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

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

The Time Structure of Hadronic Showers in highly granular Calorimeters with Tungsten and Steel Absorbers

The intrinsic time structure of hadronic showers influences the timing capability and the required integration time of hadronic calorimeters in particle physics experiments, and depends on the active medium and on the absorber of the calorimeter. With the CALICE T3B experiment, a setup of 15 small plastic scintillator tiles read out with Silicon Photomultipliers, the time structure of showers is measured on a statistical basis with high spatial and temporal resolution in sampling calorimeters with tungsten and steel absorbers. The results are compared to GEANT4 (version 9.4 patch 03) simulations with different hadronic physics models. These comparisons demonstrate the importance of using high precision treatment of low-energy neutrons for tungsten absorbers, while an overall good agreement between data and simulations for all considered models is observed for steel.Comment: 24 pages including author list, 9 figures, published in JINS

Shower development of particles with momenta from 15 GeV to 150 GeV in the CALICE scintillator-tungsten hadronic calorimeter

We present a study of showers initiated by electrons, pions, kaons, and protons with momenta from 15 GeV to 150 GeV in the highly granular CALICE scintillator-tungsten analogue hadronic calorimeter. The data were recorded at the CERN Super Proton Synchrotron in 2011. The analysis includes measurements of the calorimeter response to each particle type as well as measurements of the energy resolution and studies of the longitudinal and radial shower development for selected particles. The results are compared to Geant4 simulations (version 9.6.p02). In the study of the energy resolution we include previously published data with beam momenta from 1 GeV to 10 GeV recorded at the CERN Proton Synchrotron in 2010.Comment: 35 pages, 21 figures, 8 table

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

Discovery and optimization of narrow spectrum inhibitors of Tousled like kinase 2 (TLK2) using quantitative structure activity relationships

The oxindole scaffold has been the center of several kinase drug discovery programs, some of which have led to approved medicines. A series of two oxindole matched pairs from the literature were identified where TLK2 was potently inhibited as an off-target kinase. The oxindole has long been considered a promiscuous kinase inhibitor template, but across these four specific literature oxindoles TLK2 activity was consistent, while the kinome profile was radically different ranging from narrow to broad spectrum kinome coverage. We synthesized a large series of analogues, utilizing quantitative structure-activity relationship (QSAR) analysis, water mapping of the kinase ATP binding sites, kinome profiling, and small-molecule x-ray structural analysis to optimize TLK2 inhibition and kinome selectivity. This resulted in the identification of several narrow spectrum, sub-family selective, chemical tool compounds including 128 (UNC-CA2-103) that could enable elucidation of TLK2 biology

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