2,133 research outputs found
Tumores en ganado ovino sacrificado en matadero
Trabajo presentado al: XL Congreso Nacional y el XVI Congreso Internacional de la Sociedad Española de Ovinotecnia y Caprinotecnia. (Castellón de la Plana, España, 16-18 septiembre 2015).Peer Reviewe
<i>In Situ </i>Studies of Arylboronic Acids/Esters and R<sub>3</sub>SiCF<sub>3</sub> Reagents: Kinetics, Speciation, and Dysfunction at the CarbanionâAte Interface
[Image: see text] Reagent instability reduces the efficiency of chemical processes, and while much effort is devoted to reaction optimization, less attention is paid to the mechanistic causes of reagent decomposition. Indeed, the response is often to simply use an excess of the reagent. Two reaction classes with ubiquitous examples of this are the SuzukiâMiyaura cross-coupling of boronic acids/esters and the transfer of CF(3) or CF(2) from the RuppertâPrakash reagent, TMSCF(3). This Account describes some of the overarching features of our mechanistic investigations into their decomposition. In the first section we summarize how specific examples of (hetero)arylboronic acids can decompose via aqueous protodeboronation processes: ArâB(OH)(2) + H(2)O â ArH + B(OH)(3). Key to the analysis was the development of a kinetic model in which pH controls boron speciation and heterocycle protonation states. This method revealed six different protodeboronation pathways, including self-catalysis when the pH is close to the pK(a) of the boronic acid, and protodeboronation via a transient aryl anionoid pathway for highly electron-deficient arenes. The degree of âprotectionâ of boronic acids by diol-esterification is shown to be very dependent on the diol identity, with six-membered ring esters resulting in faster protodeboronation than the parent boronic acid. In the second section of the Account we describe (19)F NMR spectroscopic analysis of the kinetics of the reaction of TMSCF(3) with ketones, fluoroarenes, and alkenes. Processes initiated by substoichiometric âTBATâ ([Ph(3)SiF(2)][Bu(4)N]) involve anionic chain reactions in which low concentrations of [CF(3)](â) are rapidly and reversibly liberated from a siliconate reservoir, [TMS(CF(3))(2)][Bu(4)N]. Increased TMSCF(3) concentrations reduce the [CF(3)](â) concentration and thus inhibit the rates of CF(3) transfer. Computation and kinetics reveal that the TMSCF(3) intermolecularly abstracts fluoride from [CF(3)](â) to generate the CF(2), in what would otherwise be an endergonic α-fluoride elimination. Starting from [CF(3)](â) and CF(2), a cascade involving perfluoroalkene homologation results in the generation of a hindered perfluorocarbanion, [C(11)F(23)](â), and inhibition. The generation of CF(2) from TMSCF(3) is much more efficiently mediated by NaI, and in contrast to TBAT, the process undergoes autoacceleration. The process involves NaI-mediated α-fluoride elimination from [CF(3)][Na] to generate CF(2) and a [NaI·NaF] chain carrier. Chain-branching, by [(CF(2))(3)I][Na] generated in situ (CF(2) + TFE + NaI), causes autoacceleration. Alkenes that efficiently capture CF(2) attenuate the chain-branching, suppress autoacceleration, and lead to less rapid difluorocyclopropanation. The Account also highlights how a collaborative approach to experiment and computation enables mechanistic insight for control of processes
Maritime Perspective of Panama Interoceanic Railway
In 1977, when the American historian David McCullough wrote a book called âThe Path Between the Seas: The Creation of the Panama Canal, 1870-1914â, about the social and geographical environment during the Panama Canal construction, he described the transisthmic railway as a complement of the engineering department that Frenchâs company did not know how to take advantage of, because with the Californian gold fever decadence and with the Canal works it would not have had any commercial purpose other than the ridiculous price of passenger tickets. He never imagined that 100 years later this complement will be a key fact in the supply chain of the Latin-American and worldwide trade.
In this paper, we will focus in the logistical map of America, where Panama is the centre. Being the way to connect Asia and America, also both coasts of the American Continent, and the begin/end place of four of the five Feeders highways of Latin America, it turns in the link with the others and with the rest of the world. But they are separated by 76 kilometres that a logistical system converts this distance into a one-hour travel to the next connection.
The challenges of this system are raising everyday as result of di_erent regional trade facts. The
Panamanian complex is playing an important role with the trade balances, the growing economies and transoceanic services with stop in Panama, generating disequilibrium (empty containers problem). The empty containers must follow the empty container cycle since the container is emptied and the customer returns it to the owner, itâs taken to the depot for maintenance, step that is mandatory in order to return to the cycle of export
Carbon and oxygen in HII regions of the Magellanic Clouds: abundance discrepancy and chemical evolution
We present C and O abundances in the Magellanic Clouds derived from deep
spectra of HII regions. The data have been taken with the Ultraviolet-Visual
Echelle Spectrograph at the 8.2-m VLT. The sample comprises 5 HII regions in
the Large Magellanic Cloud (LMC) and 4 in the Small Magellanic Cloud (SMC). We
measure pure recombination lines (RLs) of CII and OII in all the objects,
permitting to derive the abundance discrepancy factors (ADFs) for O^2+, as well
as their O/H, C/H and C/O ratios. We compare the ADFs with those of other HII
regions in different galaxies. The results suggest a possible metallicity
dependence of the ADF for the low-metallicity objects, but more uncertain for
high-metallicity objects. We compare nebular and B-type stellar abundances and
we find that the stellar abundances agree better with the nebular ones derived
from collisionally excited lines (CELs). Comparing these results with other
galaxies we observe that stellar abundances seem to agree better with the
nebular ones derived from CELs in low-metallicity environments and from RLs in
high-metallicity environments. The C/H, O/H and C/O ratios show almost flat
radial gradients, in contrast with the spiral galaxies where such gradients are
negative. We explore the chemical evolution analysing C/O vs. O/H and comparing
with the results of HII regions in other galaxies. The LMC seems to show a
similar chemical evolution to the external zones of small spiral galaxies and
the SMC behaves as a typical star-forming dwarf galaxy.Comment: Accepted for publication in MNRAS, 17 pages, 11 figures, 8 table
Nonlinear field theories during homogeneous spatial dilation
The effect of a uniform dilation of space on stochastically driven nonlinear
field theories is examined. This theoretical question serves as a model problem
for examining the properties of nonlinear field theories embedded in expanding
Euclidean Friedmann-Lema\^{\i}tre-Robertson-Walker metrics in the context of
cosmology, as well as different systems in the disciplines of statistical
mechanics and condensed matter physics. Field theories are characterized by the
speed at which they propagate correlations within themselves. We show that for
linear field theories correlations stop propagating if and only if the speed at
which the space dilates is higher than the speed at which correlations
propagate. The situation is in general different for nonlinear field theories.
In this case correlations might stop propagating even if the velocity at which
space dilates is lower than the velocity at which correlations propagate. In
particular, these results imply that it is not possible to characterize the
dynamics of a nonlinear field theory during homogeneous spatial dilation {\it a
priori}. We illustrate our findings with the nonlinear Kardar-Parisi-Zhang
equation
Lump solitons in a higher-order nonlinear equation in 2+1 dimensions
We propose and examine an integrable system of nonlinear equations that generalizes the nonlinear Schrodinger equation to 2 + 1 dimensions. This integrable system of equations is a promising starting point to elaborate more accurate models in nonlinear optics and molecular systems within the continuum limit. The Lax pair for the system is derived after applying the singular manifold method. We also present an iterative procedure to construct the solutions from a seed solution. Solutions with one-, two-, and three-lump solitons are thoroughly discussed
The impact of chemical differentiation of white dwarfs on thermonuclear supernovae
Gravitational settling of 22Ne in cooling white dwarfs can affect the outcome
of thermonuclear supernovae. We investigate how the supernova energetics and
nucleosynthesis are in turn influenced by this process. We use realistic
chemical profiles derived from state-of-the-art white dwarf cooling sequences.
The cooling sequences provide a link between the white dwarf chemical structure
and the age of the supernova progenitor system. The cooling sequence of a 1
M_sun white dwarf was computed until freezing using an up-to-date stellar
evolutionary code. We computed explosions of both Chandrasekhar mass and
sub-Chandrasekhar mass white dwarfs, assuming spherical symmetry and neglecting
convective mixing during the pre-supernova carbon simmering phase to maximize
the effects of chemical separation. Neither gravitational settling of 22Ne nor
chemical differentiation of 12C and 16O have an appreciable impact on the
properties of Type Ia supernovae, unless there is a direct dependence of the
flame properties (density of transition from deflagration to detonation) on the
chemical composition. At a fixed transition density, the maximum variation in
the supernova magnitude obtained from progenitors of different ages is ~0.06
magnitudes, and even assuming an unrealistically large diffusion coefficient of
22Ne it would be less than ~0.09 mag. However, if the transition density
depends on the chemical composition (all other things being equal) the oldest
SNIa can be as much as 0.4 magnitudes brighter than the youngest ones (in our
models the age difference is 7.4 Gyr). In addition, our results show that 22Ne
sedimentation cannot be invoked to account for the formation of a central core
of stable neutron-rich Fe-group nuclei in the ejecta of sub-Chandrasekhar
models, as required by observations of Type Ia supernovae.Comment: 8 pages, 8 figures, 3 tables, accepted for Astronomy and
Astrophysics. Revised version with corrected typo
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