Quasiparticle interfacial level alignment of highly hybridized frontier levels: H2_2O on TiO2_2(110)

Knowledge of the frontier levels' alignment prior to photo-irradiation is necessary to achieve a complete quantitative description of H$_2$O photocatalysis on TiO$_2$(110). Although H$_2$O on rutile TiO$_2$(110) has been thoroughly studied both experimentally and theoretically, a quantitative value for the energy of the highest H$_2$O occupied levels is still lacking. For experiment, this is due to the H$_2$O levels being obscured by hybridization with TiO$_2$(110) levels in the difference spectra obtained via ultraviolet photoemission spectroscopy (UPS). For theory, this is due to inherent difficulties in properly describing many-body effects at the H$_2$O-TiO$_2$(110) interface. Using the projected density of states (DOS) from state-of-the-art quasiparticle (QP) $G_0W_0$, we disentangle the adsorbate and surface contributions to the complex UPS spectra of H$_2$O on TiO$_2$(110). We perform this separation as a function of H$_2$O coverage and dissociation on stoichiometric and reduced surfaces. Due to hybridization with the TiO$_2$(110) surface, the H$_2$O 3a$_1$ and 1b$_1$ levels are broadened into several peaks between 5 and 1 eV below the TiO$_2$(110) valence band maximum (VBM). These peaks have both intermolecular and interfacial bonding and antibonding character. We find the highest occupied levels of H$_2$O adsorbed intact and dissociated on stoichiometric TiO$_2$(110) are 1.1 and 0.9 eV below the VBM. We also find a similar energy of 1.1 eV for the highest occupied levels of H$_2$O when adsorbed dissociatively on a bridging O vacancy of the reduced surface. In both cases, these energies are significantly higher (by 0.6 to 2.6 eV) than those estimated from UPS difference spectra, which are inconclusive in this energy region. Finally, we apply self-consistent QP$GW$ (scQP$GW$1) to obtain the ionization potential of the H$_2$O-TiO$_2$(110) interface.Comment: 12 pages, 12 figures, 1 tabl

Methanol Oxidation on Model Elemental and Bimetallic Transition Metal Surfaces

Direct methanol fuel cells are a key enabling technology for clean energy conversion. Using density functional theory calculations, we study the methanol oxidation reaction on model electrodes. We discuss trends in reactivity for a set of monometallic and bimetallic transition metal surfaces, flat and stepped, which includes platinum-based alloys with ruthenium, tin, and copper, as well as nonprecious alloys, overlayer structures, and modified edges. A common lower bound on the overpotential is estimated (ca. 0.3 V). A model for bifunctional alloys is employed to investigate the nature of the active sites on the surface and to screen for novel bimetallic surfaces of enhanced activity. We suggest platinum copper surfaces as promising anode catalysts for direct methanol fuel cells

Treatment of knee osteoarthritis with pulsed electromagnetic fields: a randomized, double-blind, placebo-controlled study

SummaryObjectiveThe investigation aimed at determining the effectiveness of pulsed electromagnetic fields (PEMF) in the treatment of osteoarthritis (OA) of the knee by conducting a randomized, double-blind, placebo-controlled clinical trial.DesignThe trial consisted of 2h daily treatment 5 days per week for 6 weeks in 83 patients with knee OA. Patient evaluations were done at baseline and after 2 and 6 weeks of treatment. A follow-up evaluation was done 6 weeks after treatment. Activities of daily living (ADL), pain and stiffness were evaluated using the Western Ontario and McMaster Universities (WOMAC) questionnaire.ResultsWithin group analysis revealed a significant improvement in ADL, stiffness and pain in the PEMF-treated group at all evaluations. In the control group there was no effect on ADL after 2 weeks and a weak significance was seen after 6 and 12 weeks. Significant effects were seen on pain at all evaluations and on stiffness after 6 and 12 weeks. Between group analysis did not reveal significant improvements over time. Analysis of ADL score for the PEMF-treated group revealed a significant correlation between less improvement and increasing age. Analysis of patients <65 years using between group analysis revealed a significant improvement for stiffness on treated knee after 2 weeks, but this effect was not observed for ADL and pain.ConclusionsApplying between group analysis we were unable to demonstrate a beneficial symptomatic effect of PEMF in the treatment of knee OA in all patients. However, in patients <65 years of age there is significant and beneficial effect of treatment related to stiffness

Replication Data for: Machine Learning Prediction of H Adsorption Energies on Ag Alloys

The data underlying this published work have been made publicly available in this repository as part of the IMASC Data Management Plan. This work was supported as part of the Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC), an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0012573

Infant motor scale of alberta : validation for a population of Southern Brazil

RESUMOObjetivo: Traduzir, adaptar e verificar a validade de critérios motor e de constructo (consistência interna, validade discriminante, correlação com outros testes e validade preditiva) da versão em Português da Alberta Motor Infant Scale. Métodos: Estudo de validação transcultural. Participaram 21 profissionais e 561 crianças do Rio Grande do Sul, com idades de zero a 18 meses (291 meninos). Foram utilizados os instrumentos: Alberta Infant Motor Scale, Escala do Desenvolvimento do Comportamento da Criança e um questionário para controle de variáveis. O estudo compreendeu as fases de tradução e adaptação da escala; análise da validade de conteúdo; treinamento de profissionais; coleta de dados no ambiente familiar e em creches; análise da objetividade e fidedignidade, e validade de critério e construto. Resultados: A versão portuguesa da Alberta Infant Motor Scale continha critérios motores claros e pertinentes; apresentou ótima confiabilidade (escore total, p=0,88; prono, p=0,86; supino, p=0,89; sentado, p=0,80 e em pé, p=0,85) e poder discriminativo (desenvolvimento típico versus atípico; escore, p<0,001; percentil, p=0,04; critério de classificação, qui-quadrado: p=0,047). Demonstrou correlação moderada com a Escala do Desenvolvimento do Comportamento da Criança (rho=0,342; p=0,03), sendo que a prova de McNemar-Bowker demonstrou diferenças entre os dois métodos (p=0,047). Foi ainda observada estabilidade temporal da escala (p=0,07; rho=0,85, p<0,001) e poder preditivo (p<0,001). Conclusões: A versão em português da Alberta Infant Motor Scale demonstrou ser válida e fidedigna na avaliação das aquisições motoras de crianças brasileiras, o que a torna um instrumento útil a várias áreas da pesquisa científica e da clínica.Objective: To translate, adapt and verify the validity of the motor criteria and the construct (internal consistence, discriminatory validity, correlation with other tests and predicted validity) of the Portuguese version of the Alberta Motor Infant Scale. Methods: Cross-cultural validation study that enrolled 21 professionals and 561 children from the South of Brazil aged zero to 18 months (291 boys). The Alberta Infant Motor Scale, the Developmental Scale of Child Behavior and a questionnaire to control variables were used. Alberta Infant Motor Scale was translated, adapted and the content validity was analyzed. Professionals were then trained and the data were collected in daycares and participants’ home. Scale’s objectivity, reliability, criterion and construct were analyzed. Results: The Portuguese version of Alberta Infant Motor Scale contained clear and pertinent motor criteria; it was reliable (total score, p=0.88; prone, p=0.86; supine, p=0.89; sitting, p=0.80 and standing, p=0.85), it had discriminative power (typical versus atypical development; score, p<0.001; percentile, p=0.04; classification criteria, chi-square: p=0.047) and, also showed temporal stability (p=0.07; rho=0.85; p<0.001) and predictive power (p<0.001). The scale was moderately correlated with the Developmental Scale of Child Behavior (rho=0.342; p=0.03), considering that the McNemar-Bowker proof showed differences between both methods (p=0.047). Conclusions: The Portuguese version of Alberta Infant Motor Scale showed validity and reliability. It is a suitable tool for the assessment of motor acquisitions of Brazilian children, being valuable for researchers and practitioners