Alkene anti-dihydroxylation with malonoyl peroxides

Malonoyl peroxide 1, prepared in a single step from the commercially available diacid, is an effective reagent for the anti-dihydroxylation of alkenes. Reaction of 1 with an alkene in the presence of acetic acid at 40 °C followed by alkaline hydrolysis leads to the corresponding diol (35-92%) with up to 13:1 anti-selectivity. A mechanism consistent with experimental findings is proposed that accounts for the selectivity observed

Pesquería artesanal de elasmobranquios en la costa Pacifico de Baja California Sur, México, implicaciones para su gestión

Artisanal fisheries in Mexico account for approximately 40% of the total national catch. In 2009, Baja California Sur (BCS) had the second largest catch of elasmobranchs on the Mexican Pacific coast. This paper characterizes and describes the artisanal elasmobranch fishery of Pacific coast of BCS from 2000 to 2010. Sixty artisanal camps were documented, of which 45 targeted elasmobranchs, using primarily gillnets and longlines. We identified 52 elasmobranch species. Gillnetting accounted for 73.5% of the fishing effort and most frequently captured Rhinobatos productus, Mustelus henlei and Myliobatis californica. Longline fishing accounted for 26.5% of effort, most frequently capturing Prionace glauca and Isurus oxyrinchus. The prevalence of juveniles of several species (e.g., Cephaloscyllium ventriosum, Galeorhinus galeus, Isurus oxyrinchus, and Myliobatis californica) within landings suggests that fishing effort may be opportunistically directed at breeding or nursery areas. Despite the dominance of species with wide distributions, we observed a significant biogeographic pattern in the abundance of some species relative to Bahia Magdalena. Results of the present study will be useful to detect changes in the structure of commercially exploited elasmobranch populations, and to provide useful indications for management purposes.La pesquería artesanal en México soporta aproximadamente el 40% de la captura total nacional. En 2009 Baja California Sur (BCS) fue el segundo estado con mayor registro de captura de elasmobranquios de todo el Pacifico Mexicano. En el presente trabajo se realizó la caracterización y descripción de la pesquería artesanal de elasmobranquios en la costa Pacífico de BCS del 2000 al 2010. Se registraron 60 campos artesanales, de los cuales en 45 se capturaron elasmobranquios usando como artes de pesca redes y palangres. Se identificaron 52 especies de elasmobranquios. Las redes representaron el 73.5% del esfuerzo pesquero, las especies que se capturaron con mayor frecuencia fueron Rhinobatos productus, Mustelus henlei y Myliobatis californica. Por otra parte los palangres representaron el 26.5% del esfuerzo pesquero, las especies capturadas con mayor frecuencia fueron, Prionace glauca e Isurus oxyrinchus. La presencia de especímenes juveniles de varias especies en los desembarques (p. ej. Cephaloscyllium ventriosum, Galeorhinus galeus, Isurus oxyrinchus, Myliobatis californica) sugiere que el esfuerzo pesquero podría ser oportunista dirigido a las zonas de crianza o de reproducción. A pesar del dominio de especies con distribuciones amplias, se observó un patrón biogeográfico significativo en la abundancia de algunas especies al sur y al norte de Bahía Magdalena. Los resultados del presente estudio serán de utilidad para poder detectar los posibles cambios en la estructura poblacional de los elasmobranquios explotados comercialmente

Alkene dioxygenation with malonoyl peroxides : synthesis of ɣ-lactones, isobenzofuranones and tetrahydrofurans

Treatment of homoallylic alcohols or carboxylic acids with malonoyl peroxide 1 provides a stereoselective method for the preparation of tetrahydrofurans, ɣ-lactones and isobenzofuranones in 44–82% yield and up to 27:1 trans-selectivity. Application of this simple and effective heterocyclization in the synthesis of the antidepressant citalopram is also described

Metal triflate-promoted allylic substitution reactions of cinnamyl alcohol in the presence of orthoesters and acetals

The product distribution of ethers formed from the reaction of cinnamyl alcohol with orthoesters in the presence of indium (III) triflate (InOTf)3 is dependent on both the reaction temperature and catalyst loading. Carrying out the reaction at room temperature under low loadings of the catalyst leads to a facile reaction generating the unexpected secondary allyl ether as the major product. In contrast, carrying out the reaction under higher catalyst loadings at elevated temperatures provides the expected primary linear ether in high yield and with excellent selectivity. The etherification reaction is also effective in the presence of acetals and ketals in place of orthoesters and allows for the development of the procedure to encompass a telescoped etherification protocol in which the acetal is generated in situ

The molecular basis and biologic significance of the β-dystroglycan-emerin interaction

β-dystroglycan (β-DG) assembles with lamins A/C and B1 and emerin at the nuclear envelope (NE) to maintain proper nuclear architecture and function. To provide insight into the nuclear function of β-DG, we characterized the interaction between β-DG and emerin at the molecular level. Emerin is a major NE protein that regulates multiple nuclear processes and whose deficiency results in Emery–Dreifuss muscular dystrophy (EDMD). Using truncated variants of β-DG and emerin, via a series of in vitro and in vivo binding experiments and a tailored computational analysis, we determined that the β-DG–emerin interaction is mediated at least in part by their respective transmembrane domains (TM). Using surface plasmon resonance assays we showed that emerin binds to β-DG with high affinity (KD in the nanomolar range). Remarkably, the analysis of cells in which DG was knocked out demonstrated that loss of β-DG resulted in a decreased emerin stability and impairment of emerin-mediated processes. β-DG and emerin are reciprocally required for their optimal targeting within the NE, as shown by immunofluorescence, western blotting and immunoprecipitation assays using emerin variants with mutations in the TM domain and B-lymphocytes of a patient with EDMD. In summary, we demonstrated that β-DG plays a role as an emerin interacting partner modulating its stability and function

Convergent Akt activation drives acquired EGFR inhibitor resistance in lung cancer

EGFR-mutant non-small cell lung cancer are often resistant to EGFR tyrosine kinase inhibitor treatment. In this study, the authors show that resistant tumors display high Akt activation and that a combined treatment with AKT inhibitors causes synergistic tumour growth inhibition in vitro and in vivo

Pion and proton showers in the CALICE scintillator-steel analogue hadron calorimeter

Showers produced by positive hadrons in the highly granular CALICE scintillator-steel analogue hadron calorimeter were studied. The experimental data were collected at CERN and FNAL for single particles with initial momenta from 10 to 80 GeV/c. The calorimeter response and resolution and spatial characteristics of shower development for proton- and pion-induced showers for test beam data and simulations using Geant4 version 9.6 are compared.Comment: 26 pages, 16 figures, JINST style, changes in the author list, typos corrected, new section added, figures regrouped. Accepted for publication in JINS

Performance of the first prototype of the CALICE scintillator strip electromagnetic calorimeter

A first prototype of a scintillator strip-based electromagnetic calorimeter was built, consisting of 26 layers of tungsten absorber plates interleaved with planes of 45x10x3 mm3 plastic scintillator strips. Data were collected using a positron test beam at DESY with momenta between 1 and 6 GeV/c. The prototype's performance is presented in terms of the linearity and resolution of the energy measurement. These results represent an important milestone in the development of highly granular calorimeters using scintillator strip technology. This technology is being developed for a future linear collider experiment, aiming at the precise measurement of jet energies using particle flow techniques

Alkene oxyamination using malonoyl peroxides : preparation of pyrrolidines and isoxazolidines

Treatment of homoallylic N-tosyl amines or allylic N-tosyl hydroxylamines with 1.5 equiv of a malonoyl peroxide provides a stereoselective method to access functionalized pyrrolidines and isoxazolidines. This metal free alkene oxyamination proceeds in 50-85% yield and up to 13:1 trans-selectivity. In addition, the relative stereochemistry of the oxygen and nitrogen substituents can be inverted through an oxidation/reduction sequence or inverting the stereochemistry of the starting alkene. Mechanistic investigations show a higher reactivity for hydroxyl nucleophiles over sulfonamide nucleophiles revealing a preference for dioxygenation over oxyamination