Metal oxide clusters of sub-nm dimensions dispersed on a metal oxide support are an important class of catalytic materials for a number of key chemical reactions, showing enhanced reactivity over the ...corresponding bulk oxide. In this paper we present the results of a density functional theory study of small sub-nm TiO(2) clusters, Ti(2)O(4), Ti(3)O(6) and Ti(4)O(8) supported on the rutile (110) surface. We find that all three clusters adsorb strongly with adsorption energies ranging from -3 eV to -4.5 eV. The more stable adsorption structures show a larger number of new Ti-O bonds formed between the cluster and the surface. These new bonds increase the coordination of cluster Ti and O as well as surface oxygen, so that each has more neighbours. The electronic structure shows that the top of the valence band is made up of cluster derived states, while the conduction band is made up of Ti 3d states from the surface, resulting in a reduction of the effective band gap and spatial separation of electrons and holes after photon absorption, which shows their potential utility in photocatalysis. To examine reactivity, we study the formation of oxygen vacancies in the cluster-support system. The most stable oxygen vacancy sites on the cluster show formation energies that are significantly lower than in bulk TiO(2), demonstrating the usefulness of this composite system for redox catalysis.
Studies with a series of metal/ceria(111) (metal=Co, Ni, Cu; ceria=CeO2) surfaces indicate that metal–oxide interactions can play a very important role for the activation of methane and its reforming ...with CO2 at relatively low temperatures (600–700 K). Among the systems examined, Co/CeO2(111) exhibits the best performance and Cu/CeO2(111) has negligible activity. Experiments using ambient pressure X‐ray photoelectron spectroscopy indicate that methane dissociates on Co/CeO2(111) at temperatures as low as 300 K—generating CHx and COx species on the catalyst surface. The results of density functional calculations show a reduction in the methane activation barrier from 1.07 eV on Co(0001) to 0.87 eV on Co2+/CeO2(111), and to only 0.05 eV on Co0/CeO2−x(111). At 700 K, under methane dry reforming conditions, CO2 dissociates on the oxide surface and a catalytic cycle is established without coke deposition. A significant part of the CHx formed on the Co0/CeO2−x(111) catalyst recombines to yield ethane or ethylene.
Cobalt/ceria (Co/CeO2), with a low loading of cobalt, is an efficient catalyst for methane activation at room temperature, and for dry reforming of methane (DRM) at relatively low temperatures (700 K). Higher temperatures transform Co2+/CeO2 into the highly active catalyst Co0/CeO2−x. DRM activity depends on the metal/CeO2 combination: Co/CeO2> Ni/CeO2, and Cu/CeO2 is inactive.
To counteract excessive effort due to relative income comparison among identical agents, the literature suggests a tax response equal to the negative externality. Assuming a general income ...distribution, we show that an optimal tax must be higher under a general social welfare function, to not only reduce inefficiency but also inequality. We recommend a practical tax response to stronger comparison – to hold employment constant, which does not require unrealistic information including unobservable comparison. Surprisingly, the tax response will dominate the comparison effect and
reduce
labour supply or reverse “keeping up with the Joneses” on intensive margins, and also reverse the otherwise rising inequality.
Background Time to treatment is critical for survival from sudden cardiac arrest. Every minute delay in defibrillation results in a 7% to 10% reduction in survival. This is particularly problematic ...in rural and remote regions, where emergency medical service response is prolonged and automated external defibrillators (AEDs) are often not available. Our primary objective was to examine the feasibility of a novel AED drone delivery method for rural and remote sudden cardiac arrest. A secondary objective was to compare response times between AED drone delivery and ambulance to mock sudden cardiac arrest resuscitations. Methods and Results We conducted 6 simulations in 2 rural communities in southern Ontario, Canada. In the first 2 simulations, the drone and ambulance were dispatched from the same paramedic base. In simulations 3 and 4, the drone and ambulance were dispatched from separate paramedic bases; and in simulations 5 and 6, the drone was dispatched from an optimized location. During each simulation, a "mock" call was placed to 911 and a single AED drone and an ambulance were simultaneously dispatched to a predetermined destination. On scene, trained first responders retrieved the AED from the drone and initiated resuscitative efforts on a mannequin until paramedics arrived. No difficulties were encountered during drone activation by dispatch, ascent, landing, or bystander retrieval of the AED from the drone. During simulations 1 and 2, the distance to the scene was 6.6 km. For simulations 3 and 4, the ambulance response distance increased to 8.8 km while drone remained at 6.6 km; and in simulations 5 and 6, the ambulance response distance was 20 km compared with 9 km for the drone. During each flight, the AED drone arrived on scene before the ambulance, between 1.8 and 8.0 minutes faster. Conclusions This study suggests AED drone delivery is feasible, with the potential for improvements in response time during simulated sudden cardiac arrest scenarios. Further research is required to determine the appropriate system configuration for AED drone delivery in an integrated emergency medical service system as well as optimal strategies to simplify bystander application of a drone-delivered AED.
Fusion transcripts are formed by either fusion genes (DNA level) or trans-splicing events (RNA level). They have been recognized as a promising tool for diagnosing, subtyping and treating cancers. ...RNA-seq has become a precise and efficient standard for genome-wide screening of such aberration events. Many fusion transcript detection algorithms have been developed for paired-end RNA-seq data but their performance has not been comprehensively evaluated to guide practitioners. In this paper, we evaluated 15 popular algorithms by their precision and recall trade-off, accuracy of supporting reads and computational cost. We further combine top-performing methods for improved ensemble detection.
Fifteen fusion transcript detection tools were compared using three synthetic data sets under different coverage, read length, insert size and background noise, and three real data sets with selected experimental validations. No single method dominantly performed the best but SOAPfuse generally performed well, followed by FusionCatcher and JAFFA. We further demonstrated the potential of a meta-caller algorithm by combining top performing methods to re-prioritize candidate fusion transcripts with high confidence that can be followed by experimental validation.
Our result provides insightful recommendations when applying individual tool or combining top performers to identify fusion transcript candidates.
Cu(acac)2 is chemisorbed on TiO2 particles P-25 (anatase/rutile = 4/1 w/w), Degussa via coordination by surface Ti–OH groups without elimination of the acac ligand. Post-heating of the ...Cu(acac)2-adsorbed TiO2 at 773 K yields molecular scale copper(II) oxide clusters on the surface (CuO/TiO2). The copper loading amount (Γ/Cu ions nm–2) is controlled in a wide range by the Cu(acac)2 concentration and the chemisorption–calcination cycle number. Valence band (VB) X-ray photoelectron and photoluminescence spectroscopy indicated that the VB maximum of TiO2 rises up with increasing Γ, while vacant midgap levels are generated. The surface modification gives rise to visible-light activity and concomitant significant increase in UV-light activity for the degradation of 2-naphthol and p-cresol. Prolonging irradiation time leads to the decomposition to CO2, which increases in proportion to irradiation time. The photocatalytic activity strongly depends on the loading, Γ, with an optimum value of Γ for the photocatalytic activity. Electrochemical measurements suggest that the surface CuO clusters promote the reduction of adsorbed O2. First principles density functional theory simulations clearly show that, at Γ < 1, unoccupied Cu 3d levels are generated in the midgap region, and at Γ > 1, the VB maximum rises and the unoccupied Cu 3d levels move to the conduction band minimum of TiO2. These results suggest that visible-light excitation of CuO/TiO2 causes the bulk-to-surface interfacial electron transfer at low coverage and the surface-to-bulk interfacial electron transfer at high coverage. We conclude that the surface CuO clusters enhance the separation of photogenerated charge carriers by the interfacial electron transfer and the subsequent reduction of adsorbed O2 to achieve the compatibility of high levels of visible and UV-light activities.
We describe two component hydrogels with networks composed of self-sorted fibres. The component gelators are based on 1,4-distyrylbenzene (OPV3) and perylene bisimide (PBI) units. Self-sorted gels ...can be formed by a slow decrease in pH, which leads to sequential assembly. We demonstrate self-sorting by NMR, rheology and small angle X-ray scattering (SAXS). Photoconductive xerogels can be prepared by drying these gels. The wavelength response of the xerogel is different to that of the PBI alone.
With the intent of improving transparency in clinical research, the International Committee of Medical Journal Editors (ICMJE) established guidelines in 2005 regarding prospective clinical trial ...registration. This action worked to address bias related to selective outcome reporting in the medical literature. The objective of this study was to assess and characterize the quality of registration of clinical trials appearing in shoulder arthroplasty-related medical journals.
All randomized trials involving human subjects, pertaining to shoulder arthroplasty, published between July 1, 2005 and December 31, 2015, and indexed in either PubMed or SportDISCUS were analyzed. We assessed the prevalence of registration, the timing of registration relative to patient enrollment periods, and the variable rates of orthopedic journal compliance with ICMJE and Food and Drug Administration clinical registration standards for our study.
Of the 382 articles identified, 345 (90.3%) were excluded due to failure to meet inclusion criteria. From the remaining 37, only 12 (32.4%) studies were found to be registered in a trial registry. Ten (10/12, 83.3%) of these provided their registration information within the body of the article. None of the included studies from ICMJE-recognized journals were registered. From 34 included studies from non-ICMJE recognized journals, 12 (35.3%) were registered.
The level of compliance with clinical trial registration guidelines in the decade since their release among shoulder arthroplasty trials in orthopedic journals is poor. Given the importance of the issue, the prevalence of the problem, and the fact that many other medical specialties have already made efforts to improve ICMJE compliance, further work on the part of orthopedic surgery journal authors and editors is needed to ensure the publication of unbiased results.
UMIN000022487.
Celotno besedilo
Dostopno za:
DOBA, IZUM, KILJ, NUK, PILJ, PNG, SAZU, SIK, UILJ, UKNU, UL, UM, UPUK
As China's outward foreign direct investment (FDI) has grown, its approach to international investment agreements (IIAs) has changed. China is now one of the world's most important outward investors, ...with Chinese FDI facing widespread criticism. The challenge for China is to adapt to this new configuration of interests stemming from these developments, both in terms of its national policies and the contents of its IIAs. In so doing, it is likely to influence, perhaps significantly, the further evolution of international investment law. This article deals briefly with the salient features of China's outward FDI and the policies that support it (Section A); the perception and reception of China's outward FDI in key host countries (Section B); and the changing nature of the country's approach to international investment treaties (Section C). The article concludes (Section D) with a brief review and outlook. web URL: http://jiel.oxfordjournals.org/content/18/4/893.abstract
Perylene bisimides (PBIs) self‐assemble in solution. The solubility of the PBIs is commonly changed through the choice of substituents at the imide positions. It is generally assumed this ...substitution does not affect the electronic properties of the PBI, and that the properties of the self‐assembled aggregate are essentially that of the isolated molecule. However, substituents do affect the self‐assembly, resulting in potentially different packing in the formed aggregates. Here, we show that the photoconductivity of films formed from a library of substituted PBIs varies strongly with the substituent and demonstrate that this is due to the different ways in which they pack. Our results open the possibility for tuning the optoelectronic properties of self‐assembled PBIs by controlling the aggregate structure through careful choice of substituent, as demonstrated by us here optimising the photoconductivity of PBI films in this way.
The photoconductivity of films formed from self‐assembled perylene bisimides varies strongly with the amino acid substituent at the imide position. The substituent controls the molecular packing, and this leads to the differences.
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