Solid‐State Gas Sensors Developed from Functional Difluoroboradiazaindacene Dyes

This article describes the synthesis and characterization of several new difluoroboradiazaindacene (BODIPY?) dyes functionalized at the central 8‐position by a phenyliodo, phenylheptynoate or phenylheptynoic fragment and at the 3‐ or 3/5‐position(s) by 4‐dimethylaminophenylstyryl residue(s). Single‐crystal structural determinations confirm the planarity of the dyes, while the absorption and fluorescence spectroscopic properties are highly sensitive to the state of protonation (or alkylation) of the terminal anilino donor group(s). Reversible color tuning from green to blue for absorption and from colorless (i.e., near‐IR region) to red for fluorescence is obtained on successive addition of acid and base. The difunctionalized derivative is especially interesting in this respect and shows two well‐resolved pK_a values of 5.10 and 3.04 in acetonitrile. Addition of the first proton causes only small spectral changes and deactivates the molecule towards addition of the second proton. It is this latter step that accommodates the large change in absorption and emission properties, due to the reversible extinction of the intramolecular charge‐transfer character inherent to this type of dye. The main focus of the work is the covalent anchoring of the dyes to inert, porous polyacrylate beads so as to form a solid‐state sensor suitable for analysis of gases or flowing liquids. The final material is highly stable—its performance is undiminished after more than one year—and fully reversible over many cycles. The sensitivity is such that reactions can be followed by the naked eye and the detection limit is about 600 ppb for HCl and about 80 ppb for ammonia. Trace amounts of diphosgene can be detected, as can alkylating agents. The sensing action is indiscriminate and also operates when the beads are dispersed in aqueous media.     

Synthesis and complete assignment of the 1H and 13C NMR signals of new acetamido and aminoflavonoid derivatives

The complete ¹H and ¹³C NMR assignment of 9 acetamidochalcones, 18 acetamidoflavones, 18 aminoflavones, 9 acetamidoflavonols and 9 aminoflavonols has been performed using one‐ and two‐dimensional NMR techniques including COSY, HMQC and HMBC experiments. Copyright © 2010 John Wiley & Sons, Ltd.     

Selecting hidden Markov model state number with cross-validated likelihood

The problem of estimating the number of hidden states in a hidden Markov model is considered. Emphasis is placed on cross-validated likelihood criteria. Using cross-validation to assess the number of hidden states allows to circumvent the well-documented technical difficulties of the order identification problem in mixture models. Moreover, in a predictive perspective, it does not require that the sampling distribution belongs to one of the models in competition. However, computing cross-validated likelihood for hidden Markov models for which only one training sample is available, involves difficulties since the data are not independent. Two approaches are proposed to compute cross-validated likelihood for a hidden Markov model. The first one consists of using a deterministic half-sampling procedure, and the second one consists of an adaptation of the EM algorithm for hidden Markov models, to take into account randomly missing values induced by cross-validation. Numerical experiments on both simulated and real data sets compare different versions of cross-validated likelihood criterion and penalised likelihood criteria, including BIC and a penalised marginal likelihood criterion. Those numerical experiments highlight a promising behaviour of the deterministic half-sampling criterion.     

Experimental determination of the helicoidal electric field inside a twisted mesophase, in the selective reflection band

We consider the interface between a twisted birefringent mesophase and an isotropic medium. In the selective reflection band, when illuminated at normal incidence, the interface creates a coupling between the located dielectric reflection and the spread selective reflection. This coupling enables experimental measurement of the standing electric field orientation inside the liquid crystal.     

Binary group and Chinese postman polyhedra

A new proof of the characterization of the Chinese postman polyhedra is given. In developing this proof, a theorem of Gomory about homomorphic lifting of facets for group polyhedra is generalized to subproblems. Some results for the Chinese postman problem are generalized to binary group problems. In addition, a connection is made between Fulkerson's blocking polyhedra and a blocking pair of binary group problems. A connection is also developed between minors and lifting of facets for group problems.     

CohomologieL 2 et parabolicité

Nous donnons ici une interprétation topologique des espaces de formes harmoniques L² de variétés riemanniennes qui sont des déformations compactes d'espaces symétriques à courbure négative ou nulle ou de groupes de Lie nilpotent simplement connexe. Nous étudions aussi la cohomologie L² des variétés dont les bouts sont paraboliques, nous retrouvons en particulier des résultats de M. Atiyah, V. Patodi, I. Singer, de W. Müller et une petite partie de résultats récents de T. Hausel, E. Hunsicker, R. Mazzeo. En mémoire d' Alain Dufresnoy     

Combined Poly(alkyl cyanoacrylate)/Cyclodextrin Nanoparticles

The use of nanoparticles is of great interest for oral or parenteral administration. In fact, nanoparticles not only can protect the active ingredient, but they confer on it a large contact surface with biological membranes and a possible improvement in bioavailability. Biodegradability of nanoparticles, which can be considered as a pre-requisite in the case of parenteral administration     

Reinforcement of an inequality due to Brascamp and Lieb

In this paper, we obtain a reinforcement of an inequality due to Brascamp and Lieb and a reinforcement of Poincaré's inequality for general logarithmical concave measures on Rd. The formula used in the proof is related to theorems concerning the integration of log-concave functions (such as results of Prékopa and of Ball, Barthe and Naor). We also obtain a lower bound for the variance of the same family of measures.     

Quantization of Γ-Lie bialgebras

We introduce the notion of Γ-Lie bialgebras, where Γ is a group. These objects give rise to cocommutative co-Poisson bialgebras, for which we construct quantization functors. This enlarges the class of co-Poisson algebras for which a quantization is known. Our result relies on our earlier work, where we showed that twists of Lie bialgebras can be quantized; we complement this work by studying the behavior of this quantization under compositions of twists.     

Synthesis of simplified analogues of eleutherobin via a Claisen rearrangement/RCM strategy

The enantioselective synthesis of a number of simplified analogues of the cytotoxic natural product eleutherobin is reported.