Approche non paramétrique du filtrage de système non linéaire à temps discret et à paramètres inconnus

Particle filters are presently among the most powerful tools for filtering discrete time non linear systems. However the presence of unknown parameters in the system equations makes their use more complex and can even impair their convergence properties. This Note shows how an on-line consistent estimation of these parameters can be obtained simultaneously to that of the state variables to be filtered. This approach relies upon a kernel-based non parametric estimation of conditional probability densities from successive Monte Carlo generations of system particles. To cite this article: V. Rossi, J.-P. Vila, C. R. Acad. Sci. Paris, Ser. I 340 (2005).     

The combination technique and some generalisations

The combination technique has repeatedly been shown to be an effective tool for the approximation with sparse grid spaces. Little is known about the reasons of this effectiveness and in some cases the combination technique can even break down. It is known, however, that the combination technique produces an exact result in the case of a projection into a sparse grid space if the involved partial projections commute.

The performance of the combination technique is analysed using a projection framework and the C/S decomposition. Error bounds are given in terms of angles between the spanning subspaces or the projections onto these subspaces. Based on this analysis modified combination coefficients are derived which are optimal in a certain sense and which can substantially extend the applicability and performance of the combination technique.     

Acid digestion of geological and environmental samples using open-vessel focused microwave digestion

The application of open vessel focused microwave acid digestion is described for the preparation of geological and environmental samples for analysis using inductively coupled plasma-mass spectrometry (ICP-MS). The method is compared to conventional closed-vessel high pressure methods which are limited in the use of HF to break down silicates. Open-vessel acid digestion more conveniently enables the use of HF to remove Si from geological and plant samples as volatile SiF4, as well as evaporation-to-dryness and sequential acid addition during the procedure. Rock reference materials (G-2 granite, MRG-1 gabbros, SY-2 syenite, JA-1 andesite, and JB-2 and SRM-688 basalts) and plant reference materials (BCR and IAEA lichens, peach leaves, apple leaves, Durham wheat flour, and pine needles) were digested with results comparable to conventional hotplate digestion. The microwave digestion method gave poor results for granitic samples containing refractory minerals, however fusion was the preferred method of preparation for these samples. Sample preparation time was reduced from several days, using conventional hotplate digestion method, to one hour per sample using our microwave method.     

Solid-State and solution studies of [Ln(n)(SiW11O39)] polyoxoanions: an example of building block condensation dependent on the nature of the rare earth

The reactivity of the [alpha-SiW(11)O(39)](8-) monovacant polyoxometalate with lanthanide has been investigated for four different trivalent rare-earth cations (Ln = Nd(III), Eu(III), Gd(III), Yb(III)). The crystal structures of KCs(4)[Yb(alpha-SiW(11)O(39))(H(2)O)(2)] x 24H(2)O (1), K(0.5)Nd(0.5)[Nd(2)(alpha-SiW(11)O(39))(H(2)O)(11)] x 17H(2)O (2a), and Na(0.5)Cs(4.5)[Eu(alpha-SiW(11)O(39))(H(2)O)(2)] x 23H(2)O (3a) are reported. The solid-state structure of compound 1 consists of linear wires built up of [alpha-SiW(11)O(39)](8-) anions connected by Yb(3+) cations, while the linkage of the building blocks by Eu(3+) centers in 3a leads to the formation of zigzag chains. In 2a, dimeric [Nd(2)(alpha-SiW(11)O(39))(2)(H(2)O)(8)](10-) entities are linked by four Nd(3+) cations. The resulting chains are connected by lanthanide ions, leading to a bidimensional arrangement. Thus, the dimensionality, the organization of the polyoxometalate building units, and the Ln/[alpha-SiW(11)O(39)](8-) ratio in the solid state can be tuned by choosing the appropriate lanthanide. The luminescent properties of compound 3a have been studied, showing that, in solution, the polymer decomposes to give the monomeric complex [Eu(alpha-SiW(11)O(39))(H(2)O)(4)](5-). The lability of the four exogenous ligands connected to the rare earth must allow the functionalization of this lanthanide polyanion.     

Crosslinking‐induced morphology change of latex nanoparticles: A study of RAFT‐mediated polymerization in aqueous dispersed media using amphiphilic double‐brush copolymers as reactive surfactants

Amphiphilic double‐brush copolymers (DBCs) with each graft site quantitatively carrying both a hydrophilic poly(ethylene oxide) (PEO) graft and a hydrophobic polystyrene (PSt) graft are synthesized by sequential reversible addition‐fragmentation chain transfer (RAFT) polymerization and ring‐opening metathesis polymerization (ROMP). These DBCs are used as both surfactants and polyfunctional RAFT agents in the radical polymerization of St in aqueous dispersed media. Miniemulsions with narrowly dispersed St‐based nanodroplets are readily obtained after ultrasonication of the reaction mixtures. Without the presence of crosslinker, chain‐extension polymerization of St from the DBCs yields well‐defined polymeric latexes with narrow size distributions. However, with the presence of divinylbenzene (DVB) as the crosslinker, vesicular polymeric nanoparticles are formed as the major product. Such crosslinking‐induced change in morphology of the resulting latex nanomaterials may be ascribed to the increase of interfacial curvature in the heterophase systems during crosslinking polymerization. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 3250–3259     

Increasing Complexity: A Practical Synthetic Approach to Three-Dimensional,Cyclic Sulfoximines and First Insights into Their in Vitro Properties

A short synthetic approach with broad scope to access five- to seven-membered cyclic sulfoximines in only two to three steps from readily available thiophenols is reported. Thus, simple building blocks were converted to complex molecular structures by a sequence of S-alkylation and one-pot sulfoximine formation, followed by intramolecular cyclization. Seventeen structurally diverse cyclic sulfoximines were prepared in high overall yields. In vitro evaluation of these underrepresented, three-dimensional, cyclic sulfoximines with respect to properties relevant to medicinal chemistry did not reveal any intrinsic flaw for application in drug discovery.     

Transient spike adding in the presence of equilibria

Many models of neuronal activity exhibit complex oscillations in response to an input from other neurons in a network or to an input from a stimulus. We consider the effect of a single short stimulus on a simple model designed to mimic some features of neuronal dynamics. We focus on the transient response induced by the stimulus, particularly on the spike-adding behaviour of the response. Our main goal is to explain how the transient response is affected by the presence of unstable equilibria. We also investigate the dependence of the number of spikes on the amplitude and duration of the stimulus. In our analysis, we use numerical continuation methods and exploit the presence of different time scales in the model.     

Click‐Tag and Amine‐Tag: Chemical Tag Approaches for Efficient Protein Labeling In Vitro and on Live Cells using the Naturally Split Npu DnaE Intein

Protein labeling with synthetic moieties remains in many cases a technically challenging or unresolved task. Two new and simple concepts are presented. In both approaches, a very short tag of only a few amino acids is prepared with the desired chemical modification and, in a second step, it is transferred to the protein of interest by protein trans‐splicing. For the amine‐tag, a recombinant intein fragment free of lysine residues was generated such that the amine group of the N terminus could be selectively modified with regular amine‐reactive reagents. Thus, standard bioconjugation procedures without any chemical synthesis could be applied without modification of lysines in the protein of interest. For the click‐tag, protein trans‐splicing was combined with unnatural amino acid mutagenesis and subsequent bioorthogonal side chain modification, as demonstrated for click chemistry using p‐azidophenylalanine. By the two‐step strategy, exposure of the protein of interest to the copper catalyst was avoided.     

Stress-Induced Domain Wall Motion in a Ferroelastic Mn3+ Spin Crossover Complex

Domain wall motion is detected for the first time during the transition to a ferroelastic and spin state ordered phase of a spin crossover complex. Single-crystal X-ray diffraction and resonant ultrasound spectroscopy (RUS) revealed two distinct symmetry-breaking phase transitions in the mononuclear Mn³⁺ compound [Mn(3,5-diBr-sal₂(323))]BPh₄, 1. The first at 250 K, involves the space group change Cc→Pc and is thermodynamically continuous, while the second, Pc→P1 at 85 K, is discontinuous and related to spin crossover and spin state ordering. Stress-induced domain wall mobility was interpreted on the basis of a steep increase in acoustic loss immediately below the the Pc-P1 transition