1,385 research outputs found
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 alkylânitrogen 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 CâN 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 alkylânitrogen 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 CâN 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 customerâs 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 Shethâs (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
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