Investigation in thorium phosphate by NMR II-phosphorus dipolar networks

With through space and through bond experiments in two-dimensional NMR we analyze the transformation from the thorium phosphate-hydrogen phosphate hydrate (TPHPH) to the β form of the thorium phosphate diphosphate (β-TPD) in relation with the phosphorus networks. These techniques are complementary: the through space coupling gives an insight on the dipolar phosphorus networks while the through bond coupling is particularly efficient in the detection of the P₂O₇ groups. With these experiments we show that in a first step, by heating the precursor TPHPH above 250 °C, it transforms into an form of TPD. This transformation is due to the complete condensation of hydrogen phosphate groups HPO₄ into P₂O₇ entities. By heating -TPD above 950 °C it transforms into its well-known β form. The form is characterized by a hygroscopic behavior: some water molecules are present near the P₂O₇ groups that makes non-equivalent their phosphorus nuclei. PO₄ dipolar networks are always present in the form. The main effect of these PO₄ and P₂O₇ units is to give the system a channel structure and the water enters in them.     

Adaptive estimation of the stationary density of a stochastic differential equation driven by a fractional Brownian motion

Statistical Inference for Stochastic Processes - We build and study a data-driven procedure for the estimation of the stationary density f of an additive fractional SDE. To this end, we also prove...     

Optimization by ant algorithms: possible roles for an individual ant

In most ant algorithms, the role of each ant is to build a solution in a constructive way, basing each decision on the greedy force and the trails. However, different roles are possible for each individual ant, ranging from a negligible help in the decision process to a refined local search heuristic. In this paper, the importance of the role assigned to each ant is discussed. Three general ant methodologies are presented. Comparative results are analyzed for the well-known graph coloring problem.     

Critical reflexivity in financial markets: a Hawkes process analysis

We model the arrival of mid-price changes in the E-mini S&P futures contract as a self-exciting Hawkes process. Using several estimation methods, we find that the Hawkes kernel is power-law with a decay exponent close to ?1.15 at short times, less than ≈ 10³ s, and crosses over to a second power-law regime with a larger decay exponent ≈–1.45 for longer times scales in the range [10³ ,10⁶ ] seconds. More importantly, we find that the Hawkes kernel integrates to unity independently of the analysed period, from 1998 to 2011. This suggests that markets are and have always been close to criticality, challenging a recent study which indicates that reflexivity (endogeneity) has increased in recent years as a result of increased automation of trading. However, we note that the scale over which market events are correlated has decreased steadily over time with the emergence of higher frequency trading.     

Observation of a non-adiabatic geometric phase for elastic waves

We report the experimental observation of a geometric phase for elastic waves in a waveguide with helical shape. The setup reproduces the experiment by Tomita and Chiao [A. Tomita, R.Y. Chiao, Phys. Rev. Lett. 57 (1986) 937–940, 2471] that showed first evidence of a Berry phase, a geometric phase for adiabatic time evolution, in optics. Experimental evidence of a non-adiabatic geometric phase has been reported in quantum mechanics. We have performed an experiment to observe the polarization transport of classical elastic waves. In a waveguide, these waves are polarized and dispersive. Whereas the wavelength is of the same order of magnitude as the helix’s radius, no frequency dependent correction is necessary to account for the theoretical prediction. This shows that in this regime, the geometric phase results directly from geometry and not from a correction to an adiabatic phase.     

Superefficient drift estimation on the Wiener space

In the framework of a nonparametric functional estimation for the drift of a Brownian motion $X_t$ we construct Stein type estimators of the form $X_t+D_t\log F$ which are superefficient when $\sqrt{F}$ is a superharmonic functional on the Wiener space for the Malliavin derivative D. To cite this article: N. Privault, A. Réveillac, C. R. Acad. Sci. Paris, Ser. I 343 (2006).     

Interatomic electronic decay driven by nuclear motion

The interatomic electronic decay after inner-valence ionization of a neon atom by a single photon in a neon-helium dimer is investigated. The excited neon atom relaxes via interatomic Coulombic decay and the excess energy is transferred to the helium atom and ionizes it. We show that the decay process is only possible if the dimer's bond stretches up to 6.2 ?, i.e., to more than twice the equilibrium interatomic distance of the neutral dimer. Thus, it is demonstrated that the electronic decay, taking place at such long distances, is driven by the nuclear motion.     

Characterizing Methyl‐Bearing Side Chain Contacts and Dynamics Mediating Amyloid β Protofibril Interactions Using 13Cmethyl‐DEST and Lifetime Line Broadening

Many details pertaining to the formation and interactions of protein aggregates associated with neurodegenerative diseases are invisible to conventional biophysical techniques. We recently introduced ¹⁵N dark‐state exchange saturation transfer (DEST) and ¹⁵N lifetime line‐broadening to study solution backbone dynamics and position‐specific binding probabilities for amyloid β (Aβ) monomers in exchange with large (2–80 MDa) protofibrillar Aβ aggregates. Here we use ¹³C_methyl DEST and lifetime line‐broadening to probe the interactions and dynamics of methyl‐bearing side chains in the Aβ‐protofibril‐bound state. We show that all methyl groups of Aβ40 populate direct‐contact bound states with a very fast effective transverse relaxation rate, indicative of side‐chain‐mediated direct binding to the protofibril surface. The data are consistent with position‐specific enhancements of ¹³C_methyl‐${R{{{\rm tethered}\hfill \atop 2\hfill}}}$ values in tethered states, providing further insights into the structural ensemble of the protofibril‐bound state.     

Development of an automated in situ fracture stage for a ToF‐SIMS system

The design philosophy and implementation of an ultra high vacuum (UHV), PC controlled, automated in situ fracture stage for a surface analysis system is described. ToF‐SIMS spectra are shown to illustrate the improvement in spectral quality obtained from micro‐compact tension (CT) tests of polymer matrix fracture surfaces produced using the fracture stage in UHV compared to those obtained from a sample tested at air. This system is flexible in that by changing the capacity of the load cell it is possible to reduce or increase maximum loads as the specimen type and material demands. The stage has been designed with instrumental flexibility in mind, utilising commercial SEM‐stub type sample mounts, and can thus be used for AES/SAM and XPS investigations, as well as ToF‐SIMS analysis, in the authors' laboratory. Copyright © 2008 John Wiley & Sons, Ltd.