3-pentanone fluorescence yield measurements and modeling at elevated temperatures and pressures

Measurements of 3-pentanone fluorescence quantum yield (FQY) over a wide range of temperatures and pressures in air and nitrogen bath gases are reported and a comprehensive FQY model in support of quantitative planar laser-induced fluorescence diagnostics at elevated pressures and temperatures is presented. Measurements were made of the FQY for 20 mbar of 3-pentanone in nitrogen and air for pressures between 1 and 25 bar in a high-pressure and high-temperature cell for excitation wavelengths of 248, 266, 277, and 308 nm. The measurements were performed in nitrogen from 298 to 745 K and in air from 298 to 567 K. The 3-pentanone FQY data were used to optimize FQY model parameters, including the oxygen and nitrogen quenching rates and vibrational relaxation cascade parameters for nitrogen and oxygen. This work introduces vibrational energy dependence for cascade parameters, as well as a nitrogen quenching rate. The new 3-pentanone FQY model agrees with the measurements within 10%, as well as with fluorescence signal measurements from optical internal combustion engines at pressures and temperatures up to 28 bar and 1100 K.     

Intensity distribution in theA 2Π –X 2Σ+ system of Yttrium monoxide

The integrated intensities of a few bands in the vibrational structure of the astrophysically significant ‘orange’ system of the molecule yttrium monoxide, have been measured experimentally by the technique of photographic photometry. The effective vibrational temperatures of the source are found to be 2402±180 K and 2901±230 K for the subsystemsA ²Π_3/2−X ² Σ ⁺ andA ²Π_1/2−X ² Σ ⁺ respectively.     

Singlet molecular nitrogen in the Auroral ionosphere and under the conditions of laboratory discharge

Using the suggested model of the electron kinetics of N₂ singlet states, the population of the vibrational levels in the molecular nitrogen states (a′)¹Σ _u ⁻, a ¹Π _g , and w ¹Δ _u is calculated for the case when fast auroral electrons penetrate into the Earth’s ionosphere. It is shown for the first time that the population distribution of the vibrational levels v = 0−6 in the state a ¹Π _g in the auroral ionosphere and also in a laboratory discharge varies with atmospheric pressure insignificantly. Similar calculations for pure nitrogen atmosphere show a considerable increase in the populations of lower vibrational levels (v = 0−2) with rising pressure.     

Study of spatial characteristics of the incomplete surface discharge in atmospheric-pressure air

Spectra of plasma of the incomplete surface discharge in atmospheric-pressure air were measured. Bands of the systems 2⁺, 1⁺, and 1⁻ of nitrogen were identified. It was shown that periodic excitation at the C ³Π _u nitrogen level results in local equilibrium characterized by a vibrational temperature of 2250 K. For the 1⁺ band system of nitrogen, the structure of rotational transitions was resolved; it was found that the distribution in the 1⁺ band system is significantly nonequilibrium due to the A ³Σ _u ⁺ level metastability. Transverse and longitudinal sections of the plasma band were scanned. It was found that the transverse distribution of the emission intensity has a maximum at a distance of 1 mm from the electrode edge followed by an exponential decay. The plasma band width was ∼5 mm. The longitudinal discharge structure consisted of a system of microchannels (with a characteristic diameter of 0.4 mm) with diffuse overlapping. The average channel density was 10–15 cm⁻¹. It was shown that the spatial distribution of incomplete discharge plasma is characterized by high stability against wide-range variations of discharge electrical characteristics. For example, as the excitation voltage varies within 2–6 kV, the plasma band width changed by no more than 1 mm, and the vibrational temperature varied within 10–12%.     

The study of lithium fast ion conductors of Li3xLa0.67−xScyTi1−2yNbyO3 system

Perovskite-type lithium fast ion conductors of Li_3xLa_0.67−xSc_yTi_1−2yNb_yO₃ system were prepared by solid state reaction. X-Ray powder diffraction shows that perovskite solid solution form in the ranges of x=0.10, y≤0.10. AC impedance measurements indicate that the bulk conductivities and the total conductivities are of the order of 10⁻⁴ S·cm⁻¹ and 10⁻⁵ S·cm⁻¹ at 25 °C respectively. The compositions have low bulk activation energies of about 17 kJ/mol in the temperature ranges of 298 – 523 K and total activation energies of about 37 kJ/mol in the temperature ranges of 298 – 523 K.     

Magnetism,exchange and crystal field parameters in the orbitally unquenched Ising antiferromagnet FePS3

FePS₃ is a layered antiferromagnet (T _N=123 K) with a marked Ising anisotropy in magnetic properties. The anisotropy arises from the combined effect of the trigonal distortion from octahedral symmetry and spin-orbit coupling on the orbitally degenerate⁵ T _2g ground state of the Fe²⁺ ion. The anisotropic paramagnetic susceptibilities are interpreted in terms of the zero field Hamiltonian, ℋ=Σ_i [δ(L _iz ² −2)+|λ|L _i .S _i ]−Σ _ij J _ij S _i .S _j . The crystal field trigonal distortion parameter Δ, the spin-orbit coupling λ and the isotropic Heisenberg exchange,J _ij, were evaluated from an analysis of the high temperature paramagnetic susceptibility data using the Correlated Effective Field (CEF) theory for many-body magnetism developed by Lines. Good agreement with experiment were obtained for Δ/k=215.5 K; λ/k=166.5 K;J _nn k=27.7 K; andJ _nnn k=−2.3 K. Using these values of the crystal field and exchange parameters the CEF predicts aT _N=122 K for FePS₃, which is remarkably close to the observed value of theT _N. The accuracy of the CEF approximation was also ascertained by comparing the calculated susceptibilities in the CEF with the experimental susceptibility for the isotropic Heisenberg layered antiferromagnet MnPS₃, for which the high temperature series expansion susceptibility is available.     

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.     

Binding of Quercetin to Lysozyme as Probed by Spectroscopic Analysis and Molecular Simulation

The binding of quercetin to lysozyme (LYSO) in aqueous solution was investigated by fluorescence spectroscopy, UV-vis absorption spectroscopy and molecular simulation at pH 7.4. The fluorescence quenching of LYSO by addition of quercetin is due to static quenching, the binding constants, K _a , were 3.63 × 10⁴, 3.31 × 10⁴ and 2.85 × 10⁴ L·mol⁻¹ at 288, 298 and 308 K, respectively. The thermodynamic parameters, enthalpy change, ∆H, and entropy change, ∆S, were noted to be −7.56 kJ·mol⁻¹ and 61.07 J·mol⁻¹·K⁻¹. The results indicated that hydrophobic interaction may play a major role in the binding process. The distance r between the donor (LYSO) and acceptor (quercetin) was determined as 3.34 nm by the fluorescence resonance energy transfer. The synchronous fluorescence spectroscopy showed the polarity around the tryptophan residues increased and the hydrophobicity decreased. Furthermore, the study of molecular simulation indicated that quercetin could bind to the active site (a pocket made up of 24 amino-acid residues) of LYSO mainly via hydrophobic interactions and that there were hydrogen interactions between the residues (Gln 57, Ile 98) of LYSO and quercetin. The accessible surface area (ASA) calculation verified the important roles of tryptophan (Trp) residues during the binding process.     

Temperature dependence of self-broadening in molecular-oxygen spectrum

Summary The ^p P(k=9) magnetic-dipole transition of the oxygen 0-0 vibrational band of the red systemb ¹Σ _g ⁺ ←X ³Σ _g ⁻ was observed with absorption spectroscopy using a tunable CW diode laser. A systematic investigation of the self-collisional broadening was performed for different gas pressures and temperatures. The temperature dependence of the self-broadening coefficient was determined to beT ^{−(1.02±0.05)}. Our results are of interest for collisional theory and as reference data in atmospheric monitoring applications. The authors of this paper have agreed to not receive the proofs for correction.     

Laser photoacoustic spectroscopy of iodine molecule: Single and two-photon absorption

Photoacoustic spectroscopy of iodine molecule has been studied in gas phase using nitrogen laser-pumped tunable dye laser. The experiment yielded the vibrational spectrum corresponding toX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _g ⁺ ) transition up to the convergence limit. The photo-acoustic spectrum in the region 17580–18850 cm⁻¹ is presented along with the vibrational analysis. Five of the vibrational bands reported earlier by Venkateswarlu, Kumar and McGlynn have been partially resolved and the structure of one of them has been analyzed and shown to be due to an overlap of (14, 2) and (12, 1) bands. The analysis was based on a comparison with the highly resolved spectrum of Gerstenkorn and Luc. The structure observed in the region 20200–20750 cm⁻¹ which is beyond the convergence limit of the transitionX ¹Σ⁺(0 _g ⁺ )→B ³Π(0 _u ⁺ ) has been analyzed as due to two-photon absorption. Most of the bands could be assigned to two transitions both originating in the ground state and terminating in two different electronic states 1 _g andE(0 _g ⁺ ), atT _e=40821 cm⁻¹ (orT ₀=41355 cm⁻¹) andT _e=41411 cm⁻¹ (orT ₀=41355 cm⁻¹) respectively.     

Dynamic and spectral mixing in nanosystems

In the framework of a simple spin-boson Hamiltonian we study an interplay between dynamic and spectral roots to stochastic-like behavior. The Hamiltonian describes an initial vibrational state coupled to discrete dense spectrum reservoir. The reservoir states are formed by three sequences with rationally independent periodicities 1; 1 ± δ typical for vibrational states in many nanosize systems (e.g., large molecules containing CH₂ fragment chains, or carbon nanotubes). We show that quantum evolution of the system is determined by a dimensionless parameter δΓ, where Γ is characteristic number of the reservoir states relevant for the initial vibrational level dynamics. When δΓ > 1 spectral chaos destroys recurrence cycles and the system state evolution is stochastic-like. In the opposite limit δΓ < 1 dynamics is regular up to the critical recurrence cycle k _c and for larger k > k _c dynamic mixing leads to quasi-stochastic time evolution. Our semi-quantitative analytic results are confirmed by numerical solution of the equation of motion. We anticipate that both kinds of stochastic-like behavior (namely, due to spectral mixing and recurrence cycle dynamic mixing) can be observed by femtosecond spectroscopy methods in nanosystems in the spectral window 10¹¹–10¹³ s⁻¹     

Steady State and Time-Resolved Fluorescence Studies of a Hemagglutinin from Moringa oleifera

The saccharide binding and conformational characterization of a hemagglutinin, a low molecular weight protein from the seeds of Moringa oleifera was studied using steady state and time resolved fluorescence. The lectin binds sugars LacNAc (K _a = 1380 M⁻¹) and fructose (K _a = 975 M⁻¹), as determined by the fluorescence spectroscopy. It has a single tryptophan per monomer which is exposed on the surface and is in a strong electropositive environment as revealed by quenching with iodide. Quenching of the fluorescence by acrylamide involved both static (K _s = 0.216 M⁻¹) and collisional (K _sv = 8.19 M⁻¹) components. The native protein showed two different lifetimes, τ ₁ (1.6 ns) and τ ₂ (4.36 ns) which decrease and get converted into a single one, (2.21 ns) after quenching with 0.15 M acrylamide. The bimolecular quenching constant, k _q was 7.55 × 10¹¹ M⁻¹ s⁻¹. ANS binding studies showed that the native protein has exposed hydrophobic patches which get further exposed at extreme acidic or alkaline pH. However, they get buried in the interior of the protein in presence of 1 M GdnHCl or urea.     

Study on the Binding Behavior of Lysozyme with Cephalosporin Analogues by Fluorescence Spectroscopy

It was first found that the intrinsic fluorescence of lysozyme at 340 nm can be quenched by cephalosporin analogues through the static quenching and non-radiative energy transferring procedure. In the acetate buffer solution with pH 7.0 and 298 K, the quenching fluorescence intensity was in a good linearity over the concentration of drugs in the range of 1–100 μmol L⁻¹, 0.1–100 μmol L⁻¹, 0.5–100 μmol L⁻¹ and 0.05–100 μmol L⁻¹ for cefradine, cefuroxime, cefotaxime and ceftriaxone, respectively. The quenching ability or the binding ability of the studied drugs followed the pattern: ceftriaxone > cefotaxime > cefuroxime > cefradine, which was close to the order of their antibacterial ability. The binding parameters including the association constant and the number of binding potential point were calculated at different temperatures (288, 298 and 308 K), and thermodynamic parameters ΔH°, ΔS° and ΔG° were given. The binding mode of lysozyme with cephalosporins showed that the hydrophobic effect might play a major role. The binding distance between cephalosporin and tryptophan residue in lysozyme was obtained. The results provided the quantitative information for the binding of cephalosporin to lysozyme, and it was suggested that the drugs probably bound to the active site near Trp62 in lysozyme.     

Self-assembling effects and mechanisms of interchromophore interactions in porphyrin pentads

The directional self-assembly of nanosized, structurally organized pentads that include five tetrapyrrole macrocycles and are based on the two-point coordination interaction of two covalently bound dimers of Zn porphyrins (homo-and heterodimers) with molecules of either the free base or the Cu complex of tetrametapyridyl-substituted porphyrin extra ligand is implemented in methylcyclohexane at 295 K. Using the method of the density functional theory (DFT) in the B3LYP/6-31g(d) approximation, the geometry of the pentad is fully optimized and the main factors that determine its redox properties are determined. The energies of the lowest excited states of the pentad are calculated by the ZINDO/S method, and it is shown that the occurrence of identical molecules in the system facilitates the formation of excitonic states with different contributions from the charge-transfer component. The directional energy transfer and the photoinduced electron transfer, which leads to the formation of a low-lying charge-transfer state (CT state), are studied and the rate constants of these two processes are determined (k _ET ∼ 10¹¹ s⁻¹ and k _PET ≈ (1.8−6.0) × 10⁹ s⁻¹, respectively). The strong effect of the temperature of the solvent on the efficiency of relaxation processes in pentad complexes under study is revealed and studied. Roles played by the low-lying CT state and d-π exchange effects (the Cu-contained pentad) in fluorescence quenching of pentad complexes are determined.     

On the technique of absolutization of diffuse scattering intensity measurements based on thermal diffuse scattering measurements

Features of microdefect (MD) formation in GaAs(Si) single crystals grown by horizontally oriented crystallization were studied by X-ray diffuse scattering (XRDS). Measurements were performed at room temperature (∼298 K) and near the liquid nitrogen evaporation temperature (∼85 K) using an open-flow cooling nitrogen cryostat. A practical technique for measuring XRDS using a triple-axis X-ray diffractometer was developed and applied to separate scattering on defects and thermal diffuse scattering. For a crystal with n = 2.0 × 10¹⁸ cm⁻³, the radius of detected nonspherical MDs was determined as ∼0.2 μm; thermal diffuse scattering (TDS) was experimentally separated. For a crystal with n = 3.9 × 10¹⁸ cm⁻³, nonspherical MDs ∼0.5 μm in radius were detected; TDS was found to be a negligible fraction of total XRDS. At the same time, in the case of coinciding crystal orientations and identical experimental conditions, TDS measurement data for one crystal can be used for other GaAs(Si) crystals with the same orientation.     

Fluorescence of N,N-di(2-carboxyethyl)-<Emphasis Type="Italic">p</Emphasis>-anisidine in solution and crystalline states

The fluorescence properties of N,N-di(2-carboxyethyl)-p-anisidine (I) in solvents of various nature and in the crystalline state have been studied at room temperature (273 K) and at the boiling point of liquid nitrogen (77 K). Fluorescence in aqueous solutions of I with protonated (λ _ex /λ _fl ^max = 225/290 nm) and unprotonated (λ _ex /λ _fl ^max = 270/380 nm) amino nitrogen has been detected. On going from aqueous solutions to nonaqueous, the fluorescence band of unprotonated I experiences a blue shift and its intensity rises. The fluorescence intensity of the band in aprotic polar solvents is higher than that in protic solvents. A linear dependence of the fluorescence intensity of deprotonated I on Cu(II) concentration (ranging from 1.0 to 5.0 mg/dm³) in aqueous solution has been found. The fluorescence intensity of I in aqueous solutions at 77 K and pH 1–6 has been shown to increase in the presence of Zn(II) (1–170 mg/dm³) and Cd(II) (2–330 mg/dm³) although a similar dependence is not observed at 293 K.     

Reactivity at the oxygen/titania interface and the related charge transfer

The present paper reports the reactivity between TiO₂ and oxygen and the related charge transfer at 298 and 1,073 K. The studies were performed using work function measurements. It was found that oxidation of TiO₂ at 1,073 K and p(O₂) = 75 kPa, initially standardized at 1,173 K and p(O₂) = 10 Pa, results in work function changes that are consistent with the theoretical model of the charge transfer during oxygen chemisorption and oxygen incorporation at the absence of structural transitions. However, oxidation of TiO₂ at 298 K, p(O₂) = 75 kPa, which has been initially standardized at 1,173 K in extremely reducing conditions at p(O₂) = ∼10⁻¹⁰ Pa, results in work function changes that are consistent with low-dimensional structural changes of the surface layer. It is shown that oxidation of strongly reduced TiO₂ at 298 K results in a decrease of work function, which cannot be explained without assuming the structural changes of the outermost surface layer.     

Spectrum of Kelvin-wave turbulence in superfluids

We derive a type of kinetic equation for Kelvin waves on quantized vortex filaments with random large-scale curvature, that describes step-by-step (local) energy cascade over scales caused by 4-wave interactions. Resulting new energy spectrum E _LN(k) ∝ k ^−5/3 must replace in future theory (e.g., in finding the quantum turbulence decay rate) the previously used spectrum E _KS(k) ∝ k ^−7/5, which was recently shown to be inconsistent due to nonlocality of the 6-wave energy cascade.     

Monitoring of all hydrogen isotopologues at tritium laboratory Karlsruhe using Raman spectroscopy

We have recorded Raman spectra for all hydrogen isotopologues, using a CW Nd:YVO₄ laser (5 W output power at 532 nm) and a high-throughput (f/1.8) spectrograph coupled to a Peltier-cooled (200 K) CCD-array detector (512 × 2048 pixels). A (static) gas cell was used in all measurements. We investigated (i) “pure” fillings of the homonuclear isotopologues H₂, D₂, and T₂; (ii) equilibrated binary fillings of H₂ + D₂, H₂ + T₂, and D₂ + T₂, thus providing the heteronuclear isotopologues HD, HT, and DT in a controlled manner; and (iii) general mixtures containing all isotopologues at varying concentration levels. Cell fillings within the total pressure range 13–985 mbar were studied, in order to determine the dynamic range of the Raman system and the detection limits for all isotopologues. Spectra were recorded for an accumulation period of 1000 s. The preliminary data evaluation was based on simple peak-height analysis of the ro-vibrational Q₁-branches, yielding 3σ measurement sensitivities of 5 × 10⁻³, 7 × 10⁻³, and 25 × 10⁻³ mbar for the tritium-containing isotopologues T₂, DT, and HT, respectively. These three isotopologues are the relevant ones for the KATRIN experiment and in the ITER fusion fuel cycle. While the measurement reported here were carried out with static-gas fillings, the cells are also ready for use with flowing-gas samples.     

Rare t-quark decays t → clj+lk? and t → c?jvk induced by doublets of scalar leptoquarks within the minimal four-color-symmetry model

The rare t-quark decays t → cl _j ⁺ l _k ⁻ and t → cṽ _j k _k induced by scalar-leptoquark doublets are considered within the minimal model involving four-color quark-lepton symmetry and the Higgs mechanism of quark and lepton mass splitting. The partial widths with respect to the decays being considered and the total widths Γ(t → cl ⁺′l ⁻) = Σ_j,k Γ(t → cl _j ⁺ l _k ⁻ ) and Γ(t → cl ⁺′l ⁻) = Σ_j,kΓ(t → cṽ _j v _k ) with respect to, respectively, the charged leptonic and neutrino modes are calculated. It is shown that, at scalar-leptoquark masses higher than the t-quark mass (m _S > m _t), the branching ratios for these modes are Br(t → cl ⁺′l ⁻) ≈ (3.5−0.4) × 10⁻⁵ and Br(t → cṽ′v) ≈ (7.1−0.8) × 10⁻⁵ at m _s = 180–250 GeV and an appropriate value of the leptoquark-mixing angle (sin β ≈ 0.2) and can increase for m _S < m _t to Br(t → cl ⁺′l ⁻) ≈ 0.03−0.002 and Br(t → cl ⁺′l ⁻) ≈ 0.46−0.05 for the charged mode at m _S = 150–170 GeV for sin β ≈ 1 and sin β ≈ 0.2, respectively. In the cases being considered, t-quark decays to pairs of charged leptons can be accessible to detection at LHC. In the last case, these decays could manifest themselves (for example, in dilepton events) at the Tevatron as well. Original Russian Text ? P.Yu. Popov, A.D. Smirnov, 2006, published in Yadernaya Fizika, 2006, Vol. 69, No. 6, pp. 1006–1016.