1,277 research outputs found

    Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation

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    Catalysis makes possible a chemical reaction by increasing the transformation rate. Hydrogenation of carbon-carbon multiple bonds is one of the most important examples of catalytic reactions. Currently, this type of reaction is carried out in petrochemistry at very large scale, using noble metals such as platinum and palladium or first row transition metals such as nickel. Catalysis is dominated by metals and in many cases by precious ones. Here we report that graphene (a single layer of one-atom-thick carbon atoms) can replace metals for hydrogenation of carbon-carbon multiple bonds. Besides alkene hydrogenation, we have shown that graphenes also exhibit high selectivity for the hydrogenation of acetylene in the presence of a large excess of ethylene.This study was financially supported by the Spanish Ministry of Economy and Competitiveness (Severo Ochoa and CTQ2012-32315); and Generalidad Valenciana (Prometeo 21/013) is gratefully acknowledged.Primo Arnau, AM.; Neatu, F.; Florea, M.; Parvulescu, V.; García Gómez, H. (2014). Graphenes in the absence of metals as carbocatalysts for selective acetylene hydrogenation and alkene hydrogenation. Nature Communications. 5:1-9. https://doi.org/10.1038/ncomms6291S195Dreyer, D. R. & Bielawski, C. W. Carbocatalysis: heterogeneous carbons finding utility in synthetic chemistry. Chem. Sci. 2, 1233–1240 (2011).Machado, B. F. & Serp, P. Graphene-based materials for catalysis. Catal. Sci. Technol. 2, 54–75 (2012).Schaetz, A., Zeltner, M. & Stark, W. J. Carbon modifications and surfaces for catalytic organic transformations. 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High-pressure hydrogenation of graphene: towards graphane. Nanoscale 4, 7006–7011 (2012).Sofo, J. O., Chaudhari, A. S. & Barber, G. D. Graphane: A two-dimensional hydrocarbon. J. Phys. Chem. B 75, 153401 (2007).Elias, D. C. et al. Control of graphene’s properties by reversible hydrogenation: evidence for graphane. Science 323, 610–613 (2009).Despiau-Pujo, E. et al. Elementary processes of H2 plasma-graphene interaction: a combined molecular dynamics and density functional theory study. J. Appl. Phys. 113, 114302 (2013).Xu, L. & Ge, Q. Effects of defects and dopants in graphene on hydrogen interaction in graphene-supported NaAlH4. Int. J. Hydrogen Energy 38, 3670–3680 (2013).Perhun, T. I., Bychko, I. B., Trypolsky, A. I. & Strizhak, P. E. Catalytic properties of graphene material in the hydrogenation of ethylene. Theor. Exp. Chem. 48, 367–370 (2013).Hummers, W. S. & Offeman, R. E. Preparation of graphitic oxide. J. Am. Chem. 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The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation. Science 320, 86–89 (2008).Bridier, B., Lopez, N. & Perez-Ramirez, J. Molecular understanding of alkyne hydrogenation for the design of selective catalysts. Dalton Trans. 39, 8412–8419 (2010).Flick, K., Herion, C. & Allmann, H. Palladium-haltiger Trägerkatalysator zur selektiven katalytischen Hydrierung von Acetylen in Kohlenwasserstoffströmen. EP764463-A; EP764463-A2; DE19535402-A1; JP9141097-A; CA2185721-A; KR97014834-A; MX9604031-A1; US5847250-A; US5856262-A; TW388722-A; MX195137-B; CN1151908-A; EP764463-B1; DE59610365-G; ES2197222-T3; KR418161-B; CN1081487-C; JP3939787-B2; CA2185721-C (1997).Gartside, R. J. et al. Improved olefin plant recovery system employing a combination of catalytic distillation and fixed bed catalytic steps. 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    Simultaneous non-negative matrix factorization for multiple large scale gene expression datasets in toxicology

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    Non-negative matrix factorization is a useful tool for reducing the dimension of large datasets. This work considers simultaneous non-negative matrix factorization of multiple sources of data. In particular, we perform the first study that involves more than two datasets. We discuss the algorithmic issues required to convert the approach into a practical computational tool and apply the technique to new gene expression data quantifying the molecular changes in four tissue types due to different dosages of an experimental panPPAR agonist in mouse. This study is of interest in toxicology because, whilst PPARs form potential therapeutic targets for diabetes, it is known that they can induce serious side-effects. Our results show that the practical simultaneous non-negative matrix factorization developed here can add value to the data analysis. In particular, we find that factorizing the data as a single object allows us to distinguish between the four tissue types, but does not correctly reproduce the known dosage level groups. Applying our new approach, which treats the four tissue types as providing distinct, but related, datasets, we find that the dosage level groups are respected. The new algorithm then provides separate gene list orderings that can be studied for each tissue type, and compared with the ordering arising from the single factorization. We find that many of our conclusions can be corroborated with known biological behaviour, and others offer new insights into the toxicological effects. Overall, the algorithm shows promise for early detection of toxicity in the drug discovery process

    Adaptive migratory orientation of an invasive pest on a new continent

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    This is the final version. Available on open access from Cell Press via the DOI in this recordData and code availability: The authors declare that the data supporting the findings of this study are available within the paper and its Supplemental Information. Individual data files used to generate the figures in the paper have been deposited in Mendeley Data (https://doi.org/10.17632/6jkvpybswd.1). Custom-written Visual Basic software Flash Flight Simulator Data Acquisition System and Mapflows have been deposited in Mendeley Data (https://doi.org/10.17632/6jkvpybswd.1). Custom single-chip used for data acquisition is available from the corresponding authors upon reasonable request ([email protected], [email protected]). Any additional information required to reanalyze the data reported in this work paper is available from the lead contact upon request.Many species of insects undertake long-range, seasonally reversed migrations, displaying sophisticated orientation behaviors to optimize their migratory trajectories. However, when invasive insects arrive in new biogeographical regions, it is unclear if migrants retain (or how quickly they regain) ancestral migratory traits, such as seasonally preferred flight headings. Here we present behavioral evidence that an invasive migratory pest, the fall armyworm moth (Spodoptera frugiperda), a native of the Americas, exhibited locally adaptive migratory orientation less than three years after arriving on a new continent. Specimens collected from China showed flight orientations directed north-northwest in spring and southwest in autumn, and this would promote seasonal forward and return migrations in East Asia. We also show that the driver of the seasonal switch in orientation direction is photoperiod. Our results thus provide a clear example of an invasive insect that has rapidly exhibited adaptive migratory behaviors, either inherited or newly evolved, in a completely alien environment.National Key Research and Development Program of Chin

    Direct exfoliation and dispersion of two-dimensional materials in pure water via temperature control

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    The high-volume synthesis of two-dimensional (2D) materials in the form of platelets is desirable for various applications. While water is considered an ideal dispersion medium, due to its abundance and low cost, the hydrophobicity of platelet surfaces has prohibited its widespread use. Here we exfoliate 2D materials directly in pure water without using any chemicals or surfactants. In order to exfoliate and disperse the materials in water, we elevate the temperature of the sonication bath, and introduce energy via the dissipation of sonic waves. Storage stability greater than one month is achieved through the maintenance of high temperatures, and through atomic and molecular level simulations, we further discover that good solubility in water is maintained due to the presence of platelet surface charges as a result of edge functionalization or intrinsic polarity. Finally, we demonstrate inkjet printing on hard and flexible substrates as a potential application of water-dispersed 2D materials.close1

    The complete sequences and gene organisation of the mitochondrial genomes of the heterodont bivalves Acanthocardia tuberculata and Hiatella arctica – and the first record for a putative Atpase subunit 8 gene in marine bivalves

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    BACKGROUND: Mitochondrial (mt) gene arrangement is highly variable among molluscs and especially among bivalves. Of the 30 complete molluscan mt-genomes published to date, only one is of a heterodont bivalve, although this is the most diverse taxon in terms of species numbers. We determined the complete sequence of the mitochondrial genomes of Acanthocardia tuberculata and Hiatella arctica, (Mollusca, Bivalvia, Heterodonta) and describe their gene contents and genome organisations to assess the variability of these features among the Bivalvia and their value for phylogenetic inference. RESULTS: The size of the mt-genome in Acanthocardia tuberculata is 16.104 basepairs (bp), and in Hiatella arctica 18.244 bp. The Acanthocardia mt-genome contains 12 of the typical protein coding genes, lacking the Atpase subunit 8 (atp8) gene, as all published marine bivalves. In contrast, a complete atp8 gene is present in Hiatella arctica. In addition, we found a putative truncated atp8 gene when re-annotating the mt-genome of Venerupis philippinarum. Both mt-genomes reported here encode all genes on the same strand and have an additional trnM. In Acanthocardia several large non-coding regions are present. One of these contains 3.5 nearly identical copies of a 167 bp motive. In Hiatella, the 3' end of the NADH dehydrogenase subunit (nad)6 gene is duplicated together with the adjacent non-coding region. The gene arrangement of Hiatella is markedly different from all other known molluscan mt-genomes, that of Acanthocardia shows few identities with the Venerupis philippinarum. Phylogenetic analyses on amino acid and nucleotide levels robustly support the Heterodonta and the sister group relationship of Acanthocardia and Venerupis. Monophyletic Bivalvia are resolved only by a Bayesian inference of the nucleotide data set. In all other analyses the two unionid species, being to only ones with genes located on both strands, do not group with the remaining bivalves. CONCLUSION: The two mt-genomes reported here add to and underline the high variability of gene order and presence of duplications in bivalve and molluscan taxa. Some genomic traits like the loss of the atp8 gene or the encoding of all genes on the same strand are homoplastic among the Bivalvia. These characters, gene order, and the nucleotide sequence data show considerable potential of resolving phylogenetic patterns at lower taxonomic levels

    A new Raman metric for the characterisation of graphene oxide and its derivatives

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    Raman spectroscopy is among the primary techniques for the characterisation of graphene materials, as it provides insights into the quality of measured graphenes including their structure and conductivity as well as the presence of dopants. However, our ability to draw conclusions based on such spectra is limited by a lack of understanding regarding the origins of the peaks. Consequently, traditional characterisation techniques, which estimate the quality of the graphene material using the intensity ratio between the D and the G peaks, are unreliable for both GO and rGO. Herein we reanalyse the Raman spectra of graphenes and show that traditional methods rely upon an apparent G peak which is in fact a superposition of the G and D’ peaks. We use this understanding to develop a new Raman characterisation method for graphenes that considers the D’ peak by using its overtone the 2D’. We demonstrate the superiority and consistency of this method for calculating the oxygen content of graphenes, and use the relationship between the D’ peak and graphene quality to define three regimes. This has important implications for purification techniques because, once GO is reduced beyond a critical threshold, further reduction offers limited gain in conductivity

    Isolated and dynamical horizons and their applications

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    Over the past three decades, black holes have played an important role in quantum gravity, mathematical physics, numerical relativity and gravitational wave phenomenology. However, conceptual settings and mathematical models used to discuss them have varied considerably from one area to another. Over the last five years a new, quasi-local framework was introduced to analyze diverse facets of black holes in a unified manner. In this framework, evolving black holes are modeled by dynamical horizons and black holes in equilibrium by isolated horizons. We review basic properties of these horizons and summarize applications to mathematical physics, numerical relativity and quantum gravity. This paradigm has led to significant generalizations of several results in black hole physics. Specifically, it has introduced a more physical setting for black hole thermodynamics and for black hole entropy calculations in quantum gravity; suggested a phenomenological model for hairy black holes; provided novel techniques to extract physics from numerical simulations; and led to new laws governing the dynamics of black holes in exact general relativity.Comment: 77 pages, 12 figures. Typos and references correcte

    Low-Load High Volume Resistance Exercise Stimulates Muscle Protein Synthesis More Than High-Load Low Volume Resistance Exercise in Young Men

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    BACKGROUND: We aimed to determine the effect of resistance exercise intensity (%1 repetition maximum-1RM) and volume on muscle protein synthesis, anabolic signaling, and myogenic gene expression. METHODOLOGY/PRINCIPAL FINDINGS: Fifteen men (21+/-1 years; BMI=24.1+/-0.8 kg/m2) performed 4 sets of unilateral leg extension exercise at different exercise loads and/or volumes: 90% of repetition maximum (1RM) until volitional failure (90FAIL), 30% 1RM work-matched to 90%FAIL (30WM), or 30% 1RM performed until volitional failure (30FAIL). Infusion of [ring-13C6] phenylalanine with biopsies was used to measure rates of mixed (MIX), myofibrillar (MYO), and sarcoplasmic (SARC) protein synthesis at rest, and 4 h and 24 h after exercise. Exercise at 30WM induced a significant increase above rest in MIX (121%) and MYO (87%) protein synthesis at 4 h post-exercise and but at 24 h in the MIX only. The increase in the rate of protein synthesis in MIX and MYO at 4 h post-exercise with 90FAIL and 30FAIL was greater than 30WM, with no difference between these conditions; however, MYO remained elevated (199%) above rest at 24 h only in 30FAIL. There was a significant increase in AktSer473 at 24h in all conditions (P=0.023) and mTORSer2448 phosphorylation at 4 h post-exercise (P=0.025). Phosporylation of Erk1/2Tyr202/204, p70S6KThr389, and 4E-BP1Thr37/46 increased significantly (P<0.05) only in the 30FAIL condition at 4 h post-exercise, whereas, 4E-BP1Thr37/46 phosphorylation was greater 24 h after exercise than at rest in both 90FAIL (237%) and 30FAIL (312%) conditions. Pax7 mRNA expression increased at 24 h post-exercise (P=0.02) regardless of condition. The mRNA expression of MyoD and myogenin were consistently elevated in the 30FAIL condition. CONCLUSIONS/SIGNIFICANCE: These results suggest that low-load high volume resistance exercise is more effective in inducing acute muscle anabolism than high-load low volume or work matched resistance exercise modes

    Highly exposed {001} facets of titanium dioxide modified with reduced graphene oxide for dopamine sensing

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    Titanium dioxide (TiO2) with highly exposed {001} facets was synthesized through a facile solvo-thermal method and its surface was decorated by using reduced graphene oxide (rGO) sheets. The morphology and chemical composition of the prepared rGO/TiO2 {001} nanocomposite were examined by using suitable characterization techniques. The rGO/TiO2 {001} nanocomposite was used to modify glassy carbon electrode (GCE), which showed higher electrocatalytic activity towards the oxidation of dopamine (DA) and ascorbic acid (AA), when compared to unmodified GCE. The differential pulse voltammetric studies revealed good sensitivity and selectivity nature of the rGO/TiO2 {001} nanocomposite modified GCE for the detection of DA in the presence of AA. The modified GCE exhibited a low electrochemical detection limit of 6 μM over the linear range of 2–60 μM. Overall, this work provides a simple platform for the development of GCE modified with rGO/TiO2 {001} nanocomposite with highly exposed {001} facets for potential electrochemical sensing applications

    High-efficiency exfoliation of large-area mono-layer graphene oxide with controlled dimension

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    In this work, we introduce a novel and facile method of exfoliating large-area, single-layer graphene oxide using a shearing stress. The shearing stress reactor consists of two concentric cylinders, where the inner cylinder rotates at controlled speed while the outer cylinder is kept stationary. We found that the formation of Taylor vortex flow with shearing stress can effectively exfoliate the graphite oxide, resulting in large-area single- or few-layer graphene oxide (GO) platelets with high yields (&gt;90%) within 60 min of reaction time. Moreover, the lateral size of exfoliated GO sheets was readily tunable by simply controlling the rotational speed of the reactor and reaction time. Our approach for high-efficiency exfoliation of GO with controlled dimension may find its utility in numerous industrial applications including energy storage, conducting composite, electronic device, and supporting frameworks of catalyst
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