203 research outputs found
Ballistic resistivity in aluminum nanocontacts
One of the major industrial challenges is to profit from some fascinating
physical features present at the nanoscale. The production of dissipationless
nanoswitches (or nanocontacts) is one of such attractive applications.
Nevertheless, the lack of knowledge of the real efficiency of electronic
ballistic/non dissipative transport limits future innovations. For multi-valent
metallic nanosystems -where several transport channels per atom are involved-
the only experimental technique available for statistical transport
characterization is the conductance histogram. Unfortunately its interpretation
is difficult because transport and mechanical properties are intrinsically
interlaced. We perform a representative series of semiclassical molecular
dynamics simulations of aluminum nanocontact breakages, coupled to full quantum
conductance calculations, and put in evidence a linear relationship between the
conductance and the contact minimum cross-section for the geometrically favored
aluminum nanocontact configurations. Valid in a broad range of conductance
values, such relation allows the definition of a transport parameter for
nanomaterials, that represents the novel concept of ballistic resistivity
Toward reliable population estimates of wolves by combining spatial capture-recapture models and non-invasive DNA monitoring
Decision-makers in wildlife policy require reliable population size estimates to justify interventions, to build acceptance and support in their decisions and, ultimately, to build trust in managing authorities. Traditional capture-recapture approaches present two main shortcomings, namely, the uncertainty in defining the effective sampling area, and the spatially-induced heterogeneity in encounter probabilities. These limitations are overcome using spatially explicit capture-recapture approaches (SCR). Using wolves as case study, and non-invasive DNA monitoring (faeces), we implemented a SCR with a Poisson observation model in a single survey to estimate wolf density and population size, and identify the locations of individual activity centres, in NW Iberia over 4,378 km. During the breeding period, posterior mean wolf density was 2.55 wolves/100 km (95%BCI = 1.87-3.51), and the posterior mean population size was 111.6 ± 18.8 wolves (95%BCI = 81.8-153.6). From simulation studies, addressing different scenarios of non-independence and spatial aggregation of individuals, we only found a slight underestimation in population size estimates, supporting the reliability of SCR for social species. The strategy used here (DNA monitoring combined with SCR) may be a cost-effective way to generate reliable population estimates for large carnivores at regional scales, especially for endangered species or populations under game management.J.V.L.B. was supported by a Ramon & Cajal research contract (RYC-2015-18932) from the Spanish Ministry of Economy, Industry and Competitiveness. R.G. was supported by research contract (IF/00564/2012) from the Portuguese Foundation for Science and Technology (FCT). Tis work was partially supported by the project PTDC/BIA-EVF/2460/2014 (FCT).Peer Reviewe
Fullerene-based molecular nanobridges: A first-principles study
Building upon traditional quantum chemistry calculations, we have implemented
an {\em ab-initio} method to study the electrical transport in nanocontacts. We
illustrate our technique calculating the conductance of C molecules
connected in various ways to Al electrodes characterized at the atomic level.
Central to a correct estimate of the electrical current is a precise knowledge
of the local charge transfer between molecule and metal which, in turn,
guarantees the correct positioning of the Fermi level with respect to the
molecular orbitals. Contrary to our expectations, ballistic transport seems to
occur in this system.Comment: 4 pages in two-column forma
Regional effects of atmospheric aerosols on temperature: An evaluation of an ensemble of online coupled models
The climate effect of atmospheric aerosols is associated with their
influence on the radiative budget of the Earth due to the direct
aerosolâradiation interactions (ARIs) and indirect effects, resulting from
aerosolâcloudâradiation interactions (ACIs). Online coupled
meteorologyâchemistry models permit the description of these effects on the
basis of simulated atmospheric aerosol concentrations, although there is
still some uncertainty associated with the use of these models. Thus,
the objective of this work is to assess whether the inclusion of atmospheric
aerosol radiative feedbacks of an ensemble of online coupled models improves
the simulation results for maximum, mean and minimum temperature at 2âŻm over
Europe. The evaluated models outputs originate from EuMetChem COST Action
ES1004 simulations for Europe, differing in the inclusion (or omission) of
ARI and ACI in the various models. The cases studies cover two important
atmospheric aerosol episodes over Europe in the year 2010: (i) a heat wave event
and a forest fire episode (JulyâAugust 2010) and (ii) a more humid episode
including a Saharan desert dust outbreak in October 2010. The simulation
results are evaluated against observational data from the E-OBS gridded database.
The results indicate that, although there is only a slight improvement in the
bias of the simulation results when including the radiative feedbacks, the
spatiotemporal variability and correlation coefficients are improved for the
cases under study when atmospheric aerosol radiative effects are included
An assessment of aerosol optical properties from remote-sensing observations and regional chemistryâclimate coupled models over Europe
Atmospheric aerosols modify the radiative budget
of the Earth due to their optical, microphysical and chemical properties, and
are considered one of the most uncertain climate forcing agents. In order to
characterise the uncertainties associated with satellite and modelling
approaches to represent aerosol optical properties, mainly aerosol optical
depth (AOD) and Ă
ngström exponent (AE), their representation by
different remote-sensing sensors and regional online coupled
chemistryâclimate models over Europe are evaluated. This work also
characterises whether the inclusion of aerosolâradiation (ARI) or/and
aerosolâcloud interactions (ACI) help improve the skills of modelling
outputs.Two case studies were selected within the EuMetChem COST Action ES1004
framework when important aerosol episodes in 2010 all over Europe took
place: a Russian wildfire episode and a Saharan desert dust outbreak that
covered most of the Mediterranean Sea. The model data came from different
regional air-qualityâclimate simulations performed by working group 2 of
EuMetChem, which differed according to whether ARI or ACI was included or
not. The remote-sensing data came from three different sensors: MODIS, OMI
and SeaWIFS. The evaluation used classical statistical metrics to first
compare satellite data versus the ground-based instrument network (AERONET)
and then to evaluate model versus the observational data (both satellite and
ground-based data).Regarding the uncertainty in the satellite representation of AOD, MODIS
presented the best agreement with the AERONET observations compared to other
satellite AOD observations. The differences found between remote-sensing
sensors highlighted the uncertainty in the observations, which have to be
taken into account when evaluating models. When modelling results were
considered, a common trend for underestimating high AOD levels was observed.
For the AE, models tended to underestimate its variability, except when
considering a sectional approach in the aerosol representation. The modelling
results showed better skills when ARI+ACI interactions were included; hence
this improvement in the representation of AOD (above 30âŻ% in the model error)
and AE (between 20 and 75âŻ%) is important to provide a better description of
aerosolâradiationâcloud interactions in regional climate models
Quantitative study of hydration of C3S and C2S by thermal analysis. Evolution and composition of C-S-H gels formed
This research is part of a European project (namely, CODICE project), main objective of which is modelling, at a multi-scale, the evolution of the mechanical performance of non-degraded and degraded cementitious matrices. For that, a series of experiments were planned with pure synthetic tri-calcium silicate (C3S) and bi-calcium silicate (C2S) (main components of the Portland cement clinker) to obtain different calciumâsilicateâhydrate (CâSâH) gel structures during their hydration. The characterization of those CâSâH gels and matrices will provide experimental parameters for the validation of the multi-scale modelling scheme proposed. In this article, a quantitative method, based on thermal analyses, has been used for the determination of the chemical composition of the CâSâH gel together with the degree of hydration and quantitative evolution of all the components of the pastes. Besides, the microstructure and type of silicate tetrahedron and mean chain length (MCL) were studied by scanning electron microscopy (SEM) and 29Si magic-angle-spinning (MAS) NMR, respectively. The main results showed that the chemical compositions for the CâSâH gels have a CaO/SiO2 M ratio almost constant of 1.7 for both C3S and C2S compounds. Small differences were found in the gel water content: the H2O/SiO2 M ratio ranged from 2.9 ± 0.2 to 2.6 ± 0.2 for the C3S (decrease) and from 2.4 ± 0.2 to 3.2 ± 0.2 for the C2S (increase). The MCL values of the CâSâH gels, determined from 29Si MAS NMR, were 3.5 and 4 silicate tetrahedron, for the hydrated C3S and C2S, respectively, remaining almost constant at all hydration periods
A first-principles approach to electrical transport in atomic-scale nanostructures
We present a first-principles numerical implementation of Landauer formalism
for electrical transport in nanostructures characterized down to the atomic
level. The novelty and interest of our method lies essentially on two facts.
First of all, it makes use of the versatile Gaussian98 code, which is widely
used within the quantum chemistry community. Secondly, it incorporates the
semi-infinite electrodes in a very generic and efficient way by means of Bethe
lattices. We name this method the Gaussian Embedded Cluster Method (GECM). In
order to make contact with other proposed implementations, we illustrate our
technique by calculating the conductance in some well-studied systems such as
metallic (Al and Au) nanocontacts and C-atom chains connected to metallic (Al
and Au) electrodes. In the case of Al nanocontacts the conductance turns out to
be quite dependent on the detailed atomic arrangement. On the contrary, the
conductance in Au nanocontacts presents quite universal features. In the case
of C chains, where the self-consistency guarantees the local charge transfer
and the correct alignment of the molecular and electrode levels, we find that
the conductance oscillates with the number of atoms in the chain regardless of
the type of electrode. However, for short chains and Al electrodes the even-odd
periodicity is reversed at equilibrium bond distances.Comment: 14 pages, two-column format, submitted to PR
Actualistic taphonomic study of the rodents digested by the Achala culpeo fox (Lycalopex culpaeus smithersi) in the highlands of central Argentina
We present the first actualistic study of the rodents consumed by the South American foxLycalopex culpaeus smithersi (Achala culpeo fox), a subspecies of the culpeo fox that is endemicto the highlands of central Argentina. We provide a taphonomic characterization of this canidbased on digested micromammal bones, and compare it to other carnivores. We studied over 1000bones derived from 83 scats collected in Quebrada del Condorito National Park, CĂłrdobaprovince, Argentina, corresponding to caviomorph and myomorph rodents. Galea leucoblepharawas the main prey (59.8% MNI, 93.1% biomass). Average relative abundance for the totalassemblage was 26.7. Cranial and, to a lesser extent, proximal limb bones were the most abundantelements. A high degree of breakage was observed in cranial elements and, to a lesser extent, inlimb bones. A high proportion of heavy and extreme digestion was inferred, while some elementsbear light or no digestion traces at all. Overall, the Achala culpeo fox fits best with othermammalian carnivores in the category of extreme modification, and shows types and proportionsof taphonomic attributes similar to other South American mammalian predators. These resultscontribute to the understanding of regional taphonomic processes and of digestivemodifications by Lycalopex foxes generally, and are thus relevant to interpreting the presence of micromammal remains in the archaeological and palaeontological recordsand the impact of these foxes in their formation.Fil: Coll, Daiana Geraldine. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales; ArgentinaFil: Montalvo, Claudia InĂ©s. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales; ArgentinaFil: FernĂĄndez, Fernando JuliĂĄn. Universidad de Buenos Aires. Facultad de IngenierĂa; Argentina. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas; ArgentinaFil: Pia, Monica Valeria. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Instituto de Ciencias de la Tierra y Ambientales de La Pampa. Universidad Nacional de La Pampa. Facultad de Ciencias Exactas y Naturales. Instituto de Ciencias de la Tierra y Ambientales de La Pampa; ArgentinaFil: Mondini, Nora Mariana. Consejo Nacional de Investigaciones CientĂficas y TĂ©cnicas. Centro CientĂfico TecnolĂłgico Conicet - CĂłrdoba. Instituto de AntropologĂa de CĂłrdoba. Universidad Nacional de CĂłrdoba. Facultad de FilosofĂa y Humanidades. Instituto de AntropologĂa de CĂłrdoba; Argentin
Generalized Structural Description of CalciumâSodium Aluminosilicate Hydrate Gels: The Cross-Linked Substituted Tobermorite Model
Structural models for the primary strength and durability-giving reaction product in modern cements, a calcium (alumino)silicate hydrate gel, have previously been based solely on non-cross-linked tobermorite structures. However, recent experimental studies of laboratory-synthesized and alkali-activated slag (AAS) binders have indicated that the calciumâsodium aluminosilicate hydrate [C-(N)-A-S-H] gel formed in these systems can be significantly cross-linked. Here, we propose a model that describes the C-(N)-A-S-H gel as a mixture of cross-linked and non-cross-linked tobermorite-based structures (the cross-linked substituted tobermorite model, CSTM), which can more appropriately describe the spectroscopic and density information available for this material. Analysis of the phase assemblage and Al coordination environments of AAS binders shows that it is not possible to fully account for the chemistry of AAS by use of the assumption that all of the tetrahedral Al is present in a tobermorite-type C-(N)-A-S-H gel, due to the structural constraints of the gel. Application of the CSTM can for the first time reconcile this information, indicating the presence of an additional activation product that contains highly connected four-coordinated silicate and aluminate species. The CSTM therefore provides a more advanced description of the chemistry and structure of calciumâsodium aluminosilicate gel structures than that previously established in the literature
Hetero-cycloreversions Mediated by Photoinduced Electron Transfer
[EN] Discovered more than eight decades ago, the Diels-Alder (DA) cycloaddition (CA) remains one of the most versatile tools in synthetic organic chemistry. Hetero-DA processes are powerful methods for the synthesis of densely functionalized six-membered heterocycles, ubiquitous substructures found in natural products and bioactive compounds. These reactions frequently employ azadienes and oxadienes, but only a few groups have reported DA processes with thiadienes. The electron transfer (ET) version of the DA reaction, though less investigated, has emerged as a subject of increasing interest.
In the last two decades, researchers have paid closer attention to radical ionic hetero-cycloreversions, mainly in connection with their possible involvement in the repair of pyrimidine(6-4)pyrimidone photolesions in DNA by photolyases. In biological systems, these reactions likely occur through a reductive photosensitization mechanism. In addition, photooxidation can lead to cycloreversion (CR) reactions, and researchers can exploit this strategy for DNA repair therapies.
In this Account, we discuss electron-transfer (ET) mediated hetero-CR reactions. We focus on the oxidative and reductive ET splitting of oxetanes, azetidines, and thietanes. Photoinduced electron transfer facilitates the splitting of a variety of four-membered heterocycles. In this context, researchers have commonly examined oxetanes, both experimentally and theoretically. Although a few studies have reported the cycloreversion of azetidines and thietanes carried out under electron transfer conditions, the number of examples remains limited.
In general, the cleavage of the ionized four-membered rings appears to occur via a nonconcerted two-step mechanism. The trapping of the intermediate 1,4-radical ions and transient absorption spectroscopy data support this hypothesis, and it explains the observed loss of stereochemistry in the products. In the initial step, either C-C or C-X bond breaking may occur, and the preferred route depends on the substitution pattern of the ring, the type of heteroatom, and various experimental conditions. To better accommodate spin and charge, C-X cleavage happens more frequently, especially in the radical anionic version of the reaction.
The addition or withdrawal of a single electron provides a new complementary synthetic strategy to activate hetero-cycloreversions. Despite its potential, this strategy remains largely unexplored. However, it offers a useful method to achieve C=X/olefin metathesis or, upon ring expansion, to construct six-membered heterocyclic rings.Financial support from the Spanish Government (Grants CTQ2010-14882, SEV2012-0267, and JCI-2010-06204) and the Generalitat Valenciana (Prometeo II/2013/005) is gratefully acknowledged.PĂ©rez Ruiz, R.; JimĂ©nez Molero, MC.; Miranda Alonso, MĂ. (2014). Hetero-cycloreversions Mediated by Photoinduced Electron Transfer. Accounts of Chemical Research. 47(4):1359-1368. https://doi.org/10.1021/ar4003224S1359136847
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