Expressing Forest Origins in the Chemical Composition of Cooperage Oak Woods and Corresponding Wines by Using FTICR‐MS

A non‐targeted, ultra‐high‐resolution mass spectrometric, direct analysis of oak‐wood extracts from two species (Quercus robur L. and Quercus petraea Liebl.) from three French forests, and of a wine aged in barrels derived therefrom has been performed to identify families of metabolites that could discriminate both the species and the geographical origin of woods. From 12 T ultra‐high‐resolution Fourier transform ion cyclotron resonance mass spectra of wood extracts, hundreds of mass signals were identified as possible significant biomarkers of the two species, with phenolic and carbohydrate moieties leading the differentiation between Q. robur and Q. petraea, respectively, as corroborated by both FTMS and NMR data. For the first time, it is shown that oak woods can also be discriminated on the basis of hundreds of forest‐related compounds, and particular emphasis is put on sessile oaks from the Tronçais forest, for which sugars are significantly discriminant. Despite the higher complexity and diversity of wine metabolites, forest‐related compounds can also be detected in wines aged in related barrels. It is only by using these non‐targeted analyses that such innovative results, which reveal specific chemodiversities of natural materials, can be obtained.     

Spatially resolved measurements of soot and gaseous precursors in ethylene counterflow diffusion flames up to 32 atm

We investigate the effect of pressure on both flame structure and soot formation in nitrogen diluted counterflow diffusion flames of ethylene in the 8–32atm pressure range. Capillary-probe gas sampling is performed to resolve spatially the profiles of gaseous species up to three-ring aromatics by GC/MS analysis and multi-color pyrometry is used to quantify the soot volume fraction and dispersion exponent. Self-similarity of flames is preserved by keeping constant mixture fraction and strain rate, so that profiles of concentrations and temperature, normalized with respect to their peak values, are unaffected by changes in pressure, once the axial coordinate is nondimensionalized with respect to the pressure-dependent diffusion length scale. When conditions are chosen so that the overall soot loading is approximately constant and compatible with the diagnostics, it is found that both the soot volume fraction and the profiles of key aromatics in the high-temperature nucleation region are virtually invariant. For it to happen, a twofold increase in pressure must be compensated by a ～100 K decrease in peak flame temperature and, therefore, in the temperature across the soot forming region. The implication is that from the perspective of the chemical kinetics of soot formation these two actions counterbalance each other. As pressure increases (and temperature decreases) the peak production rate of the high-temperature soot mechanism decreases and, further downstream, towards the particle stagnation plane, a low-temperature soot mechanism sets in, yielding an increase in soot H/C content. This mechanism is enhanced as the pressure is raised, causing a higher overall soot volume production rate in the 16atm flame and, especially, in the 32atm one. The role of C4/C2 species in the formation of C₆H₆ increases with increasing pressure and dominates over the recombination of propargyl radical at sufficiently high pressures. A comprehensive database is established for soot models at high pressures of relevance to applications.     

Structural and dynamical analysis of monodisperse and polydisperse colloidal systems

We present a semigrand ensemble Monte Carlo and Brownian dynamics simulation study of structural and dynamical properties of polydisperse soft spheres interacting via purely repulsive power-law potentials with a varying degree of "softness." Comparisons focus on crystal and amorphous phases at their coexistence points. It is shown through detailed structural analysis that as potential interactions soften, the "quality of crystallinity" of both monodisperse and polydisperse systems deteriorates. In general, polydisperse crystalline phases are characterized by a more ordered structure than the corresponding monodisperse ones (i.e., for the same potential softness). This counter-intuitive feature originates partly from the fact that particles of different sizes may be accommodated more flexibly in a crystal structure and from the reality that coexistence (osmotic) pressure is substantially higher for polydisperse systems. These trends diminish for softer potentials. Potential softness eventually produces substitutionally disordered crystals. However, substitutional order is apparent for the hard-spherelike interactions. Diffusionwise, crystals appear quite robust with a slight difference in the vibrational amplitudes of small and large particles. This difference, again, diminishes with potential softness. Overcrowding in amorphous polydisperse suspensions causes "delayed" diffusion at intermediate times.     

Kinetics of comet formation in single‐cell gel electrophoresis: Loops and fragments

We investigated the mechanisms of DNA exit during single‐cell gel electrophoresis (the comet assay) by measuring the kinetics of the comet tail formation. In the neutral comet assay, the rate of DNA exit was found to be dependent on the topological state of DNA, which was influenced by either ethidium bromide or a low radiation dose. The results clearly show that the comet tail is formed by extended DNA loops: the loop extension, being reversible when the DNA torsional constraint remains in the loops, is favored when the constraint is relaxed. The kinetics of the comet formation in the case of a high radiation dose points out that accumulation of the single‐strand breaks causes DNA fragmentation. In contrast to the neutral comet assay, the alkaline comet assay is not related to the chromatin loops. Our results imply that the alkaline treatment induces detachment of the loops from the nuclear matrix, and the comet tail is formed by ssDNA fragments, the ends of which are pulled out from the comet head by electric force. We suggest that the kinetic approach can be considered as an important improvement of the comet assay.     

Cyclic voltammetry of nitrophenyl N‐glycosides on mercury electrode

Ten nitrophenyl N‐glycosides have been studied electrochemically in neutral (at pH 7) water–organic solutions by cyclic voltammetry using static mercury drop electrode. For all compounds under investigation the two electrochemical processes have been observed: the four‐electron irreversible reduction of their nitro groups to the corresponding phenylhydroxylamine derivatives, as well as the two‐electron quasi‐reversible process between phenylhydroxylamine and nitroso derivatives. For three compounds the additional electrochemical processes have been also observed, which can be connected with the formation of azoxybenzene derivatives. The potentials of both redox processes: a two‐electron quasi‐reversible R? NHOH/R? NO (E_f) and four‐electron irreversible R? NO₂/R? NHOH (E_pc(I)) systems have been determined and discussed according to crystal structures of selected compounds. E_f and E_pc(I) depended strongly on the positive mesomeric effect (caused by glycosidic nitrogen atom), as well as on the intramolecular hydrogen bond between electroactive nitro group and the hydrogen atom at the glycosidic atom observed in N‐o‐nitrophenyl‐2,3,4,6‐tetra‐O‐acetyl‐β‐D ‐glucopyranosylamine. Moreover, the chirality of selected reactants has had the pronounced effect on the E_pc(I). Copyright © 2011 John Wiley & Sons, Ltd.     

On the completeness of root vectors generated by systems of coupled hyperbolic equations

The paper is the second in a set of two papers, which are devoted to a unified approach to the problem of completeness of the generalized eigenvectors (the root vectors) for a specific class of linear non‐selfadjoint unbounded matrix differential operators. The list of the problems for which such operators are the dynamics generators includes the following: (a) initial boundary‐value problem (IBVP) for a non‐homogeneous string with both distributed and boundary damping; (b) IBVP for small vibrations of an ideal filament with a one‐parameter family of dissipative boundary conditions at one end and with a heavy load at the other end; this filament problem is treated for two cases of the boundary parameter: non‐singular and singular; (c) IBVP for a three‐dimensional damped wave equation with spherically symmetric coefficients and both distributed and boundary damping; (d) IBVP for a system of two coupled hyperbolic equations constituting a Timoshenko beam model with variable coefficients and boundary damping; (e) IBVP for a coupled Euler‐Bernoulli and Timoshenko beam model with boundary energy dissipation (the model known in engineering literature as bending‐torsion vibration model); (f) IBVP for two coupled Timoshenko beams model, which is currently accepted as an appropriate model describing vibrational behavior of a longer double‐walled carbon nanotube. Problems have been discussed in the first paper of the aforementioned set. Problems are discussed in the present paper.     

A networking method to compare theories: metacognition in problem solving reformulated within the Anthropological Theory of the Didactic

An important role of theory in research is to provide new ways of conceptualizing practical questions, essentially by transforming them into scientific problems that can be more easily delimited, typified and approached. In mathematics education, theoretical developments around ‘metacognition’ initially appeared in the research domain of Problem Solving closely related to the practical question of how to learn (and teach) to solve non-routine problems. This paper presents a networking method to approach a notion as ‘metacognition’ within a different theoretical perspective, as the one provided by the Anthropological Theory of the Didactic. Instead of trying to directly ‘translate’ this notion from one perspective to another, the strategy used consists in going back to the practical question that is at the origin of ‘metacognition’ and show how the new perspective relates this initial question to a very different kind of phenomena. The analysis is supported by an empirical study focused on a teaching proposal in grade 10 concerning the problem of comparing mobile phone tariffs.     

Logical structures and genus of proofs

Any arbitrarily complicated non-oriented graph, that is a graph of arbitrarily large genus, can be encoded in a cut-free proof. This unpublished result of Statman was shown in the early seventies. We provide a proof of it, and of a number of other related facts.     

Shear and necking instabilities in nonlinear elasticity

This paper examines the behavior of a class of nonlinearly elastic rods under tension. These rods can suffer longitudinal extension, transverse contraction, shear, and flexure. The deformation is governed by an eighth order, quasilinear system of ordinary differential equations. A convergent perturbation process shows that there is a very rich collection of solutions that bifurcate from the trivial affine configuration. Global results are obtained for hyperelastic rods. These solutions describe instabilities of the shear and necking type and can exhibit hysteresis.

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Résumé On considère le comportement d'une classe de poutres nonlinéairement élastiques en état de tension. Ces poutres peuvent souffrir une extension longitudinale, une contraction transversale, un cisaillement et une fiexion. La déformation est gouvernée par un système quasi-linéaire d'équations différentielles ordinaires du huitième ordre. Un procès convergeant de perturbations montre qu'il y a une collection très riche de solutions qui bifurquent de la configuration banale affine. Dans le cas hypérélastique on obtient des résultats globaux. On montre que ces solutions décrivent des instabilités du type de cisaillement et d'étranglement et peuvent exhiber une hystérésis.

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The research of the first author was supported by National Science Foundation Grant MPS 73-08587 A02. Some of the results reported here were obtained by the second author in his master's thesis.