Preparation of CuCr<Subscript>2</Subscript>O<Subscript>4</Subscript> nanopowders using two different chromium sources

CuCr₂O₄ spinel powders were synthesized starting from different chromium sources, namely (i) chromium oxide (α-Cr₂O₃) and (ii) ammonium dichromate ((NH₄)₂Cr₂O₇). The copper source was a Cu(II) carboxylate-type complex. The Cu(II) carboxylate complex was obtained by the redox reaction between Cu(NO₃)₂·3H₂O and 1,3-propanediol (1,3PG) at 130 °C. In the first case (i), we have started from a mixture of α-Cr₂O₃, Cu(NO₃)₂·3H₂O and 1,3PG that upon heating formed the copper malonate complex, which decomposed around 220 °C forming an oxide mixture (CuO + α-Cr₂O₃). In the second case (ii), (NH₄)₂Cr₂O₇, Cu(NO₃)₂·3H₂O and 1,3PG were homogenously mixed. Heating this mixture at 130 °C resulted, in situ, in the Cu(II) complex. On controlled temperature increase, the violent decomposition of (NH₄)₂Cr₂O₇ took place at 180 °C along with the decomposition of the Cu(II) complex, leading to an amorphous oxide mixture of Cr₂O_3+x and CuO. By annealing the samples in the temperature range 400–1000 °C, the spinel phase (CuCr₂O₄) was obtained in both cases: (i) at 800 °C and (ii) at 600 °C as a result of the interactions between the precursors used, when the oxide system was amorphous and highly reactive. The presence of CuCr₂O₄ was highlighted by XRD and FTIR analyses.     

Upward Propagation of Very Lean Methane-Air Flames in Vertical Tubes

The upward propagation of a lean methane-air flame front in a vertical tube is investigated. The velocity of the flame front has been measured with an array of photodiodes set along the tube wall and, independently, from photographic records. A PIV system triggered by a photodiode signal has been used to measure the velocity of the flow induced by the flame front in a vertical plane through the axis of the tube. The contour of the luminous region of the flame front, assumed cylindrically symmetric, has been extracted from the recorded images. As expected, the shape and velocity of a very lean flame front, and the velocity of the fresh gas relative to the front, are similar to those of a bubble rising in the tube. The flow of the burnt gas features a region of low velocity (relative to the flame front) which enhances radiation losses and seems to play an important role in the extinction of the flame at the flammability limit. This limit is found to depend very sensitively on the temperature of the tube wall. A simple model is proposed of the flow around the axis of the tube and the combustion around the tip of the flame front. This model uses the measured gas velocity at the axis of the tube together with simplified conservation equations to compute the temperature and species concentrations along the axis for a given kinetic scheme and radiation law. The results for a single overall Arrhenius reaction and for a four-step reduced scheme, both in an optically thin gas, are in reasonable agreement with our experimental data and shed some light on the roles played by radiation losses and kinetic effects on the flammability limit measured in the standard flammability tube. The model can also be used to test other kinetic schemes and radiation laws.     

Measurement of hypoiodous acid concentration by a novel type iodide selective electrode and a new method to prepare HOI. Monitoring HOI levels in the Briggs-Rauscher oscillatory reaction

A new type of iodide selective electrode prepared by dipping a silver wire into molten silver iodide is reported. The electrode was calibrated for silver and iodide ions and the measured electromotive force for various Ag(+) and I(-) concentrations was close to the theoretical within a few millivolts. Besides Ag(+) and I(-) ions, however, the electrode also responds to hypoiodous acid. Thus, the electrode was calibrated for HOI as well, and for that purpose a new method of hypoiodous acid preparation was developed. To explain the close to Nernstian electrode response for HOI and also the effect of hydrogen ion and iodine concentration on that response, the corrosion potential theory suggested earlier by Noszticzius et al. was modified and developed further. Following oscillations in the Briggs-Rauscher reaction with the new electrode the potential crosses the "solubility limit potential" (SLP) of silver iodide. Potentials below SLP are controlled by the concentration of I(-), but potentials above SLP are corrosion potentials determined by the concentration of HOI. Finally, the measured HOI oscillations are compared with calculated ones simulated by a model by Furrow et al.     

Well-posedness of a moving-boundary problem with two moving reaction strips

We deal with a one-dimensional coupled system of semi-linear reaction-diffusion equations in two a priori unknown moving phases driven by a non-local kinetic condition. The PDEs system models the penetration of gaseous carbon dioxide in unsaturated porous materials (like concrete). The main issue is that the strong competition between carbon dioxide diffusion and the fast reaction of carbon dioxide with calcium hydroxide–which are the main active reactants–leads to a sudden drop in the alkalinity of concrete near the steel reinforcement. This process–called concrete carbonation–facilitates chemical corrosion and drastically influences the lifetime of the material. We present details of a class of moving-boundary models with kinetic condition at the moving boundary and address the local existence, uniqueness and stability of positive weak solutions. We also point out our concept of global solvability. The application of such moving-boundary systems to the prediction of carbonation penetration into ordinary concrete samples is illustrated numerically.     

Thermal Studies of the Hardening of the Systems Calcium Silicates–Electrolyte–Water

Thermal studies, sometimes together with X-ray analysis, were applied to investigate the process of hydration in the systems calcium silicates (tricalcium silicate or dicalcium silicate) - water - electrolyte. Alkali metal or alkaline-earth metal salts were used as electrolytes. Results and conclusions are presented concerning the action of electrolytes upon the kinetics of hardening of the calcium silicates and the composition and phase transformation of calcium hydrosilicate in the presence of low proportions of electrolytes (0.5, 2 and 5 mass%), these effects being due to ionic substitution. A higher proportion of electrolyte (above 2%) in the systems calcium silicate-water can determine the formation of a complex salt, e.g. calcium hydroxysalts or double hydrosilicates. This revised version was published online in August 2006 with corrections to the Cover Date.     

Magnetic resonance investigations of phase transitions and modulation wave motions in incommensurate solids

We measured⁸⁷Rb nuclear magnetic resonance (NMR) and³⁵Cl nuclear quadrupole resonance (NQR) Hahn spin-echo magnetization decays in the incommensurate (I) phase of Rb₂ZnCl₄ and, in each case, obtained a Hahn echo decay that was shorter than the Carr-Purcell-Meiboom-Gill decay and one which decayed with a time constant proportional to the cube of the echo time. From these measurements we obtained from both the⁸⁷Rb NMR and³⁵Cl NQR measurements values for the diffusion coefficients that are comparable in magnitude, a fact that strongly supports the existence of slow modulation wave diffusionlike motions in the I phase, since such motions should affect both Rb and Cl ions similarly. In addition, we used⁸⁷Rb two-dimensional exchange-difference NMR to study atomic motions in the incommensurate (I) and paraelectric (P) phases to elucidate the nature of the I-P transition. We measured as a function of the mixing time the frequency shifts of the cross peaks from the main diagonal and observed a gradual increase towards an asymptotic value in the I phase but a sudden jump to the final value in the P phase. We interpreted the motions observed in the P phase as normal modes arising from simultaneous reorientations of ZnCl₄ tetrahedra and corresponding Rb ions displacements between two sites. These normal modes freeze out in the I phase and change to the diffusionlike motion of the modulation wave. We also performed³⁵Cl NQR lineshape andT ₁ measurements in K₂ZnCl₄ and obtained conclusive evidence for the presence of a narrow 1q (singly modulated) I phase between 146 and 149 K.     

Dynamics of pedestrians in regions with no visibility— A lattice model without exclusion

We investigate the motion of pedestrians through obscure corridors where the lack of visibility (due to smoke, fog, darkness, etc.) hides the precise position of the exits. We focus our attention on a set of basic mechanisms, which we assume to be governing the dynamics at the individual level. Using a lattice model, we explore the effects of non-exclusion on the overall exit flux (evacuation rate). More precisely, we study the effect of the buddying threshold (of no-exclusion per site) on the dynamics of the crowd and investigate to which extent our model confirms the following pattern revealed by investigations on real emergencies: If the evacuees tend to cooperate and act altruistically, then their collective action tends to favor the occurrence of disasters. The research reported here opens many fundamental questions and should be seen therefore as a preliminary investigation of the very complex behavior of the people and their motion in dark regions.     

Surface‐enhanced Raman spectroscopy of genomic DNA from in vitro grown plant species

Surface‐enhanced Raman scattering (SERS) effect was used to demonstrate ultrasensitive optical detection of nucleic acids. In this work, the SERS spectra of seven genomic DNAs from leaves of Arnica montana (L.), Fam. Compositae, Astragalus peterfii (Jáv.), Fam. Fabaceae, Kalanchoe x hybrida, Fam. Crassulaceae, strawberry (Fragaria x ananassa Duch.), Fam. Rosaceae, carnation (Dianthus caryophyllus L.), Fam. Caryophyllaceae, apple (Malus domestica Borkh.), Fam. Rosaceae and Persian violet (Exacum affine Balf.), Fam. Gentianaceae were analyzed in the wavenumber range 200–1800 cm⁻¹. SERS signatures, spectroscopic band assignments and structural interpretations of these plant genomic DNAs are reported. SERS spectra of nucleic acids are compared here with caution, because these signals are time‐dependent. The SERS spectra corresponding to DNA from Arnica, Dianthus, Fragaria and Kalanchoe leaves show well‐resolved, accurate bands, providing thus a high molecular structural information content. Based on this work, specific plant DNA–ligand interactions or DNA structural changes induced by plant stress conditions associated with their natural environment might be further investigated using SERS spectroscopy. Besides, this study will generate information that is valuable in the development of label‐free DNA‐based nanosensors for chemical probing in the living cell. Copyright © 2011 John Wiley & Sons, Ltd.     

A multiscale Galerkin approach for a class of nonlinear coupled reaction-diffusion systems in complex media

A Galerkin approach for a class of multiscale reaction-diffusion systems with nonlinear coupling between the microscopic and macroscopic variables is presented. This type of models are obtained e.g. by upscaling of processes in chemical engineering (particularly in catalysis), biochemistry, or geochemistry. Exploiting the special structure of the models, the functions spaces used for the approximation of the solution are chosen as tensor products of spaces on the macroscopic domain and on the standard cell associated to the microstructure. Uniform estimates for the finite dimensional approximations are proven. Based on these estimates, the convergence of the approximating sequence is shown. This approach can be used as a basis for the numerical computation of the solution.     

The influence of divalent metal ions on low pH induced LacDNA structural changes as probed with UV resonance Raman spectroscopy

UV (275 nm) resonance Raman spectra of LacDNA 22‐mer duplex [d(TAATGTGAGTTAGCTCACTCAT) · d(ATGAGTGAGCTAACTCACATTA)], which contain protein binding sites within the E. coli lac promoter, were measured at two pH values (6.4 and 3.45) in the absence and presence of Mn²⁺ and Ca²⁺ metal ions, respectively. Also, the UV (275 nm) resonance Raman markers of the corresponding oligonucleotide d(TAATGTGAGTTAGCTCACTCAT) and of its complementary anti‐sense strand d(ATGAGTGAGCTAACTCACATTA) were established and tentatively assigned. Large changes in the UV (275 nm) resonance Raman spectra of LacDNA duplex were observed at pH 3.45 as compared with the corresponding spectrum at pH 6.4, in the absence of divalent metal ions and at low concentrations of Ca²⁺ ions, respectively. Major changes comprise: adenine protonation, GC base pair protonation, DNA bases unstacking and changes in the hydrogen bonding strength between the strands of different LacDNA complexes, respectively. Divalent metal ions (Mn²⁺ and Ca²⁺) were found to inhibit LacDNA protonation even at low concentrations. Manganese(II) ions are much more effective in this regard, as compared with calcium(II) ions. Binding of Mn²⁺ ions to N7 of guanine and, possibly, in a lesser extent to adenine was observed as judging from the difference Raman bands at 1315, 1354 and 1493 cm⁻¹. Copyright © 2013 John Wiley & Sons, Ltd.