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ABSTRACT BACKGROUND: Current research supports the fact that prophylactic ankle taping (AT) is effective in preventing ankle injuries in amateur and elite sports athletes. OBJECTIVE: This study aimed to investigate the effect of AT on balance, knee valgus during drop jump and single-leg countermovement jump (SL-CMJ) landings, and ankle range of motion (ROM) restriction in healthy participants. DESIGN AND SETTING: A cross-sectional observational study was conducted at the Universidad Europea de Madrid, Madrid, Spain. METHODS: Participants: Thirty-nine healthy individuals participated in this study and performed the movements under two conditions (with and without tape). Outcome measurements: ankle ROM, balance, SL-CMJ height, flight time, ground time, and knee valgus. Before any intervention, a random process was developed with a 1:1 allocation ratio, and the participants were assigned to groups A (tape-no tape) and B (no tape-tape). RESULTS: Significant differences between tape and no-tape moments were observed for drop jump knee valgus flexion (P = 0.007), with an increase in knee valgus in participants with ankle taping. Similarly, the Y-balance testshowed a significant decrease in all variables (P = 0.001 and), ankle dorsiflexion (P = 0.001) in participants with ankle taping. CONCLUSIONS: AT is effective for immediate ankle ROM restriction. However, an increase in knee valgus during drop jump task and a decrease in lower limb balance were observed during drop jump task. Based on these results, it can be concluded that AT application in healthy individuals should not be recommended as it results in increase in injury risk factors.
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Given the improvements to network flexibility and programmability, software-defined wireless sensor networks (SDWSNs) have been paired with IEEE 802.15.4e time-slotted channel hopping (TSCH) to increase network efficiency through slicing. Nonetheless, ensuring the quality of service (QoS) level in a scalable SDWSN remains a significant difficulty. To solve this issue, we introduce the application-aware (AA) scheduling approach, which isolates different traffic types and adapts to QoS requirements dynamically. To the best of our knowledge, this approach is the first to support network scalability using shared timeslots without the use of additional hardware while maintaining the application's QoS level. The AA approach is deeply evaluated compared with both the application traffic isolation (ATI) approach and the application's QoS requirements using the IT-SDN framework and by varying the number of nodes up to 225. The evaluation process took into account up to four applications with varying QoS requirements in terms of delivery rate and delay. In comparison with the ATI approach, the proposed approach enhanced the delivery rate by up to 28% and decreased the delay by up to 57%. Furthermore, even with four applications running concurrently, the AA approach proved capable of meeting a 92% delivery rate requirement for up to 225 nodes and a 900 ms delay requirement for up to 144 nodes.
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The triatomic system NeI2 is studied under the consideration that the diatom is found in an excited electronic stateâ (B). The vibrational levels (v=13, , 23) are considered within two well-known theoretical procedures: quasi-classical trajectories (QCT), where the classical equations of motion for nuclei are solved on a single potential energy surface (PES), and the trajectory surface hopping (TSH) method, where the same are solved in a bunch of crossed vibrational PES (diabatic representation). The trajectory surface hopping fewest switches (TSHFS) is implemented to minimize the number of hoppings, thus allowing the calculations of hopping probability between the different PES's, and the kinetic mechanism to track the dissociation path. From these calculations, several observables such as, the lifetimes, vibrational and rotational energies (I2 ), dissociation channels, are obtained. Our results are compared with previous experimental and theoretical work.
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In this work, the electronic transport properties of Te roll-like nanostructures were investigated in a broad temperature range by fabricating single-nanostructure back-gated field-effect-transistors via photolithography. These one-dimensional nanostructures, with a unique roll-like morphology, were produced by a facile synthesis and extensively studied by scanning and transmission electron microscopy. The nanostructures are made of pure and crystalline Tellurium with trigonal structure (t-Te), and exhibit p-type conductivity with enhanced field-effect hole mobility between 273 cm2/Vs at 320 K and 881 cm2/Vs at 5 K. The thermal ionization of shallow acceptors, with small ionization energy between 2 and 4 meV, leads to free-hole conduction at high temperatures. The free-hole mobility follows a negative power-law temperature behavior, with an exponent between -1.28 and -1.42, indicating strong phonon scattering in this temperature range. At lower temperatures, the electronic conduction is dominated by nearest-neighbor hopping (NNH) conduction in the acceptor band, with a small activation energy E NNH ≈ 0.6 meV and an acceptor concentration of N A ≈ 1 × 1016 cm-3. These results demonstrate the enhanced electrical properties of these nanostructures, with a small disorder, and superior quality for nanodevice applications.
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Intermolecular electron-transfer reactions are key processes in physics, chemistry, and biology. The electron-transfer rates depend primarily on the system reorganization energy, that is, the energetic cost to rearrange each reactant and its surrounding environment when a charge is transferred. Despite the evident impact of electron-transfer reactions on charge-carrier hopping, well-controlled electronic transport measurements using monolithically integrated electrochemical devices have not successfully measured the reorganization energies to this date. Here, it is shown that self-rolling nanomembrane devices with strain-engineered mechanical properties, on-a-chip monolithic integration, and multi-environment operation features can overcome this challenge. The ongoing advances in nanomembrane-origami technology allow to manufacture the nCap, a nanocapacitor platform, to perform molecular-level charge transport characterization. Thereby, employing nCap, the copper-phthalocyanine (CuPc) reorganization energy is probed, ≈0.93 eV, from temperature-dependent measurements of CuPc nanometer-thick films. Supporting the experimental findings, density functional theory calculations provide the atomistic picture of the measured CuPc charge-transfer reaction. The experimental strategy demonstrated here is a consistent route towards determining the reorganization energy of a system formed by molecules monolithically integrated into electrochemical nanodevices.
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ElétronsRESUMO
Neuraminidase (NA) of influenza viruses enables the virus to access the cell membrane. It degrades the sialic acid contained in extracellular mucin. Later, it is responsible for releasing newly formed virions from the membrane of infected cells. Both processes become key functions within the viral cycle. Therefore, it is a therapeutic target for research of the new antiviral agents. Structure-activity relationships studies have revealed which are the important functional groups for the receptor-ligand interaction. Influenza virus type A NA activity was inhibited by five scaffolds without structural resemblance to sialic acid. Intending small organic compound repositioning along with drug repurposing, this study combined in silico simulations of ligand docking into the known binding site of NA, along with in vitro bioassays. The five proposed scaffolds are N-acetylphenylalanylmethionine, propanoic 3-[(2,5-dimethylphenyl) carbamoyl]-2-(piperazin-1-yl) acid, 3-(propylaminosulfonyl)-4-chlorobenzoic acid, ascorbic acid (vitamin C), and 4-(dipropylsulfamoyl) benzoic acid (probenecid). Their half maximal inhibitory concentration (IC50) was determined through fluorometry. An acidic reagent 2'-O-(4-methylumbelliferyl)-α-dN-acetylneuraminic acid (MUNANA) was used as substrate for viruses of human influenza H1N1 or avian influenza H5N2. Inhibition was observed in millimolar ranges in a concentration-dependent manner. The IC50 values of the five proposed scaffolds ranged from 6.4 to 73 mM. The values reflect a significant affinity difference with respect to the reference drug zanamivir (p < 0.001). Two compounds (N-acetyl dipeptide and 4-substituted benzoic acid) clearly showed competitive mechanisms, whereas ascorbic acid reflected non-competitive kinetics. The five small organic molecules constitute five different scaffolds with moderate NA affinities. They are proposed as lead compounds for developing new NA inhibitors which are not analogous to sialic acid.
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Inibidores Enzimáticos/química , Vírus da Influenza A Subtipo H1N1/enzimologia , Vírus da Influenza A Subtipo H5N2/enzimologia , Neuraminidase/antagonistas & inibidores , Antivirais/química , Antivirais/metabolismo , Ácido Benzoico/química , Ácido Benzoico/metabolismo , Sítios de Ligação , Ligação Competitiva , Inibidores Enzimáticos/metabolismo , Humanos , Cinética , Ligantes , Simulação de Acoplamento Molecular , Ácido N-Acetilneuramínico/química , Neuraminidase/metabolismo , Relação Estrutura-Atividade , Zanamivir/química , Zanamivir/metabolismoRESUMO
A series of cis-[Ru(LL)(dcbH2)(NCS)2] compounds, where dcbH2 = 2,2'-bipyridine-4,4'-dicarboxylic acid and LL = 1,10-phenanthroline (Ru(phen)), 4,7-dipyrrole-1,10-phenanthroline (Ru(pyr)), 4,7-diindole-1,10-phenanthroline (Ru(ind)), or 4,7-dicarbazole-1,10-phenanthroline (Ru(cbz)), was investigated for application as sensitizers in mesoporous TiO2 dye-sensitized solar cells (DSSCs). A systematic increase in the number of rings of the aromatic substituents at the 4,7-positions of the 1,10-phenanthroline allowed tuning of the molecular size of the sensitizers and the energy stored in the excited state while maintaining the same ground-state Ru3+/2+ reduction potentials. These small structural changes had a significant influence on the rates and/or efficiencies of electron injection, back-electron transfer, recombination to oxidized mediators, lateral self-exchange electron transfer, and regeneration through iodide oxidation that were reflected in distinct photoelectrochemical performance of full operating DSSCs. The global efficiencies, open-circuit voltages, and short-circuit current densities of the DSSCs consistently followed the trend Ru(pyr) < Ru(ind) < Ru(phen) < Ru(cbz), and the most optimal performance of Ru(cbz) was ascribed to dramatically slower recombination to the oxidized redox mediators. Transient photovoltage and transient absorption experiments both revealed significantly slower recombination as the size of the aromatic substituents increased with Ru(cbz) providing the most promising behavior for application in dye sensitization.
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Charge hopping based on Marcus theory is often used to predict charge carrier mobilities in organic crystals, although it is known to systematically underestimate the values. Here we show that this deficiency may lie on a fundamental aspect of quantum statistical averages, rather than on the approximation itself. Under adequate Boltzmann weighing procedure used to evaluate electron and hole transfer integrals, a kinetic Monte Carlo model is employed to describe mobilities in an azacene derivative. The values are in good agreement with experimental data suggesting that the evaluation of transfer integrals may be the weak link in hopping transport models.
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The UV-induced photochemistry of HCFC-132b (CF2 ClCH2 Cl) was investigated by computing excited-state properties with time-dependent density functional theory (TDDFT), multiconfigurational second-order perturbation theory (CASPT2), and coupled cluster with singles, doubles, and perturbative triples (CCSD(T)). Excited states calculated with TDDFT show good agreement with CASPT2 and CCSD(T) results, correctly predicting the main excited-states properties. Simulations of ultrafast nonadiabatic dynamics in the gas phase were performed, taking into account 25 electronic states at TDDFT level starting in two different spectral windows (8.5 ± 0.25 and 10.0 ± 0.25 eV). Experimental data measured at 123.6 nm (10 eV) is in very good agreement with our simulations. The excited-state lifetimes are 106 and 191 fs for the 8.5 and 10.0 eV spectral windows, respectively. Internal conversion to the ground state occurred through several different reaction pathways with different products, where 2Cl, C-Cl bond breakage, and HCl are the main photochemical pathways in the low-excitation region, representing 95% of all processes. On the other hand, HCl, HF, and C-Cl bond breakage are the main reaction pathways in the higher excitation region, with 77% of the total yield. © 2015 Wiley Periodicals, Inc.
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Two secretory phospholipase A2 (sPLA2s) from Glycine max, GmsPLA2-IXA-1 and GmsPLA2-XIB-2, have been purified as recombinant proteins and the activity was evaluated in order to obtain the optimum conditions for catalysis using mixed micelles and lipid monolayers as substrate. Both sPLA2s showed a maximum enzyme activity at pH 7 and a requirement of Ca(2+) in the micromolar range. These parameters were similar to those found for animal sPLA2s but a surprising optimum temperature for catalysis at 60 °C was observed. The effect of negative interfacial charges on the hydrolysis of organized substrates was evaluated through initial rate measurements using short chain phospholipids with different head groups. The enzymes showed subtle differences in the specificity for phospholipids with different head groups (DLPC, DLPG, DLPE, DLPA) in presence or absence of NaCl. Both recombinant enzymes showed lower activity toward anionic phospholipids and a preference for the zwitterionic ones. The values of the apparent kinetic parameters (Vmax and KM) demonstrated that these enzymes have more affinity for phosphatidylcholine compared with phosphatidylglycerol, in contrast with the results observed for pancreatic sPLA2. A hopping mode of catalysis was proposed for the action of these sPLA2 on mixed phospholipid/triton micelles. On the other hand, Langmuir-monolayers assays indicated an optimum lateral surface pressure for activity in between 13 and 16 mN/m for both recombinant enzymes.
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Biocatálise , Membrana Celular/enzimologia , Glycine max/enzimologia , Fosfolipases A2 Secretórias/metabolismo , Ar , Estabilidade Enzimática , Cinética , Fosfolipases A2 Secretórias/química , Especificidade por Substrato , Temperatura , Água/químicaRESUMO
Se presentan los modelos de hopping de rango variable (variable range hopping; VRH), vecinos cercanos (nearest neighbor hopping; NNH) y barreras de potencial presentes en las fronteras de grano; como mecanismos de transporte eléctrico predominantes en los materiales semiconductores para aplicaciones fotovoltaicas. Las medidas de conductividad a oscuras en función de temperatura fueron realizadas para región de bajas temperaturas entre 120 y 400 K con Si y compuestos Cu3BiS2 y Cu2ZnSnSe4. Siguiendo la teoría de percolación, se obtuvieron parámetros hopping y la densidad de estados cerca del nivel de Fermi, N(E F), para todas las muestras. A partir de los planteamientos dados por Mott para VRH, se presentó el modelo difusional, que permitió establecer la relación entre la conductividad y la densidad de estados de defecto o estados localizados en el gap del material. El análisis comparativo entre modelos, evidenció, que es posible obtener mejora hasta de un orden de magnitud en valores para cada uno de los parámetros hopping que caracterizan el material.
Here, we present variable range hopping (VRH) models, nearest neighbor hopping (NNH) and potential barriers present at the grain boundaries, as well as mechanisms of electrical transport predominant in semiconductor materials for photovoltaic applications. We performed dark conductivity measures according to temperature for low temperature regions between 120 and 400 K in Si and Cu3BiS2 and Cu2ZnSnSe4 compounds. Using the percolation theory, we obtained hopping parameters and the density of states near the Fermi, N(E F) level for all samples. Using the approach by Mott for VRH, we obtained the diffusion model, which established the relationship between conductivity and density of defect states or localized gap states of the material. The comparative analysis between models evidenced that it is possible to obtain improvement of an order of magnitude in the values of each of the hopping parameters that characterize the material.
Apresentam-se os modelos de hopping de categoria variável (variable range hopping; VRH), vizinhos próximos (nearest neighbor hopping, NNH) e barreiras de potenciais presentes nas fronteiras de grãos; como mecanismo de transporte elétrico predominantes nos materiais semicondutores para aplicações fotovoltaicas. As medidas de condutividade no escuro em função da temperatura foram realizadas para região de baixas temperaturas entre 120 e 400 K com Si e compostos Cu3BiS2 e Cu2ZnSnSe4. Seguindo a teoria da percolação obtiveram-se parâmetros hopping e a densidade de estados próximos do nível Fermi[BO1] N(E F) para toda a amostra. A partir das abordagens seguidas por Mott para VRH, apresentou-se o modelo de difusão, que permitiu estabelecer a relação entre a condutividade e a densidade de estados de defeito ou estados localizados no gap do material. A análise comparativa dos modelos mostrou que é possível obter melhoria até de uma amplitude de magnitude em valores para cada um dos parâmetros hopping que caracterizam o material.
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Se presentan propiedades eléctricas y de transporte en películas nanocristalinas del compuesto cuaternario Cu2ZnSnSe4 (CZTSe) por método de co-evaporación física. Las muestras fueron crecidas sobre sustratos de vidrio soda-lime y variando en rango los parámetros de síntesis: masa de Cu y temperatura de sustrato. A partir de termopotencia a temperatura ambiente y de transmitancia espectral, se encontró que el material está caracterizado por conductividad tipo n y ancho de banda de energía prohibida de 1.7 eV, respectivamente. Las medias de conductividad eléctrica (región de bajas temperaturas; 90-200 K) mostraron que los procesos de conducción se realizan vía hopping de rango de variable entre estados extendidos. Los parámetros que caracterizaron éste mecanismo, energía de activación (Whopp) y rango hopping (Rhopp), fueron obtenidos mediante teoría de percolación y modelo difusional. Se obtuvo, que para las muestras CZTSe la densidad de estados de defecto cerca del nivel de Fermi del material, N(Ef), está alrededor de 3,403x10(18) cm-3 eV-1. Se presentó correlación entre parámetros de depósito y propiedades eléctricas. Se observó influencia de parámetros sobre formación de fases adicionales en el compuesto.
Here, we present electronic and transport properties of quaternary Cu2ZnSnSe4 (CZTSe) nanocrystalline films fabricated by physical co-evaporation. The samples were grown on soda-lime glass substrates and synthesis parameter ranges, Cu mass and substrate temperature were varied. Using thermopower at room temperature and spectral transmittance we found that the material is characterized by n-type conductivity and forbidden energy bandwidth of 1.7 eV, respectively. Electrical conductivity means (low temperature region; 90-200 K) showed that conductivity processes occur via variable range hopping between extended states. We obtained the parameters characterizing this mechanism, activation energy (Whopp), and range hopping (Rhopp), by employing the percolation theory and diffusion model. The density of defect states near the Fermi level of the material, N (Ef) of the CZTSe samples is about 3,403x10(18) cm-3 eV-1. We found a correlation between deposition parameters and electrical properties and observed a parameter influence on the formation of additional phases in the compound.
Apresentam-se propriedades elétricas e de transporte em películas nano-cristalinas do composto quaternário Cu2ZnSnSe4 (CZTSe) pelo método de co-evaporação física. As amostras foram crescidas sobre substratos de vidro soda-lime e variando a amplitude dos parâmetros de síntese: massa de Cu e temperatura do substrato. A partir de termo-potência a temperatura ambiente e de transmissão espectral, encontrou-se que o material está caracterizado pela condutividade tipo n e largura de banda de energia proibida de 1.7 eV, respetivamente. As medidas de condutividade elétrica (regiões de baixas temperaturas; 90-200 K) mostraram que os processos de condução se realizam via hopping de amplitude variável entre estados estendidos. Os parâmetros que caracterizaram este mecanismo, energia de ativação (Whopp) e amplitude hopping (Rhopp), foram obtidos mediante a teoria de percolação e o modelo de difusão. Obteve-se que, para as amostras CZTSe, a densidade de estados de defeito próximos do nível de Fermi do material, N(EF), está ao redor de, 3,403x10(18) cm-3 eV-1. Apresentou-se correlação entre parâmetros de depósito e propriedades elétricas. Observou-se influencia de parâmetros sobre a formação de fases no composto.