Multilayered electrochemical cell for NOx decomposition at moderate temperatures

A new multilayered electrochemical cell for NO_x decomposition was prepared. The cell demonstrated good characteristics at moderate temperatures (350–450 °C) and possessed much higher selectivity with respect to NO_x decomposition than previous one. It was found that the “crossover” process from high selective regime to the normal regime depends on the chemical composition of the catalytic electrode.     

NH3NO interaction at low-temperatures: An experimental and modeling study

The present work provides new insight into NH₃NO interaction under low-temperature conditions. The oxidation process of neat NH₃ and NH₃ doped with NO (450, 800 ppm) was experimentally investigated in a Jet Stirred Flow Reactor at atmospheric pressure for the temperature range 900–1350 K. Results showed NO concentration is entirely controlled by DeNO_x reactions in the temperature range 1100–1250 K, while NH₃NO interaction does not develop through a sensitizing NO effect, for these operating conditions.A detailed kinetic model was developed by systematically updating rate constants of controlling reactions and declaring new reactions for N₂H₂ isomers (cis and trans). The proposed mechanism well captures target species as NO and H₂ profiles. For NH₃NO mixtures, NO profiles were properly reproduced through updated DeNO_x chemistry, while NH₂ recombination reactions were found to be essential for predicting the formation of H₂. The role of ammonia as a third-body species is implemented in the updated mechanism, with remarkable effects on species predictions. For neat NH₃ mixture, the reaction H+O₂(+M)=HO₂(+M) was crucial to predict NO formation via the reaction NH₂+HO₂H₂NO+OH.     

Spin glasses with long-range interaction at high temperatures

We study the Ising andN-vector spin glasses with exchange couplings J=(J _ij ;i, jZ ^d ), which are independent random variables with EJ_ij=0 andEJ ⁿ _ij ⁿ n!¦i–j¦ ^–nd , forn, some finite constant >0, and >1/2. For sufficiently small, we show that forE-a.a.J there is a weakly unique, extremal, infinite-volume Gibbs measure _J for which the expectation of a single (component of) spin vanishes and which has the cluster property inL ₂(E) with the same decay as interaction. This work is based on results and methods of Fröhlich and Zegarlinski.     

Study on the interaction between tabersonine and human serum albumin by optical spectroscopy and molecular modeling methods

The mechanism of interaction between tabersonine (TAB) and human serum albumin (HSA) was investigated by the methods of fluorescence spectroscopy, UV–vis absorption spectroscopy and molecular modeling under simulative physiological conditions. Results obtained from analysis of fluorescence spectrum and fluorescence intensity indicated that TAB has a strong ability to quench the intrinsic fluorescence of HSA through a static quenching procedure. The binding site number n and apparent binding constant K_a, corresponding thermodynamic parameters ΔG, ΔH and ΔS at different temperatures were calculated. The distance r between donor (human serum albumin) and acceptor (tabersonine) was obtained according to the Förster theory of non-radiation energy transfer. The effect of common ions on binding constant was also investigated. The synchronous fluorescence and three-dimensional fluorescence spectra were used to investigate the structural change of HSA molecules with addition of TAB. Furthermore, the study of molecular modeling indicated that TAB could bind to the site I of HSA and hydrophobic interaction was the major acting force, which was in agreement with the binding mode study.     

Insights into the Discrepancy between Single Molecule Experiments

Sharp bending as one of the mechanical properties of double-stranded DNA(dsDNA) on the nanoscale is essential for biological functions and processes. Force sensors with optical readout have been designed to measure the forces inside short, strained loops composed of both dsDNA and single-stranded DNA(ssDNA). Recent FRET singlemolecule experiments were carried out based on the same force sensor design, but provided totally contrary results. In the current work, Monte Carlo simulations were performed under three conditions to clarify the discrepancy between the two experiments. The criterion that the work done by the force exerted on dsDNA by ssDNA should be larger than the nearest-neighbor(NN) stacking interaction energy is used to identify the generation of the fork at the junction of dsDNA and ssDNA. When the contour length of dsDNA in the sensor is larger than its critical length, the fork begins to generate at the junction of dsDNA and ssDNA, even with a kink in dsDNA. The forces inferred from simulations under three conditions are consistent with the ones inferred from experiments, including extra large force and can be grouped into two different states, namely, fork states and kink states. The phase diagrams constructed in the phase space of the NN stacking interaction energy and excited energy indicate that the transition between the fork state and kink state is difficult to identify in the phase space with an ultra small or large number of forks, but it can be detected in the phase space with a medium number of forks and kinks.     

Experimental evidence for the direct interaction between two-level systems in glasses at very low temperatures

We have measured the direct interaction between two-level systems in glasses at low temperatures. This interaction results in a strong broadening of the excited state in addition to the natural linewidth. A theoretical explanation of our result is given regarding the two-level systems as an elastic dipole.     

Phonon spectrum and interaction between nanotubes in single-walled carbon nanotube bundles at high pressures and temperatures

The Raman spectra of single-walled carbon nanotubes at temperatures up to 730 K and pressures up to 7 GPa have been measured. The behavior of phonon modes and the interaction between nanotubes in bundles have been studied. It has been found that the temperature shift of the vibrational G mode is completely reversible, whereas the temperature shift of radial breathing modes is partially irreversible and the softening of the modes and narrowing of phonon bands are observed. The temperature shift and softening of radial breathing modes are also observed when samples are irradiated by laser radiation with a power density of 6.5 kW/mm². The dependence of the relative frequency Ω/Ω₀ for G ⁺ and G ^? phonon modes on the relative change A ₀/A in the triangular lattice constant of bundles of nanotubes calculated using the thermal expansion coefficient and compressibility coefficient of nanotube bundles shows that the temperature shift of the G mode is determined by the softening of the C-C bond in nanotubes. An increase in the equilibrium distances between nanotubes at the breaking of random covalent C-C bonds between nanotubes in bundles of nanotubes is in my opinion the main reason for the softening of the radial breathing modes.     

Characterization of the interaction between human lactoferrin and lomefloxacin at physiological condition: Multi-spectroscopic and modeling description

The interaction between lomefloxacin (LMF) and human lactoferrin (Hlf) was studied by using fluorescence, circular dichroism (CD) spectroscopic and molecular modeling measurements. By the fluorescence quenching results, it was found that the binding constant K_A=8.69×10⁵ L mol⁻¹, and number of binding sites n=1.75 at physiological condition. Experimental results observed showed that the binding of LMF to Hlf induced conformational changes of Hlf. The participation of tyrosyl and tryptophanyl residues of protein was also estimated in the drug-Hlf complex by synchronous fluorescence. The quantitative analysis data of far-UV CD spectra from that of the α-helix 37.4% in free Hlf to 30.2% in the LMF-Hlf complex further confirmed that secondary structure of the protein was changed by LMF. Near-UV CD showed perturbations around tryptophan and tyrosine residues which involves perturbations of tertiary structure. The thermodynamic parameters like, ΔH° and ΔS°, have been calculated to be 63.411 kJ mol⁻¹ and 231.104 J mol⁻¹ K⁻¹, respectively. Thermodynamic analysis showed that hydrophobic interactions were the main force in the binding site but the hydrogen bonding and electrostatic interaction could not be excluded which in agreement with the result of molecular docking study. The distance r between donor and acceptor was obtained according to fluorescence resonance energy transfer (FRET) and found to be 1.78 nm. The interaction between LMF and Hlf has been verified as consistent with the static quenching procedure and the quenching mechanism is related to the energy transfer. Furthermore, the study of molecular modeling that LMF could bind to the α-helixes between Pro145-Asn152 and Phe167-Gln172 regions and hydrophobic interaction was the major acting force for the binding site, which was in agreement with the thermodynamic analysis.     

Shock tube study of the interaction between ammonia and nitric oxide at high temperatures using laser absorption spectroscopy

The interaction between ammonia (NH₃) and nitric oxide (NO) at high temperatures is studied in this work using a shock tube combined with laser absorption diagnostics. The system simultaneously measured the NH₃ and NO time-histories during the reaction processes of the shock-heated NH₃/NO/CO/Ar mixtures (NH₃:NO ≈ 0.9:1.0 and 1.4:1.0). The absorption cross-sections of NH₃ near 1122.10 cm^–1 and NO at 1900.52 cm^–1 (characterized in this study) were used for measuring NH₃ and NO time-histories with the temperature measured by two CO absorption lines. The measured NH₃ and NO time-histories at 1614–1968 K and 2.4–2.8 atm were compared with predictions of seven recent kinetics models. The predictions that based on different mechanisms are very different and the measured profiles are within the range of the predictions. The Glarborg, NUI Galway Syngas-NOx, and Mathieu mechanisms give the closest predictions to the measurements. Kinetics analyses indicate that the NH₃ and NO consumption rates are extremely sensitive to the rate constants and branching ratio of NH₂ + NO = N₂ + H₂O and NH₂ + NO = NNH + OH, which are more reliably represented in the Glarborg and NUI Galway Syngas-NOx mechanisms. The performances of Glarborg mechanisms at lower initial temperatures can be apparently improved by revising the rate constants and branching ratio of NH₂ + NO = N₂ + H₂O and NH₂ + NO = NNH + OH. These two reactions are also the primary pathways for NO reduction and NH₃ is mainly consumed via NH₃ + OH = NH₂ + H₂O and NH₃ + H = NH₂ + H₂. Trace amounts of NO₂ and N₂O impurities decompose to form O radical followed by the generation of OH radical via H-abstraction reactions, which significantly affects the predictions of NH₃ and NO according to kinetics analyses.     

Strong explosive interaction of hydrogenated porous silicon with oxygen at cryogenic temperatures

We report new types of heterogeneous hydrogen-oxygen and silicon-oxygen branched chain reactions which have been found to proceed explosively after the filling of pores of hydrogen-terminated porous silicon (Si) by condensed or liquid oxygen in the temperature range of 4.2-90 K. Infrared vibrational absorption spectroscopy shows that, while initially Si nanocrystals assembling the layers have hydrogen-terminated surfaces, the final products of the reaction are SiO2 and H2O. Time-resolved optical experiments show that the explosive reaction develops in a time scale of 10(-6) s. We emphasize the remarkable structural properties of porous Si layers which are crucial for the strong explosive interaction.     

Insights into the oxidation of propylene oxide through the analysis of experiments and kinetic modeling

Cyclic ethers are important intermediates in the oxidation of hydrocarbons and biofuels. Studying the oxidation and pyrolysis of cyclic ethers will help in improving our understanding of this functional group and provide consistency to the base mechanism where they play an important role. In this aspect, propylene oxide has been investigated in this study by obtaining ignition delay time measurements in the rapid compression machine and shock tube. The experiments were performed in a range of pressures varying from 10 to 40 bar at different equivalence ratios (0.5–2.0) and dilution percentages. Additionally, speciation measurements in the shock tube at pyrolysis conditions have been performed at a pressure of 40 bar to explore the isomerization pathways. A detailed kinetic mechanism was developed to describe both the oxidation and pyrolysis chemistry of propylene oxide. The mechanism is not only able to predict the data obtained from this study but also reproduces the data from the literature in a consistent trend. For a better understanding of the oxidation and pyrolysis chemistry of propylene oxide, the kinetic analyses were performed using the developed mechanism to comprehend the important reaction pathways and sensitive reactions. At the investigated regime, the consumption of propylene oxide through its isomerization channels is the critical pathway that controls the reactivity of the fuel.     

Effect of ultrasound on binding interaction between emodin and micellar casein and its microencapsulation at various temperatures

Emodin is a bioactive compound with strong anti-inflammatory and antioxidant properties. Micellar casein is casein concentrates close to the native state of casein micelles. The interaction of emodin and micellar casein under heat treatment in the absence and presence of ultrasound was investigated, and the properties of microencapsulated emodin in micellar casein were compared. Fluorescence experiments proved that the major interaction between emodin and micellar casein was through hydrophobic forces under heat treatment in the absence and presence of ultrasound. However, ΔH, ΔS and ΔG of emodin-casein complexation without sonication were higher than those with sonication, in contradiction to binding constants. The particle sizes of emodin-casein complexes in the presence of ultrasound were smaller than those without sonication, while the specific surface area showed an opposite trend. As to encapsulation, emodin-casein capsules under heat-sonication treatment showed higher antioxidant properties than those of heat treatment alone under similar experimental conditions. Interestingly, micellar casein-emodin encapsulation in the presence of ultrasound showed a lower release rate of emodin in gastrointestinal conditions than that without ultrasound at the emdoin concentration of 10 μmol per gram casein. Ultrasound has been shown to be a potential processing technology for customizing the release kinetics of bioactive compounds.     

Diffusion coefficient of krypton atoms in helium gas at low and moderate temperatures

In the present work, using the Chapman–Enskog method for dilute gases, the diffusion coefficients of ground krypton atoms in a very weakly ionized helium buffer gas are revisited. The calculations are carried out quantum mechanically in the range of low and moderate temperatures. The ¹ Σ⁺ potential-energy curve via which Kr approaches He is constructed from the most recent ab initio energy points. The reliable data points used in the construction are smoothly connected to adequate long- and short-range forms. The calculations of the classical second virial coefficients and the Boyle temperature of the helium–krypton mixture are also discussed. These coefficients and their variations in terms of temperature are analysed by adopting the constructed HeKr potential and the Lennard–Jones form that fits it. The diffusion and elastic cross sections are also explored and the resonance features they exhibit are closely examined. The variation law of the diffusion coefficients with temperature is determined for typical values of density and pressure. The coefficients show excellent agreement with the available experimental data; the discrepancies do not exceed 5%.     

Structural relaxation of formic acid and its interaction with water and Xe at cryogenic temperatures

The glass-liquid transition of the amorphous HCOOH films and the reorganization of hydrogen-bonds of HCOOH during interactions with adsorbed D₂O and Xe have been investigated on the basis of temperature-programmed TOF-SIMS and TPD. On the as-deposited HCOOH film at 15 K, the physisorbed Xe atom permeates through pores and is trapped in the bulk during pore collapse upon heating. The hydrogen bonds of the HCOOH film are persistent up to 125 K as revealed from the interaction with the adsorbed D₂O molecules. The translational molecular diffusion commences at 125 K and dewetting of the HCOOH film follows at 150 K. The Xe atom incorporated in the bulk of the HCOOH film desorbs at 150 K concomitantly with dewetting of the film. These phenomena can be explained in terms of the glass-liquid transition of formic acid and the slow evolution of fluidity in the supercooled liquid phase.     

3-Pentanone LIF at elevated temperatures and pressures: measurements and modeling

The objective of this study is to investigate 3-pentanone fluorescence experiments in a constant volume vessel at high temperature and high pressure to underline the influent parameters in conditions close to those encountered in internal combustion engines. To obtain quantitative analysis, measured fluorescence signals must be corrected by considering the influence of preponderant parameters such as temperature, pressure and gas composition. Quantitative dependences of fluorescence on thermodynamic parameters are measured and compared with the predictions of a photophysical model, which combines the effects of temperature, pressure, excitation wavelength on fluorescence quantum yield. The increase of 3-pentanone fluorescence with pressure is due to the vibrational relaxation of energy levels. The fluorescence decreases with increasing temperature, except at low temperature where the fluorescence increase is due to an activation of intersystem crossing between triplet toward singlet levels. The influences of thermodynamic parameters are based on an increase of the non-radiative decay rate with the vibrational energy level of excited electronic state and the important collisions to remove the excess vibrational energy. Experimental and calculated results show a satisfactory agreement. PACS 33.20; 33.50; 34.90     

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.     

Plasma-field structures during relativistic laser interaction with overdense plasmas at finite electron temperatures

A simple model taking into account the effect of electron temperature is derived to define the plasma-field structures which may arise during relativistically intense laser interaction with overdense plasmas. We show that there exist multilayer solutions with electron cavitation, allowing for both relativistic and ponderomotive nonlinearities. The influence of finite electron temperature on such structures is studied. Examples of these plasma-field structures for the cases of an infinite plasma and a plasma layer are presented.