The Quest for Palladium-Catalysed Alkyl-Nitrogen Bond Formation

Our interest in the development of transition-metal catalysis for the realisation of vicinal diamination reactions of alkenes started about a decade ago. A number of successful transformations in this area have been developed using palladium catalysis. As a challenging aspect of major importance, the palladium-catalysed coupling of alkyl–nitrogen bonds constitutes the second step in diaminations of alkenes. We here discuss the details that led us to consider high-oxidation-state palladium catalysis as a key feature in such C–N bond-forming reactions. This work discusses both our own contributions and the ones from colleagues and combines the discussion of catalytic reactions and stoichiometric control experiments. It demonstrates that reductive alkyl–nitrogen bond formation from palladium(IV) proceeds with a low activation barrier and through a linear transition state of nucleophilic displacement

Influence of shower fluctuations and primary composition on studies of the shower longitudinal development

We study the influence of shower fluctuations, and the possible presence of different nuclear species in the primary cosmic ray spectrum, on the experimental determination of both shower energy and the proton air inelastic cross section from studies of the longitudinal development of atmospheric showers in fluorescence experiments. We investigate the potential of track length integral and shower size at maximum as estimators of shower energy. We find that at very high energy (~10^19-10^20 eV) the error of the total energy assignment is dominated by the dependence on the hadronic interaction model, and is of the order of 5%. At lower energy (~10^17-10^18 eV), the uncertainty of the energy determination due to the limited knowledge of the primary cosmic ray composition is more important. The distribution of depth of shower maximum is discussed as a measure of the proton-air cross section. Uncertainties in a possible experimental measurement of this cross section introduced by intrinsic shower fluctuations, the model of hadronic interactions, and the unknown mixture of primary nuclei in the cosmic radiation are numerically evaluated.Comment: 12 pages, 11 figures, 4 table

Sterically Congested 2,6-Disubstituted Anilines from Direct C−N Bond Formation at an Iodine(III) Center

2,6-Disubstituted anilines are readily prepared from the direct reaction between amides and diaryliodonium salts. As demonstrated for 24 different examples, the reaction is of unusually broad scope with respect to the sterically congested arene and the nitrogen source, occurs without the requirement for any additional promoter, and proceeds through a direct reductive elimination at the iodine(III) center. The efficiency of the coupling procedure is further demonstrated within the short synthesis of a chemerin binding inhibitor

Characterization of neutrino signals with radiopulses in dense media through the LPM effect

We discuss the possibilities of detecting radio pulses from high energy showers in ice, such as those produced by PeV and EeV neutrino interactions. It is shown that the rich radiation pattern structure in the 100 MHz to few GHz allows the separation of electromagnetic showers induced by photons or electrons above 100 PeV from those induced by hadrons. This opens up the possibility of measuring the energy fraction transmitted to the electron in a charged current electron neutrino interaction with adequate sampling of the angular distribution of the signal. The radio technique has the potential to complement conventional high energy neutrino detectors with flavor information.Comment: 5 pages, 4 ps figures. Submitted to Phys. Rev. Let

Observation of the Askaryan Effect: Coherent Microwave Cherenkov Emission from Charge Asymmetry in High Energy Particle Cascades

We present the first direct experimental evidence for the charge excess in high energy particle showers predicted nearly 40 years ago by Askaryan. We directed bremsstrahlung photons from picosecond pulses of 28.5 GeV electrons at the SLAC Final Focus Test Beam facility into a 3.5 ton silica sand target, producing electromagnetic showers several meters long. A series of antennas spanning 0.3 to 6 GHz were used to detect strong, sub-nanosecond radio frequency pulses produced whenever a shower was present. The measured electric field strengths are consistent with a completely coherent radiation process. The pulses show 100% linear polarization, consistent with the expectations of Cherenkov radiation. The field strength versus depth closely follows the expected particle number density profile of the cascade, consistent with emission from excess charge distributed along the shower. These measurements therefore provide strong support for experiments designed to detect high energy cosmic rays and neutrinos via coherent radio emission from their cascades.Comment: 10 pages, 4 figures. Submitted to Phys. Rev. Let

Prospects for observations of high-energy cosmic tau neutrinos

We study prospects for the observations of high-energy cosmic tau neutrinos (E \geq 10^6 GeV) originating from proton acceleration in the cores of active galactic nuclei. We consider the possibility that vacuum flavor neutrino oscillations induce a tau to muon neutrino flux ratio greatly exceeding the rather small value expected from intrinsic production. The criterias and event rates for under water/ice light Cerenkov neutrino telescopes are given by considering the possible detection of downgoing high-energy cosmic tau neutrinos through characteristic double shower events.Comment: 10 pages, Revtex, 3 figures included with eps

Energy and Flux Measurements of Ultra-High Energy Cosmic Rays Observed During the First ANITA Flight

The first flight of the Antarctic Impulsive Transient Antenna (ANITA) experiment recorded 16 radio signals that were emitted by cosmic-ray induced air showers. For 14 of these events, this radiation was reflected from the ice. The dominant contribution to the radiation from the deflection of positrons and electrons in the geomagnetic field, which is beamed in the direction of motion of the air shower. This radiation is reflected from the ice and subsequently detected by the ANITA experiment at a flight altitude of 36km. In this paper, we estimate the energy of the 14 individual events and find that the mean energy of the cosmic-ray sample is 2.9 EeV. By simulating the ANITA flight, we calculate its exposure for ultra-high energy cosmic rays. We estimate for the first time the cosmic-ray flux derived only from radio observations. In addition, we find that the Monte Carlo simulation of the ANITA data set is in agreement with the total number of observed events and with the properties of those events.Comment: Added more explanation of the experimental setup and textual improvement

Neutrino Induced Upward Going Muons from a Gamma Ray Burst in a Neutrino Telescope of Km^2 Area

The number of neutrino induced upward going muons from a single Gamma Ray Burst (GRB) expected to be detected by the proposed kilometer scale IceCube detector at the South Pole location has been calculated. The effects of the Lorentz factor, total energy of the GRB emitted in neutrinos and its distance from the observer (red shift) on the number of neutrino events from the GRB have been examined. The present investigation reveals that there is possibility of exploring the early Universe with the proposed kilometer scale IceCube neutrino telescope.Comment: 18pages, 5 figures. Physical Review D in pres

Customer Engagement in Emerging Markets: Framework and Propositions

[EN] Emerging markets are a major contributor to global GDP, thus offering a primary source for economic growth. However, despite these acclaimed benefits, little remains known regarding customer engagement (i.e., a customer’s resource investment in his/her brand interactions) in emerging markets, thus exposing a pertinent literature-based gap. The development of enhanced insight into customer engagement dynamics in emerging (vs. developed) markets is important, given the idiosyncrasies characterizing these markets (e.g., chronic resource shortages, inadequate infrastructure), thus warranting the undertaking of further research in this integrative area. In response to this gap, this paper develops a framework and an associated set of Propositions of emerging market-based customer engagement, by drawing on Sheth’s (2011) emerging market hallmarks. Specifically, our Propositions postulate that the emerging market tenets of socio-political governance, inadequate infrastructure, market heterogeneity, chronic resource shortages, and unbranded competition uniquely affect emerging market-based customer engagement. We conclude by discussing our findings and by outlining key implications that arise from our analyses.S

Indole modifies the central carbon flux in the anaerobic metabolism of Escherichia coli: application to the production of hydrogen and other metabolites.

Indole is a bicyclic signaling molecule with effects on both eukaryotic and prokaryotic cells. The majority of studies of indole action have been performed with bacteria cultured under aerobic conditions and little information is available about its effects under anaerobic conditions. Here the effect of the indole on anaerobic metabolism of Escherichia coli WDHL was studied. Indole in the range 0.5-8mM was added to the culture medium and cell growth, hydrogen and metabolite production were compared to cultures lacking indole. Results showed that while 8mM indole abolished growth completely, 4mM indole had a partial bacteriostatic effect and the maximum optical density of the culture decreased by 44% compared to the control cultures. In addition, 4mM indole had an important effect on anaerobic metabolism. Hydrogen production increased from 650±115 to 1137±343mL H2/L, and hydrogen yield increased from 0.45±0.1 to 0.94±0.34mol H2/mol glucose, compared to the control culture. Carbon flux was also affected and the composition of the final by-products changed. Lactate (41mM) was the main metabolite in the control cultures, whereas ethanol (56.2mM) and acetate (41.2mM) were the main metabolites in the cultures with 2mM indole. We conclude that the supplementation of E. coli cultures with exogenous indole is a simple and novel strategy to improve the production of hydrogen as well as other metabolites such as ethanol used as biofuels.Partial financial support from CONACyT Grant Pro Nal 247498, SENER-Cemie Bio249564, and CONACyT sabbatical fellowship 259644.This is the author accepted manuscript. The final version is available from Elsevier via https://doi.org/10.1016/j.nbt.2016.09.00