data was proposed, which makes it possible to quantitatively predict the extent of surface enrichment of a wetted binary salt coating in doping salt and its dependence on the humidity and the content of this salt in the binary mixture. It was established that the relative surface density σ_X of X doping salt depends on its mole fraction μ_X in the X-NaCl binary salt as σ_X = aμ_X (a = 2.2 for MgBr₂ and 13.1 for MgCl₂) over the entire humidity range covered. The contributions of the X salts to the overall uptake of NO₃ at NO₃ concentration typical of the tropospheric conditions ([NO₃] ∼ 10⁷ cm⁻³ and relative humidities of RH ≤ 20%) were estimated.     

Determination of absorption cross sections for oxygen molecules in the Schumann-Runge band region at high temperatures

We have measured the absorption cross sections of oxygen molecules in oxygen and in an oxygen-argon mixture heated by a shock wave, in the wavelength range 190–250 nm at temperatures of 1500–7000 K, for thermal equilibrium conditions behind the shock wave front. Analysis of the absorption cross sections obtained allowed us to select a data set that adequately describes the absorption characteristics of the electronic transition X³Σ _g ⁻ → B³Σ _u ⁻ for the oxygen molecule. In order to approximate the temperature dependence of these cross sections at a temperature of 1500–4500 K, we chose the function σ(λ, T) = σ₀(λ)(1 − exp (−θ/T)) exp (− n*θ/T) where θ₀ = 1.4·10⁻¹⁷, 1.4·10⁻¹⁷, 1.2·10^{− 17}, and 1.3·10⁻¹⁷ cm², n* = 3.1, 4.1, 5.6, and 7.47 for wavelengths 190, 210, 230, and 250 nm, respectively; θ = 2240 K is the characteristic temperature of the O₂ molecules. The approximation error was 19–25% and did not exceed the experimental error. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 1, pp. 13–17, January–February, 2006.     

Fast nonequilibrium induction detectors based on thin superconducting films

A new type of fast detector is proposed. The operation of the detector is based on the change induced in the kinetic inductance of NbN and YBa₂Cu₃O_7−δ superconducting films by nonequilibrium quasiparticles produced by electromagnetic radiation. The speed of a NbN detector is essentially temperature-independent and is less than 1 ps. A model based on the Omen-Scalapino scheme describes well the experimental dependence of the voltage-power sensitivity of a NbN detector on the modulation frequency of the radiation. A low equilibrium quasiparticle density and a high quantum yield give detecting power D*=10¹²W⁻¹ · cm · Hz^1/2 at temperature T=4.2 K and D*=10¹⁶ W⁻¹ · cm · Hz^1/2 at temperature T=1.6 K. The time constant of the low-temperature YBaCuO induction detector is determined only by the electron-phonon interaction time τ _e-ph ^d in the nodal regions. Zh. Tekh. Fiz. 68, 63–69 (October 1998)     

EPR studies of Cu2+ and V4+ ions in phosphate glasses

Two lead-phosphate glass systems doped with both copper and vanadium ions in different ratios were studied by EPR (electron paramagnetic resonance) method. EPR spectra and parameters (g_‖ = 2.44, g_⊥ = 2.08 andA _‖ = 117.6 · 10⁻⁴ cm⁻¹) obtained for x(CuO · V₂O₅)(l−x)[2P₂O₅ · PbO] glasses withx ≤ 10 mol% suggest a tetrahedral (Td) coordination of Cu²⁺ ions and not a tetragonally elongated octahedron as has been assumed in previous works. The ground state of the paramagnetic electron is thed _xy copper orbital with a 4p_z contribution of 6%. For 20 ≤x ≤ 40 mol% a broad line (ΔB = 307 G) characteristic for clustered ions appears atg = 2.18. The V⁴⁺ ions are evidenced only in the spectra of x(CuO · 2V₂O₅)(1 −x)[2P₂O₅ · PbO] glasses and the resonance parameters suggest a pentacoordinated C_4v local symmetry for these ions. The hyperfine structures characteristic for Cu²⁺ and V⁴⁺ ions disappear for 10 ≤x ≤ 40 mol% due to the mixed exchange Cu²⁺−V⁴⁺ pair formation in these glasses.     

Reaction of β-carotene with nitrite anion in a homogeneous acid system. An electron paramagnetic resonance and ultraviolet-visible study

Ultraviolet and visible spectroscopy was applied to characterize and to measure the concentration of β-carotene dissolved in a dioxane and water mixture. The reaction of β-carotene in the presence of nitrite anion and acid medium was studied at different temperatures. The reaction systems were homogeneous and were kept anaerobic. Pseudo-first-order rate constants in respect of β-carotene were measured in the range from 293 to 313 K and pH 5.8 ± 0.2. The energy of activation was calculated to be E _a = 67.2 ± 3.4 kJ/mol. We interpolate a value that may have biological interest, k _β-carotene(310 K) = (9.70±0.78) · 10⁻³ s⁻¹, in the presence of 9.3 · 10⁻³ M nitrite anion. Electron paramagnetic resonance spectroscopy was applied to characterize and quantify a persistent intermediate radical generated in the reaction system described. The recorded spectra showed triplet-type signals with a peak-to-peak value of 12.7 G. Nearly the same triplet radical-type intermediates were detected when studying the following reaction systems in pure dioxane: nitrogen dioxide (NO₂)/β-carotene, nitric oxide (NO)/β-carotene and NO/NO₂/β-carotene. Therefore, we proposed that the nitrogen oxides have also been intermediates in the reaction system of β-carotene, nitrite anion and acid medium, in the dioxane and water mixture. A mechanism was proposed and checked by employing the chemical kinetics simulation. The explanations developed would lead to a better understanding of the behavior of carotenoids in the presence of nitrite anion and nitrogen oxides.     

Defects and transport in SrFe1−xCoxO3−δ

The non-stoichiometry and chemical diffusion coefficient of SrFe_1−xCo_xO_3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10⁻⁴ – 7·10⁻⁴ cm²/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects in SrFe_1−xCo_xO_3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe_1−xCo_xO_3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to the formation of carbonates and sulphates. Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999.     

An electron paramagnetic resonance study of nitrogen dioxide dissolved in water, carbon tetrachloride and some organic compounds

Electron paramagnetic resonance spectrometry was used to characterize and measure the concentration of nitrogen dioxide dissolved in water, carbon tetrachloride, n-hexane, acetone and benzene at 290 K. Solutions were monitored by ultraviolet spectrometry. We measured the equilibrium constant for N₂O₄ plus NO₂ dissolved in n-hexane and carbon tetrachloride. In order to investigate the formation of organic nitroxide type intermediates, some experiments were designed to examine the role of NO and NO plus NO₂ mixtures.     

An investigation of the Al2O3-CdSe interface in accumulation

The Al₂O₃−CdSe interface of a thin-film transistor is investigated in the frequency range 30 Hz-30 kHz under weak depletion and accumulation. The surface states are, most likely, located in the insulator Al₂O₃ with a concentration varying from 4·10¹⁸ to 10¹⁹ cm⁻³ eV⁻¹. The surface states have a negligible influence on the thin-film transistor operation.     

Role of charge-transfer complexes in oxygen quenching of excited states of anthracene derivatives in the gas phase

Oxygen quenching of excited triplet and singlet states of gas-phase anthracene and its derivatives that have similar energies of the lower triplet levels but widely different oxidation potentials (0.44 < E_ox < 1.89 V) was studied. Quenching rate constants for singlet (k_S^O2) and triplet (k_T^O2) states in addition to the fraction of oxygen-quenched singlet and triplet states q_{S 1}(T₁^O2 were determined from the decay rates, fluorescence intensities, and delayed fluorescence as functions of oxygen pressure. It was found that k_S^O2 values vary from 2·10⁴ (9,10-dicyanoanthracene) to 1.2·10⁷ sec⁻¹·torr⁻¹ (anthracene, 9-methylanthracene, 2-aminoanthracene) and k_S^O2 values from 5·10² to 1·10⁵ sec⁻¹·torr⁻¹. The k_S^O2 values for anthracene, 9-methylanthracene, and 2-aminoanthracene, which have fast rates of interconversion from S₁ to T₁, are close to the rate constants for gas-kinetic collisions and are independent of the oxidation potentials (E_ox). The quenching rate constants k_S^O2 for the other anthracene derivatives and k_T^O2 for all studied compounds decrease with increasing free energy of electron transfer ΔG_ET, which indicates the important role of charge-transfer interactions in the oxygen quenching of singlet S_1- and triplet T₁ states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 36–42, January–February, 2008.     

Thermomechanical and conductivity studies of doped niobium titanates as possible current collector material in the SOFC anode

In the reducing atmosphere of the SOFC anode at operating temperatures of 800 °C and above Nb₂TiO₇ is reduced to Nb_1.33Ti_0.67O₄. This material displays very high electronic conductivity of >100 Scm⁻¹, suitable for use in such applications as a current collector. It has a low thermal expansion coefficient of 3 × 10⁻⁶ K⁻¹, however, which may cause problems due to mismatch with other SOFC components, e.g. YSZ. Doping with Fe₂O₃ successfully increased the thermal expansion to a maximum of 6 × 10⁻⁶ K⁻¹. A conductivity of 140 Scm⁻¹ at 900 °C in dry 5% H₂/Ar, with an activation energy of 0.18 eV, was achieved for the Nb_1.344Ti_0.642Fe_0.014O₄, making it suitable for the use as a current collector. Conductivity runs in wet 5%H₂/Ar showed lower conductivities of 15–18 Scm⁻¹ and lower activation energies of 0.08 − 0.09 eV. Single cell tests of Nb_1.33Ti_0.67O₄ showed power outputs of 5.5 − 7.2 mW·cm⁻² at 850 °C, lower than for Ni with 150 − 200 mW·cm⁻² at 850 °C, however, this material displayed much better stability at high temperatures than Ni. Paper presented at the 9th EuroConference on Ionics, Ixia, Rhodes, Greece, Sept. 15 – 21, 2002.     

Critical point phenomena in the electrical resistivity of binary liquid systems: CS2 + CH3CN and CS2 + CH3NO2

Electrical resistance measurements are reported on the binary liquid mixtures CS₂ + CH₃CN and CS₂ + CH₃NO₂ with special reference to the critical region. Impurity conduction seems to be the dominant mechanism for charge transport. For the liquid mixture filled at the critical composition, the resistance of the system aboveT _c follows the relationR=R _c−A(T−T _c) ^b withb=0·6±0·1. BelowT _c the conductivities of the two phases obey a relation σ₂−σ₁=B(T _c−T)^β with β=0·34±0·02, the exponent of the transport coefficient being the same as the exponent of the order parameter, an equilibrium property.     

Optical properties of the ternary compound Cd<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript>Hg<Subscript>1−<Emphasis Type="Italic">x</Emphasis></Subscript>Se:Co

We present the results of experimental studies of the optical properties of cobalt-doped Cd _x H_1−x Se (x = 0.18) single crystals with cobalt ion concentrations of NCo = 5·10¹⁸, 5·10¹⁹, and 1·10²⁰ cm⁻³ at T = 90 K and 300 K. The composition (x = 0.18) of the Cd _x Hg_1−x Se solid solution was selected so that the hypothetical resonance level is found on the bottom of the conduction band. We show that the cobalt ions in the mercury selenide can form a resonance donor level only for cobalt concentrations N_Co < 5·10¹⁸ cm⁻³. For N_Co ∼ 5·10¹⁸ cm⁻³, the cobalt ions substitute for mercury atoms, forming a solid solution and leading to an increase in the bandgap width and a change in the physical properties. The solubility of cobalt in the HgSe lattice can be greater than 5%–10%. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 1, pp. 73–77, January–February, 2007.     

Fluorescent Method for the Determination of Sulfide Anion with ZnS:Mn Quantum Dots

Water-soluble Mn²⁺-doped ZnS quantum dots (QDs) were prepared using mercaptoacetic acid as the stabilizer. The optical properties and structure features were characterized by X-Ray, absorption spectrum, IR spectrum and fluorescence spectrum. In pH 7.8 Tris-HCl buffer, the QDs emitted strong fluorescence peaked at 590 nm with excitation wavelength at 300 nm. The presence of sulfide anion resulted in the quenching of fluorescence and the intensity decrease was proportional to the S²⁻ concentration. The linear range was from 2.5 × 10⁻⁶ to 3.8 × 10⁻⁵ mol L⁻¹ with detection limit as 1.5 × 10⁻⁷ mol L⁻¹. Most anions such as F⁻, Cl⁻, Br⁻, I⁻, CH₃CO₂ ⁻, ClO₄ ⁻, CO₃ ²⁻, NO₂ ⁻, NO₃ ⁻, S₂O₃ ²⁻, SO₃ ²⁻ and SO₄ ²⁻ did not interfere with the determination. Thus a highly selective assay was proposed and applied to the determination of S²⁻ in discharged water with the recovery of ca. 103%.     

Interaction of muonium with oxygen on silica powder surfaces

Results of the first μSR studies using Merck FO Optipur silica powder, which contains paramagnetic impurities at the ppb level and has a surface area of 610±20 m²/g. are reported. Above 20 K, the transverse field muonium relaxation rate is roughly constant at 0.5 μs⁻¹. Upon the addition of oxygen at ppm levels, the relaxation rate increases linearly with O₂ concentration in the temperature range from 40–100 K yielding two-dimensional depolarization rate constants on the order of 10⁻⁴ cm² molecule⁻¹ s⁻¹. As the temperature is increased further, both oxygen and muonium desorb from the surface yielding a three-dimensional rate constants at 300 K of 3.1(3)×10–10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, in agreement with the gas phase value. Longitudinal field measurements suggest that MuO₂ is formed and is able to spin exchange with other oxygen molecules.     

Influence of additional metal ions on the ratio of the rates of intermediate product transformations in the hydrolysis of adenizine-5′-triphosphoric acid catalyzed by divalent Cu ions

It was shown earlier that the hydrolysis of the (CuATP²⁻)₂ dimeric complex to CuADP⁻ and inorganic phosphate P _i was an irreversible reaction. The main intermediate hydrolysis product, the formation of which should be taken into account at comparatively early hydrolysis stages, was the IntK pentacovalent intermediate. It was formed in parallel with hydrolysis to CuADP⁻ and P _i through the common intermediate product (CuATP²⁻)₂OH⁻ — DOH⁻. We studied the influence of the addition of various concentrations of Mg²⁺ ions to the reaction mixture at pH 7.1–7.2, a range for which the kinetics of hydrolysis is sensitive to the rate constants of deactivation of DOH⁻ active centers (conjugated with CuADP⁻ formation and occurring via the formation of IntK). The conversion of ATP above which stationary hydrolysis regime was observed decreased as the concentration of Mg²⁺ grew. The DOH⁻ $ \underset{{OH^ - }}{\overset{{OH^ - }}{\longleftrightarrow}}$ \underset{{OH^ - }}{\overset{{OH^ - }}{\longleftrightarrow}} IntK equilibrium according to the conversion of ATP was established more rapidly, and it was to a greater extent shifted toward IntK. It was assumed that hydrated Mg²⁺ linked as a second metal ion with ATP β and γ phosphate groups hydrated IntK much stronger than DOH⁻. The Cu · OH₂ · AMP complex played the role of a common acid catalyst and hydrated DOH⁻ better than Mg²⁺ · OH₂. The selective hydration of DOH⁻ by the CuOH₂ · AMP complex at early hydrolysis stages directed the process toward the formation of IntK, which caused the appearance of an induction period in the formation of CuADP⁻.