62 research outputs found

    Conformable Nanowire-in-Nanofiber Hybrids for Low-Threshold Optical Gain in the Ultraviolet

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    The miniaturization of diagnostic devices that exploit optical detection schemes requires the design of light sources combining small size, high performance for effective excitation of chromophores, and mechanical flexibility for easy coupling to components with complex and nonplanar shapes. Here, ZnO nanowire-in-fiber hybrids with internal architectural order are introduced, exhibiting a combination of polarized stimulated emission, low propagation losses of light modes, and structural flexibility. Ultrafast transient absorption experiments on the electrospun material show optical gain which gives rise to amplified spontaneous emission with a threshold lower than the value found in films. These systems are highly flexible and can conveniently conform to curved surfaces, which makes them appealing active elements for various device platforms, such as bendable lasers, optical networks, and sensors, as well as for application in bioimaging, photo-cross-linking, and optogenetics

    Placebo Effect of Caffeine on Substrate Oxidation during Exercise

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    By using deceptive experiments in which participants are informed that they received caffeine when, in fact, they received an inert substance (i.e., placebo), several investigations have demonstrated that exercise performance can be enhanced to a similar degree as a known caffeine dose. This ‘placebo effect’ phenomenon may be part of the mechanisms explaining caffeine’s ergogenicity in exercise. However, there is no study that has established whether the placebo effect of caffeine is also present for other benefits obtained with acute caffeine intake, such as enhanced fat oxidation during exercise. Therefore, the aim of this investigation was to investigate the placebo effect of caffeine on fat oxidation during exercise. Twelve young men participated in a deceptive doubleblind cross-over experiment. Each participant completed three identical trials consisting of a step incremental exercise test from 30 to 80% of . VO2max. In the two first trials, participants ingested either 3 mg/kg of cellulose (placebo) or 3 mg/kg of caffeine (received caffeine) in a randomized order. In the third trial, participants were informed that they had received 3 mg/kg of caffeine, but a placebo was provided (informed caffeine). Fat oxidation rates were derived from stoichiometric equations. In received caffeine, participants increased their rate of fat oxidation over the values obtained with the placebo at 30%, 40%, 50%, and 60% of . VO2max (all p < 0.050). In informed caffeine, participants increased their rate of fat oxidation at 30%, 40%, 50% 60%, and 70% of . VO2max (all p < 0.050) over the placebo, while there were no differences between received versus informed caffeine. In comparison to placebo (0.32 ± 0.15 g/min), the rate of maximal fat oxidation was higher in received caffeine (0.44 ± 0.22 g/min, p = 0.045) and in informed caffeine (0.41 ± 0.20 g/min, p = 0.026) with no differences between received versus informed caffeine. However, the intensity at which maximal fat oxidation rate was obtained (i.e., Fatmax) was similar in placebo, received caffeine, and informed caffeine trials (42.5 ± 4.5, 44.2 ± 9.0, and 41.7 ± 10.5% of . VO2max, respectively, p = 0.539). In conclusion, the expectancy of having received caffeine produced similar effects on fat oxidation rate during exercise than actually receiving caffeine. Therefore, the placebo effect of caffeine is also present for the benefits of acute caffeine intake on substrate oxidation during exercise and it may be used to enhance fat oxidation during exercise in participants while reducing any risks to health that this substance may have.Francisco de Vitoria University UFV-18/202

    A Unified Experimental/Theoretical Description of the Ultrafast Photophysics of Single and Double Thionated Uracils

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    Photoinduced processes in thiouracil derivatives have lately attracted considerable attention due to their suitability for innovative biological and pharmacological applications. Here, sub-20 fs broadband transient absorption spectroscopy in the near-UV are combined with CASPT2/MM decay path calculations to unravel the excited-state decay channels of water solvated 2-thio and 2,4-dithiouracil. These molecules feature linear absorption spectra with overlapping ππ* bands, leading to parallel decay routes which we systematically track for the first time. The results reveal that different processes lead to the triplet states population, both directly from the ππ* absorbing state and via the intermediate nπ* dark state. Moreover, the 2,4-dithiouracil decay pathways is shown to be strongly correlated either to those of 2- or 4-thiouracil, depending on the sulfur atom on which the electronic transition localizes

    Coherent vibrational modes promote the ultrafast internal conversion and intersystem crossing in thiobases

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    Thionated nucleobases are obtained by replacing oxygen with sulphur atoms in the canonical nucleobases. They absorb light efficiently in the near-ultraviolet, populating singlet states which undergo intersystem crossing to the triplet manifold on an ultrashort time scale with a high quantum yield. Nonetheless there are still important open questions about the primary mechanisms responsible for this ultrafast transition. Here we track both the electronic and the vibrational ultrafast excited-state dynamics towards the triplet state for solvated 4-thiothymidine (4TT) and 4-thiouracil (4TU) with sub-30 fs broadband transient absorption spectroscopy in the ultraviolet. A global and target analysis allows us to simultaneously resolve the contributions of the different electronically and vibrationally excited states to the whole data set. Our experimental results, combined with state-of-the-art quantum mechanics/molecular mechanics simulations and Damped Oscillation Associated Spectra (DOAS) and target analysis, support that the relaxation to the triplet state is mediated by conical intersections promoted by vibrational coherences through the population of an intermediate singlet state. In addition, the analysis of the coherent vibrational dynamics reveals that, despite sharing the same relaxation mechanism and similar chemical structures, 4TT and 4TU exhibit rather different geometrical deformations, characterized by the conservation of planarity in 4TU and its partial rupture in 4TT

    Electron and ion spectroscopy of azobenzene in the valence and core shells

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    Azobenzene is a prototype and a building block of a class of molecules of extreme technological interest as molecular photo-switches. We present a joint experimental and theoretical study of its response to irradiation with light across the UV to x-ray spectrum. The study of valence and inner shell photo-ionization and excitation processes combined with measurement of valence photoelectron-photoion coincidence and mass spectra across the core thresholds provides a detailed insight into the site- and state-selected photo-induced processes. Photo-ionization and excitation measurements are interpreted via the multi-configurational restricted active space self-consistent field method corrected by second order perturbation theory. Using static modeling, we demonstrate that the carbon and nitrogen K edges of azobenzene are suitable candidates for exploring its photoinduced dynamics thanks to the transient signals appearing in background-free regions of the NEXAFS and XPS

    HELP: the Herschel Extragalactic Legacy Project

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    We present the Herschel Extragalactic Legacy Project (HELP). This project collates, curates, homogenizes, and creates derived data products for most of the premium multiwavelength extragalactic data sets. The sky boundaries for the first data release cover 1270 deg2 defined by the Herschel SPIRE extragalactic survey fields; notably the Herschel Multi-tiered Extragalactic Survey (HerMES) and the Herschel Atlas survey (H-ATLAS). Here, we describe the motivation and principal elements in the design of the project. Guiding principles are transparent or ‘open’ methodologies with care for reproducibility and identification of provenance. A key element of the design focuses around the homogenization of calibration, meta data, and the provision of information required to define the selection of the data for statistical analysis. We apply probabilistic methods that extract information directly from the images at long wavelengths, exploiting the prior information available at shorter wavelengths and providing full posterior distributions rather than maximum-likelihood estimates and associated uncertainties as in traditional catalogues. With this project definition paper, we provide full access to the first data release of HELP; Data Release 1 (DR1), including a monolithic map of the largest SPIRE extragalactic field at 385 deg2 and 18 million measurements of PACS and SPIRE fluxes. We also provide tools to access and analyse the full HELP data base. This new data set includes far-infrared photometry, photometric redshifts, and derived physical properties estimated from modelling the spectral energy distributions over the full HELP sky. All the software and data presented is publicly available

    Rapid Detection of the H275Y Oseltamivir Resistance Mutation in Influenza A/H1N1 2009 by Single Base Pair RT-PCR and High-Resolution Melting

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    Introduction: We aimed to design a real-time reverse-transcriptase-PCR (rRT-PCR), high-resolution melting (HRM) assay to detect the H275Y mutation that confers oseltamivir resistance in influenza A/H1N1 2009 viruses.Findings: A novel strategy of amplifying a single base pair, the relevant SNP at position 823 of the neuraminidase gene, was chosen to maintain specificity of the assay. Wildtype and mutant virus were differentiated when using known reference samples of cell-cultured virus. However, when dilutions of these reference samples were assayed, amplification of nonspecific primer-dimer was evident and affected the overall melting temperature (Tm) of the amplified products. Due to primer-dimer appearance at .30 cycles we found that if the cycle threshold (CT) for a dilution was .30, the HRM assay did not consistently discriminate mutant from wildtype. Where the CT was ,30 we noted an inverse relationship between CT and Tm and fitted quadratic curves allowed the discrimination of wildtype, mutant and 30:70 mutant:wildtype virus mixtures. We compared the CT values for a TaqMan H1N1 09 detection assay with those for the HRM assay using 59 clinical samples and demonstrated that samples with a TaqMan detection assay CT.32.98 would have an H275Y assay CT.30. Analysis of the TaqMan CT values for 609 consecutive clinical samples predicted that 207 (34%) of the samples would result in an HRM assay CT.30 and therefore not be amenable to the HRM assay.Conclusions: The use of single base pair PCR and HRM can be useful for specifically interrogating SNPs. When applied to H1N1 09, the constraints this placed on primer design resulted in amplification of primer-dimer products. The impact primer-dimer had on HRM curves was adjusted for by plotting Tm against CT. Although less sensitive than TaqMan assays, the HRM assay can rapidly, and at low cost, screen samples with moderate viral concentrations

    HELP: the Herschel Extragalactic Legacy Project

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    We present the Herschel Extragalactic Legacy Project (HELP). This project collates, curates, homogenises, and creates derived data products for most of the premium multi-wavelength extragalactic data sets. The sky boundaries for the first data release cover 1270 deg2 defined by the Herschel SPIRE extragalactic survey fields; notably the Herschel Multi-tiered Extragalactic Survey (HerMES) and the Herschel Atlas survey (H-ATLAS). Here, we describe the motivation and principal elements in the design of the project. Guiding principles are transparent or “open” methodologies with care for reproducibility and identification of provenance. A key element of the design focuses around the homogenisation of calibration, meta data and the provision of information required to define the selection of the data for statistical analysis. We apply probabilistic methods that extract information directly from the images at long wavelengths, exploiting the prior information available at shorter wavelengths and providing full posterior distributions rather than maximum likelihood estimates and associated uncertainties as in traditional catalogues. With this project definition paper we provide full access to the first data release of HELP; Data Release 1 (DR1), including a monolithic map of the largest SPIRE extragalactic field at 385 deg2 and 18 million measurements of PACS and SPIRE fluxes. We also provide tools to access and analyse the full HELP database. This new data set includes far-infrared photometry, photometric redshifts, and derived physical properties estimated from modelling the spectral energy distributions over the full HELP sky. All the software and data presented is publicly available
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