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The pronounced effects of the composition of four-atom monometallic Cu and Pd and bimetallic CuPd clusters and the support on the catalytic activity and selectivity in the oxidative dehydrogenation of cyclohexene are reported. The ultra-nanocrystalline diamond supported clusters are highly active and dominantly produce benzene; some of the mixed clusters also produce cyclohexadiene, which are all clusters with a much suppressed combustion channel. The also highly active TiO2-supported tetramers solely produce benzene, without any combustion to CO2. The selectivity of the zirconia-supported mixed CuPd clusters and the monometallic Cu cluster is entirely different; though they are less active in comparison to clusters with other supports, these clusters produce significant fractions of cyclohexadiene, with their selectivity towards cyclohexadiene gradually increasing with the increasing number of copper atoms in the cluster, reaching about 50% for Cu3Pd1. The zirconia-supported copper tetramer stands out from among all the other tetramers in this reaction, with a selectivity towards cyclohexadiene of 70%, which far exceeds those of all the other cluster-support combinations. The findings from this study indicate a positive effect of copper on the stability of the mixed tetramers and potential new ways of fine-tuning catalyst performance by controlling the composition of the active site and via cluster-support interactions in complex oxidative reactions under the suppression of the undesired combustion of the feed.
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The effect of particle size and support on the catalytic performance of supported subnanometer copper clusters was investigated in the oxidative dehydrogenation of cyclohexene. From among the investigated seven size-selected subnanometer copper particles between a single atom and clusters containing 2-7 atoms, the highest activity was observed for the titania-supported copper tetramer with 100% selectivity toward benzene production and being about an order of magnitude more active than not only all the other investigated cluster sizes on the same support but also the same tetramer on the other supports, Al2O3, SiO2, and SnO2. In addition to the profound effect of cluster size on activity and with Cu4 outstanding from the studied series, Cu4 clusters supported on SiO2 provide an example of tuning selectivity through support effects when this particular catalyst also produces cyclohexadiene with about 30% selectivity. Titania-supported Cu5 and Cu7 clusters supported on TiO2 produce a high fraction of cyclohexadiene in contrast to their neighbors, while Cu4 and Cu6 solely produce benzene without any combustion, thus representing odd-even oscillation of selectivity with the number of atoms in the cluster.
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The standard for diagnosing metopic craniosynostosis (CS) utilizes computed tomography (CT) imaging and physical exam, but there is no standardized method for determining disease severity. Previous studies using interfrontal angles have evaluated differences in specific skull landmarks; however, these measurements are difficult to readily ascertain in clinical practice and fail to assess the complete skull contour. This pilot project employs machine learning algorithms to combine statistical shape information with expert ratings to generate a novel objective method of measuring the severity of metopic CS.Expert ratings of normal and metopic skull CT images were collected. Skull-shape analysis was conducted using ShapeWorks software. Machine-learning was used to combine the expert ratings with our shape analysis model to predict the severity of metopic CS using CT images. Our model was then compared to the gold standard using interfrontal angles.Seventeen metopic skull CT images of patients 5 to 15 months old were assigned a severity by 18 craniofacial surgeons, and 65 nonaffected controls were included with a 0 severity. Our model accurately correlated the level of skull deformity with severity (Pâ<â0.10) and predicted the severity of metopic CS more often than models using interfrontal angles (χâ=â5.46, Pâ=â0.019).This is the first study that combines shape information with expert ratings to generate an objective measure of severity for metopic CS. This method may help clinicians easily quantify the severity and perform robust longitudinal assessments of the condition.
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Craniossinostoses/diagnóstico por imagem , Face/diagnóstico por imagem , Crânio/diagnóstico por imagem , Craniossinostoses/cirurgia , Face/cirurgia , Humanos , Lactente , Aprendizado de Máquina , Projetos Piloto , Crânio/cirurgia , Tomografia Computadorizada por Raios XRESUMO
TiO2 films were prepared via a two-step fabrication process, i.e. deposition of Ti films by magnetron sputtering on an FTO glass substrate followed by thermal oxidation at 600-725 °C. The investigated parameters were Ti layer thickness, temperature of oxidation and deposition conditions (pre-treatment and substrate heating). Such TiO2 films have a rutile structure and contain metallic Sn which is the result of a thermal reaction at the interface between SnO2 and Ti at temperatures above 500 °C. A calcination temperature of 600 °C is optimal for fabricating TiO2 films with significant photoelectrochemical response. Heating of the FTO substrate during magnetron sputtering deposition of Ti films results in a significant improvement of the compactness of the TiO2 films. A similar but not so pronounced improvement was observed for the TiO2 films deposited on the FTO substrate pre-treated with radio-frequency plasma under Ar-O2 and N2-H2 atmosphere. The observed correlation between the increased content of Sn in the TiO2 films and compactness of the TiO2 films supports the explanation of both positive effects by better adhesion of the Ti films to the FTO substrate.
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Redox mediators play a major role determining the photocurrent and the photovoltage in dye-sensitized solar cells (DSCs). To maintain the photocurrent, the reduction of oxidized dye by the redox mediator should be significantly faster than the electron back transfer between TiO2 and the oxidized dye. The driving force for dye regeneration with the redox mediator should be sufficiently low to provide high photovoltages. With the introduction of our new copper complexes as promising redox mediators in DSCs both criteria are satisfied to enhance power conversion efficiencies. In this study, two copper bipyridyl complexes, Cu(II/I)(dmby)2TFSI2/1 (0.97 V vs SHE, dmby = 6,6'-dimethyl-2,2'-bipyridine) and Cu(II/I)(tmby)2TFSI2/1 (0.87 V vs SHE, tmby = 4,4',6,6'-tetramethyl-2,2'-bipyridine), are presented as new redox couples for DSCs. They are compared to previously reported Cu(II/I)(dmp)2TFSI2/1 (0.93 V vs SHE, dmp = bis(2,9-dimethyl-1,10-phenanthroline). Due to the small reorganization energy between Cu(I) and Cu(II) species, these copper complexes can sufficiently regenerate the oxidized dye molecules with close to unity yield at driving force potentials as low as 0.1 V. The high photovoltages of over 1.0 V were achieved by the series of copper complex based redox mediators without compromising photocurrent densities. Despite the small driving forces for dye regeneration, fast and efficient dye regeneration (2-3 µs) was observed for both complexes. As another advantage, the electron back transfer (recombination) rates were slower with Cu(II/I)(tmby)2TFSI2/1 as evidenced by longer lifetimes. The solar-to-electrical power conversion efficiencies for [Cu(tmby)2]2+/1+, [Cu(dmby)2]2+/1+, and [Cu(dmp)2]2+/1+ based electrolytes were 10.3%, 10.0%, and 10.3%, respectively, using the organic Y123 dye under 1000 W m-2 AM1.5G illumination. The high photovoltaic performance of Cu-based redox mediators underlines the significant potential of the new redox mediators and points to a new research and development direction for DSCs.
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A novel procedure is developed for chemical modification of H-terminated B-doped diamond surfaces with a donor-π-bridge-acceptor molecule (P1). A cathodic photocurrent near 1 µA cm(-2) flows under 1 Sun (AM 1.5) illumination at the interface between the diamond electrode and aqueous electrolyte solution containing dimethylviologen (electron mediator). The efficiency of this new electrode outperforms that of the non-covalently modified diamond with the same dye. The found external quantum efficiency of the P1-sensitized diamond is not far from that of the flat titania electrode sensitized by a standard organometallic dye used in solar cells. However, the P1 dye, both pure and diamond-anchored, shows significant instability during illumination by solar light. The degradation is a two-stage process in which the initially photo-generated products further decompose in complicated dark reactions. These findings need to be taken into account for optimization of organic chromophores for solar cells in general.
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Tuning the electronic structure of 2D materials is a very powerful asset toward tailoring their properties to suit the demands of future applications in optoelectronics. Strain engineering is one of the most promising methods in this regard. We demonstrate that even very small out-of-plane axial compression readily modifies the electronic structure of monolayer MoS2. As we show through in situ resonant and nonresonant Raman spectroscopy and photoluminescence measurements combined with theoretical calculations, the transition from direct to indirect band gap semiconductor takes place at â¼0.5 GPa, and the transition to a semimetal occurs at stress smaller than 3 GPa.
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A novel simple and versatile synthetic strategy is developed for the surface modification of boron-doped diamond. In a two-step procedure, polyethyleneimine is adsorbed on the hydrogenated diamond surface and subsequently modified with a model light-harvesting donor-π-bridge-acceptor molecule (coded P1). The sensitized diamond exhibits stable cathodic photocurrents under visible-light illumination in aqueous electrolyte solution with dimethylviologen serving as an electron mediator. In spite of the simplicity of the surface sensitization protocol, the photoelectrochemical performance is similar to or better than that of other sensitized diamond electrodes which were reported in previous studies (2008-2014).
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Fullerenes, carbon nanotubes, nanodiamond, and graphene find various applications in the development of solar cells, including dye sensitized solar cells. Nanocarbons can be used as (1) active light-absorbing component, (2) current collector, (3) photoanode additive, or (4) counter electrode. Graphene-based materials have attracted considerable interest for catalytic counter electrodes, particularly in state-of-the-art dye sensitized solar cells with Co-mediators. The understanding of electrochemical charge-transfer at carbon surfaces is key to optimization of these solar cells, but the electrocatalysis on carbon surfaces is still a subject of conflicting debate. Due to the rich palette of problems at the interface of nanocarbons and photovoltaics, this review is selective rather than comprehensive. Its motivation was to highlight selected prospective inputs from nanocarbon science towards the development of novel dye sensitized solar cells with improved efficiency, durability, and cost.
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Compact, thin TiO2 films are grown on F-doped SnO2 (FTO) by dip-coating from precursor solutions containing poly(hexafluorobutyl methacrylate) or hexafluorobutyl methacrylate as the structure-directing agents. The films are quasi-amorphous, but crystallize to TiO2 (anatase) upon heat treatment at 500 °C in air. Cyclic voltammetry experiments performed using Fe(CN)6(3-/4-) or spiro-OMeTAD as model redox probes selectively indicate the pinholes, if any, in the layer. The pinhole-free films on FTO represent an excellent rectifying interface at which no anodic faradaic reactions occur in the depletion state. The flat-band potentials of the as-grown films are upshifted by 0.2-0.4 V against the values predicted for a perfect anatase single-crystal surface, but they still follow the Nernstian pH dependence. The optimized buffer layer is characterized by a combination of quasi-amorphous morphology (which is responsible for the blocking function) and calcination-induced crystallinity (which leads to fast electron injection and electron transport in the conduction band). The latter manifests itself by a reversible charging of the chemical capacitance of TiO2 in its accumulation state. The capacitive-charging capability and pinhole formation significantly depend on the post-deposition heat treatment.
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Raman spectroscopy and in situ Raman spectroelectrochemistry were applied to study the lithium vapor doping of C70@SWCNTs (peapods). A strong degree of doping was proved by the vanishing of the single walled carbon nanotubes (SWCNT's) radial breathing mode (RBM) and by the attenuation of the tangential (TG) band intensity. In contrast to potassium vapor doping, the strong downshift of the frequency of the TG band has not been observed for Li-doping. The Li vapor treated peapods remained partly doped even if they were exposed to humid air. This has been reflected by a reduced intensity of the nanotube and the fullerene modes and by the change of the shape of the RBM band as compared to that of the undoped sample. The modes of the intratubular fullerene were almost unresolved after the contact of the Li-doped sample with water. A lithium insertion into the interior of a peapod and its strong interaction with the intratubular fullerene is suggested to be responsible for the air-insensitive residual doping. This residual doping was studied by spectroelectrochemical measurements. The TG band of the Li doped peapods is partly upshifted during the anodic doping, which points to the different state of C70@SWCNTs and C60@SWCNTs studied previously.
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Statistical shape modeling (SSM) characterizes anatomical variations in a population of shapes generated from medical images. Statistical analysis of shapes requires consistent shape representation across samples in shape cohort. Establishing this representation entails a processing pipeline that includes anatomy segmentation, image re-sampling, shape-based registration, and non-linear, iterative optimization. These shape representations are then used to extract low-dimensional shape descriptors that are anatomically relevant to facilitate subsequent statistical analyses in different applications. However, the current process of obtaining these shape descriptors from imaging data relies on human and computational resources, requiring domain expertise for segmenting anatomies of interest. Moreover, this same taxing pipeline needs to be repeated to infer shape descriptors for new image data using a pre-trained/existing shape model. Here, we propose DeepSSM, a deep learning-based framework for learning the functional mapping from images to low-dimensional shape descriptors and their associated shape representations, thereby inferring statistical representation of anatomy directly from 3D images. Once trained using an existing shape model, DeepSSM circumvents the heavy and manual pre-processing and segmentation required by classical models and significantly improves the computational time, making it a viable solution for fully end-to-end shape modeling applications. In addition, we introduce a model-based data-augmentation strategy to address data scarcity, a typical scenario in shape modeling applications. Finally, this paper presents and analyzes two different architectural variants of DeepSSM with different loss functions using three medical datasets and their downstream clinical application. Experiments showcase that DeepSSM performs comparably or better to the state-of-the-art SSM both quantitatively and on application-driven downstream tasks. Therefore, DeepSSM aims to provide a comprehensive blueprint for deep learning-based image-to-shape models.
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Aprendizado Profundo , Humanos , Imageamento Tridimensional/métodos , Modelos Estatísticos , Processamento de Imagem Assistida por Computador/métodosRESUMO
We present the first Raman spectroscopic study of Bernal bilayer graphene flakes under uniaxial tension. Apart from a purely mechanical behavior in flake regions where both layers are strained evenly, certain effects stem from inhomogeneous stress distribution across the layers. These phenomena such as the removal of inversion symmetry in bilayer graphene may have important implications in the band gap engineering, providing an alternative route to induce the formation of a band gap.
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Grafite/química , Membranas Artificiais , Fônons , Estrutura Molecular , Polímeros/química , Análise Espectral RamanRESUMO
Titania nanofibers were fabricated using the industrial Nanospider(TM) technology. The preparative protocol was optimized by screening various precursor materials to get pure anatase nanofibers. Composite films were prepared by mixing a commercial paste of nanocrystalline anatase particles with the electrospun nanofibers, which were shortened by milling. The composite films were sensitized by Ru-bipyridine dye (coded C106) and the solar conversion efficiency was tested in a dye-sensitized solar cell filled with iodide-based electrolyte solution (coded Z960). The solar conversion efficiency of a solar cell with the optimized composite electrode (η = 7.53% at AM 1.5 irradiation) outperforms that of a solar cell with pure nanoparticle film (η = 5.44%). Still larger improvement was found for lower light intensities. At 10% sun illumination, the best composite electrode showed η = 7.04%, referenced to that of pure nanoparticle film (η = 4.69%). There are non-monotonic relations between the film's surface area, dye sorption capacity and solar performance of nanofiber-containing composite films, but the beneficial effect of the nanofiber morphology for enhancement of the solar efficiency has been demonstrated.
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2,2'-Dipiridil/análogos & derivados , Corantes/química , Fontes de Energia Elétrica , Nanofibras/química , Compostos Organometálicos/química , Energia Solar , Titânio/química , 2,2'-Dipiridil/química , Eletrodos , Eletrólitos/química , Nanofibras/ultraestrutura , Nanopartículas/química , Polímeros/químicaRESUMO
A novel lithiated high-entropy oxychloride Li0.5(Zn0.25Mg0.25Co0.25Cu0.25)0.5Fe2O3.5Cl0.5 (LiHEOFeCl) with spinel structure belonging to the cubic Fd3Ìm space group is synthesized by a mechanochemical-thermal route. Cyclic voltammetry measurement of the pristine LiHEOFeCl sample confirms its excellent electrochemical stability and the initial charge capacity of 648 mA h g-1. The reduction of LiHEOFeCl starts at ca. 1.5 V vs. Li+/Li, which is outside the electrochemical window of the Li-S batteries (1.7/2.9 V). The addition of the LiHEOFeCl material to the composite of carbon with sulfur results in improved long-term electrochemical cycling stability and increased charge capacity of this cathode material in Li-S batteries. The carbon/LiHEOFeCl/sulfur cathode provides a charge capacity of 530 mA h g-1 after 100 galvanostatic cycles, which represents ca. 33% increase as compared to the charge capacity of the blank carbon/sulfur composite cathode after 100 cycles. This considerable effect of the LiHEOFeCl material is assigned to its excellent structural and electrochemical stability within the potential window of 1.7 V/2.9 V vs. Li+/Li. In this potential region, our LiHEOFeCl has no inherent electrochemical activity. Hence, it acts solely as an electrocatalyst accelerating the redox reactions of polysulfides. This can be beneficial for the performance of Li-S batteries, as evidenced by reference experiments with TiO2 (P90).
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BACKGROUND: Quantifying the severity of head shape deformity and establishing a threshold for operative intervention remains challenging in patients with metopic craniosynostosis (MCS). This study combines three-dimensional skull shape analysis with an unsupervised machine-learning algorithm to generate a quantitative shape severity score (cranial morphology deviation) and provide an operative threshold score. METHODS: Head computed tomography scans from subjects with MCS and normal controls (5 to 15 months of age) were used for objective three-dimensional shape analysis using ShapeWorks software and in a survey for craniofacial surgeons to rate head-shape deformity and report whether they would offer surgical correction based on head shape alone. An unsupervised machine-learning algorithm was developed to quantify the degree of shape abnormality of MCS skulls compared to controls. RESULTS: One hundred twenty-four computed tomography scans were used to develop the model; 50 (24% MCS, 76% controls) were rated by 36 craniofacial surgeons, with an average of 20.8 ratings per skull. The interrater reliability was high (intraclass correlation coefficient, 0.988). The algorithm performed accurately and correlates closely with the surgeons assigned severity ratings (Spearman correlation coefficient, r = 0.817). The median cranial morphology deviation for affected skulls was 155.0 (interquartile range, 136.4 to 194.6; maximum, 231.3). Skulls with ratings of 150.2 or higher were very likely to be offered surgery by the experts in this study. CONCLUSIONS: This study describes a novel metric to quantify the head shape deformity associated with MCS and contextualizes the results using clinical assessments of head shapes by craniofacial experts. This metric may be useful in supporting clinical decision making around operative intervention and in describing outcomes and comparing patient population across centers.
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Craniossinostoses , Aprendizado de Máquina não Supervisionado , Humanos , Lactente , Reprodutibilidade dos Testes , Craniossinostoses/diagnóstico por imagem , Craniossinostoses/cirurgia , Crânio/diagnóstico por imagem , Crânio/cirurgiaRESUMO
The Raman spectra of two-layered graphene on a silicon substrate were studied in the temperature range from 298 to 1073 K in an inert atmosphere. Isotopic engineering was used to fabricate two-layer graphene specimens containing (13)C atoms in the top layer and (12)C atoms in the bottom layer, which allowed the behavior of each particular layer to be distinguished as a function of temperature. It is demonstrated that the top layer exhibits much lower Raman temperature coefficients than the bottom one for both the G and the G' modes. We suggest that the changes in the Raman spectra of graphene observed during thermal cycling are predominantly caused by a superposition of two effects, namely, the mechanical stress in graphene exerted by the substrate and the intrinsic changes in the graphene lattice caused by the temperature itself. The top graphene layer is proposed to be more relaxed than the bottom graphene layer and thus reflects almost exclusively the temperature variations as a freestanding graphene layer would.
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Selected problems of electrochemical synthesis, characterization and applications of titanium dioxide are reviewed. These issues have attracted considerable attention from addressing purely academic questions up to promising applications in devices for energy storage and energy conversion.
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Six representative isotope-labeled samples of titanium dioxide were synthesized: Ti(16)O(2), Ti(17)O(2) and Ti(18)O(2), each in anatase and rutile forms. Their Raman scattering was analyzed at temperatures down to 5 K. Spectral assignment was supported by numerical simulation using DFT calculations. The combination of experimental and theoretical Raman frequencies with the corresponding isotopic shifts allowed us to address various still-open questions about the second-order Raman scattering in rutile, and the analysis of overlapping features in the anatase spectrum.
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Titânio/química , Isótopos de Oxigênio/química , Teoria Quântica , Análise Espectral Raman , TemperaturaRESUMO
Graphene nanoplatelets (GNP) in the form of thin semitransparent films on F-doped SnO2 (FTO) exhibit high electrocatalytic activity for the Co(bpy)3(3+/2+) redox couple in acetonitrile electrolyte solution. The GNP film is superior to the traditional electrocatalyst, that is, platinum, both in charge-transfer resistance (exchange current) and in electrochemical stability under prolonged potential cycling. The good electrochemical performance of GNP is readily applicable for dye-sensitized solar cells with Y123-sensitized TiO2 photoanodes and Co(bpy)3(3+/2+) as the redox shuttle. The dye-sensitized solar cell with GNP cathode is superior to that with the Pt-FTO cathode particularly in fill factor and in power conversion efficiency at higher illumination intensity.