Photochemical isomerization of norbornadiene‐containing polytriazoles obtained by click chemistry polyaddition

Polyesters and polyethers containing norbornadiene (NBD) and 1,2,3‐triazole units in the main chain are prepared by step growth polymerization of diester or diether NBD‐based dialkynes with different aromatic diazides using copper‐catalyzed azide–alkyne cycloaddition. The solubility and the physical properties of the resulting polytriazoles are investigated by differential scanning calorimetry, thermogravimetric analysis, size exclusion chromatography, and ¹H NMR spectroscopy, and are discussed taking into account of the chemical structures of the monomers. All of them are amorphous with glass transition temperatures ranging from 51 to 117 °C, number average molecular weight (M_n) values from 16 to 43 kDa and thermal degradation (T_d10) values from 175 to 292 °C. The photochemical valence isomerization (PVI) of the NBD units into quadricyclanes (QC) is investigated using UV–vis spectroscopy of polymer films spin‐coated onto quartz substrates. For the first time the PVI of NBD into QC is demonstrated by ¹H NMR spectroscopy. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 223–231     

A new look at probability-weighted moments estimators

In this article, we propose to study, in more generality, the probability-weighted moments method used by Hosking and Wallis (1987) in the case of generalized Pareto distributions which depend on two parameters γ and σ. The objective is to extend the domain of validity: γ<1/2 required in order to obtain the asymptotic properties of their estimators. By simulations, we show the efficiency of our technique. To cite this article: J. Diebolt et al., C. R. Acad. Sci. Paris, Ser. I 338 (2004).     

Hydrogen-induced reduction of electric field gradient in La2Fe14BHx studied by NMR on La

The ¹³⁹La NMR spin-echo spectra of La₂Fe₁₄BH_x are reported. Since lanthanum has no 4f electrons, the observed quadrupole splittings are directly proportional to the lattice part of the electric field gradient, V_zz^lat. This quantity decreases as the content of interstitial hydrogen x grows. To describe the fall-off of V_zz^lat, a dimensionless function f₂(x) is introduced, normalised so that f₂(0)=1. Analysis of the new and earlier published data obtained by several experimental techniques demonstrates that the reduction of both the second-order crystal field parameter A₂₀ and the lattice electric field gradient V_zz^lat is described by the same function f₂(x) in all R₂Fe₁₄BH_x. The only distinction that needs to be made is between R being a light and a heavy rare earth.     

Explicit characterization of the super-replication strategy in financial markets with partial transaction costs

We consider a continuous time multivariate financial market with proportional transaction costs and study the problem of finding the minimal initial capital needed to hedge, without risk, European-type contingent claims. The model is similar to the one considered in Bouchard and Touzi [B. Bouchard, N. Touzi, Explicit solution of the multivariate super-replication problem under transaction costs, The Annals of Applied Probability 10 (3) (2000) 685–708] except that some of the assets can be exchanged freely, i.e. without paying transaction costs. In this context, we generalize the result of the above paper and prove that the super-replication price is given by the cost of the cheapest hedging strategy in which the number of non-freely exchangeable assets is kept constant over time. Our proof relies on the introduction of a new auxiliary control problem whose value function can be interpreted as the super-hedging price in a model with unbounded stochastic volatility (in the directions where transaction costs are non-zero). In particular, it confirms the usual intuition that transaction costs play a similar role to stochastic volatility.     

Purification and Characterization of a Cu,Zn-SOD from Garlic (Allium sativum L.). Antioxidant Effect on Tumoral Cell Lines

Crude garlic extract contains one Mn-superoxide dismutase designated as SOD1 and two Cu,Zn superoxide dismutases as SOD2 and SOD3. The major isoform SOD2 was purified to homogeneity by Sephacryl S200-HR gel filtration, DEAE Sepharose ion exchange chromatography, and chromatofocusing using PBE 94. SOD2 was purified 82-fold with a specific activity of 4,960 U/mg protein. This enzyme was stable in a broad pH range from 5.0 to 10.0 and at various temperatures from 25 to 60°C. The native molecular mass of SOD2 estimated by high performance liquid chromatography on TSK gel G2000SW column was 39 kDa. Sodium dodecyl sulfate–polyacrylamide gel electrophoresis analysis showed a single band near 18 kDa, suggesting that native enzyme was homodimeric. The isoelectric point as determined by chromatofocusing was 5. Analysis of its N terminal amino acid sequence revealed high sequence homology with several other cytosolic Cu,Zn-SODs from plants. Exposure of cancer cell lines to garlic Cu,Zn-SOD2 led to a significant decrease in superoxide content with a concomitant rise in intracellular peroxides, indicating that the enzyme is active in mammalian cells and could, therefore, be used in pharmacological applications.     

Isolation and Characterization of Putative Endophytic Bacteria Antagonistic to Phoma tracheiphila and Verticillium albo-atrum

A collection of 200 bacterial isolates recovered from citrus plants (Citrus limon, Citrus sinensis, and Citrus reticulata), Medicago truncatula and Laurus nobilis, was established. In vitro screening indicated that 28 isolates exhibited an inhibitory activity against the vascular pathogens Phoma tracheiphila and Verticillium albo-atrum. Isolates were screened according to their hydrolytic activities, plant growth-promoting bacteria (PGPB) abilities, as well as for the presence of nonribosomal peptide synthetase (NRPS) genes responsible of the lipopeptide biosynthesis. The results were positive for 16 isolates which exhibited at least two PGPB activities and a single NRPS gene. Genetic diversity of the selected isolates was studied using random amplified polymorphic DNA (RAPD) and repetitive element PCR (REP) tools that showed clustering of strains into three major groups (I, II, and III) (i, ii, and iii), respectively. Clustering was further confirmed by the 16S rDNA sequencing that assigned nine isolates to Bacillus velezensis, four isolates to Bacillus methyltrophicus, one isolate to Bacillus amyloliquefaciens, and two isolates to Bacillus mojavensis. Organ-bacterial genotype interaction as well as positive correlation with NRPS genes are discussed.     

Production of Anti-Methicillin-Resistant <Emphasis Type="Italic">Staphylococcus</Emphasis> Activity from <Emphasis Type="Italic">Bacillus subtilis</Emphasis> sp. Strain B38 Newly Isolated from Soil

B38 bacterial strain, isolated from Tunisian soil showed a strong antimicrobial activity. Based on biochemical characterization and 16S rDNA sequence analysis, B38 strain was identified as Bacillus subtilis. Cell culture supernatant showed antibacterial activity against clinical isolates of methicillin-resistant Staphylococcus species and several Gram-positive and Gram-negative bacteria. Antifungal activity against phytopathogenic fungi was also observed. Antibacterial activity production started at early exponential growth phase, and maximum activity was reached at the stationary phase. This antibacterial activity was neither affected by proteases, lipase, and organic solvents, nor by surfactants. It was stable over a wide pH range and still active after autoclaving at 121 °C during 20 min. Thin layer chromatography followed by bioautography assay allowed the detection of four active spots with R _f values of 0.30, 0.47, 0.70, and 0.82. The single spot with R _f 0.30 showed antifungal activity, whereas the spots with R _f values of 0.47, 0.70, and 0.82 exhibited antibacterial activity.     

Implementation of a Biometric Interface in Voice Controlled Wheelchairs

In order to assist physically handicapped persons in their movements, we developed an embedded isolated word speech recognition system (ASR) applied to voice control of smart wheelchairs. However, in spite of the existence in the industrial market of several kinds of electric wheelchairs, the problem remains the need to manually control this device by hand via joystick; which limits their use especially by people with severe disabilities. Thus, a significant number of disabled people cannot use a standard electric wheelchair or drive it with difficulty. The proposed solution is to use the voice to control and drive the wheelchair instead of classical joysticks. The intelligent chair is equipped with an obstacle detection system consisting of ultrasonic sensors, a moving navigation algorithm and a speech acquisition and recognition module for voice control embedded in a DSP card. The ASR architecture consists of two main modules. The first one is the speech parameterization module (features extraction) and the second module is the classifier which identifies the speech and generates the control word to motors power unit. The training and recognition phases are based on Hidden Markov Models (HMM), K-means, Baum-Welch and Viterbi algorithms. The database consists of 39 isolated speaker words (13 words pronounced 3 times under different environments and conditions). The simulations are tested under Matlab environment and the real-time implementation is performed by C language with code composer studio embedded in a TMS 320 C6416 DSP kit. The results and experiments obtained gave promising recognition ratio and accuracy around 99% in clean environment. However, the system accuracy decreases considerably in noisy environments, especially for SNR values below 5 dB (in street: 78%, in factory: 52%).     

General and Efficient Transesterification of β-Keto Esters with Various Alcohols Using Et3N as a Brønsted Base Additive

Transesterification of β-keto esters with a wide variety of allyl, benzyl, propargyl, and alkyl alcohols using, for the first time, commercially available and inexpensive Et₃N as a Brønsted base additive, is efficiently performed in toluene at reflux. The corresponding esters are exclusively obtained in 57–98% yields with no trace amounts of γ,δ-ketones, usually expected from the decarboxylative Carroll rearrangement.