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Two unusual phorbol esters, namely 20-deoxyphorbol-3,4,12-triacetate-13-phenylacetate (1) and phorbol-3,4,12,13-tetraacetate-20-phenylacetate (2) plus ingol-3,8,12-triacetate-7-phenylacetate (3) were isolated from the latex of Euphorbia umbellata and identified by HRESIMS and 2D NMR. Compound 1 is herein described for the first time. Assignment of the phenylacetyl group at C-7 in compound 3 was suggested by the HMBC and NOESY spectra obtained in pyridine-d5. In addition to the latex and its distinct terpenoid fractions, the isolated compounds were tested as latent reversal agents against HIV-1-infected J-Lat cells, with reference to phorbol-12-myristate-13-acetate and ingenol-B. Compound 2 reverted 75-80% the viral latency on the GFP-positive cells, resulting EC50 3.70 µg/mL (SI 6.7), while 1 induced 34-40% reactivation at the same concentration range (4-20 µg/mL). The ingol derivative 3 was ineffective. Phorbol esters were confirmed as effective constituents in the latex since the fraction containing them was 2.4-fold more active than the lyophilised latex at the lowest concentration assayed.

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Three known compounds, 20-deoxyphorbol-5ß-hydroxy-12-tiglate-13-isobutyrate (1), 20-deoxyphorbol-5ß-hydroxy-12-tiglate-13-phenylacetate (2), and 4-deoxy-4ß-phorbol-12-tiglate-13-phenylacetate (3), were reisolated from the latex of Euphorbia umbellata through a bioguided fractionation process to target HIV-1 latency reactivation. The in vitro bioassay using infected T-cell lymphoblasts (J-Lat 10.6), complemented with surface CD4 receptor downregulation assessment, led to isolation of the compounds as a highly active ternary mixture. Effective purification of the individual compounds was achieved by first subjecting a phorbol-enriched fraction (previously prepared from crude latex) to MPLC, followed by semipreparative HPLC and characterization by 1D and 2D NMR spectroscopy and (+)-HRESIMS. Compared with a positive control, the isolated compounds were effective in reactivating 68-75% of the virus latency in the range of 9.7-0.097 µM for compound 1, 8.85-0.088 µM for compound 2, and 9.1-0.091 µM for compound 3, with the latter maintaining steady effectiveness down to a 10-5 dilution. Accordingly, compound 3 may serve as a promising lead compound for the development of anti-HIV drugs based on latency reactivation therapy.

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BACKGROUND: Stevia serrata Cav. (Asteraceae), widely found in Guatemala, is used to treat gastrointestinal problems. The aim of this study was to demonstrate the antinociceptive and anti-inflammatory effects of the essential oil (EO) and the mechanism of action. METHODS: EO was tested in chemical (capsaicin- and glutamate-induced licking response) or thermal (hot plate) models of nociception at 10, 30 or 100 mg/kg doses. The mechanism of action was evaluated using two receptor antagonists (naloxone, atropine) and an enzyme inhibitor (L-NAME). The anti-hyperalgesic effect was evaluated using carrageenan-induced nociception and evaluated in the hot plate. RESULTS: All three doses of EO reduced licking response induced by glutamate, and higher doses reduced capsaicin-induced licking. EO also increased area under the curve, similar to the morphine-treated group. The antinociceptive effect induced by EO was reversed by pretreatment of mice with naloxone (1 mg/kg, ip), atropine (1 mg/kg, ip) or L-NAME (3 mg/kg, ip). EO also demonstrated an anti-hyperalgesic effect. The 100 mg/kg dose increased the latency time, even at 1 h after oral administration and this effect has been maintained until the 96th hour, post-administration. CONCLUSIONS: Our data suggest that essential oil of S. serrata presents an antinociceptive effect mediated, at least in part, through activation of opioid, cholinergic and nitrergic pathways.

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Abstract The aim of this study was to analyse the stability of the breaststroke technique in five elite swimmers in a 200m event using a qualitative analysis. The codification of the behaviour of each swimmer during the execution of 20 cycles was achieved using an ad hoc observational instrument comprised of a system of categories and field formats to detect the behavioural patterns (T-patterns); software was used for identifying the technical behaviour of stable structures. The results showed that the stability behaviour varied depending on the swimmer, as the variations of codes in each round produced distinct configurations to determine the differences between cycles for the same swimmer. It was concluded that the instrument used in this study plays an important role through the existence of stable behaviour in the breaststroke technique. It was also concluded that there are distinct patterns and behaviours between swimmers during each lap of the race.

Resumo O objetivo deste estudo foi analisar a estabilidade da técnica de bruços em cinco nadadores de elite numa prova de 200m usando uma análise qualitativa. A codificação do comportamento de cada nadador durante a execução de vinte ciclos de nado foi alcançado usando um instrumento de observação ad-hoc composto por um sistema de categorias e formatos de campo para detectar os padrões comportamentais (T-patterns); o software foi utilizado para identificar o comportamento técnico de estruturas estáveis. Os resultados indicaram que o comportamento da estabilidade dos nadadores variou de acordo com o nadador, como as variações de códigos em cada ronda produzido configurações distintas para determinar as diferenças entre os ciclos para o mesmo nadador. Concluiu-se que o instrumento utilizado neste estudo desempenha um papel importante, através da existência de um comportamento estável na técnica de nado de peito. Concluiu-se também que existem padrões distintos e comportamentos entre nadadores durante cada percurso de nado.

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In this Letter, we study the structural and electronic properties of single-layer and bilayer phosphorene with graphene. We show that both the properties of graphene and phosphorene are preserved in the composed heterostructure. We also show that via the application of a perpendicular electric field, it is possible to tune the position of the band structure of phosphorene with respect to that of graphene. This leads to control of the Schottky barrier height and doping of phosphorene, which are important features in the design of new devices based on van der Waals heterostructures.

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The main purpose of this study was to follow-up the intra- and inter-individual variability of young swimmers' performance and determinant factors over two competitive seasons. Thirty young swimmers (14 boys: 12.33±0.65 years-old; 16 girls: 11.15±0.55 years-old) were followed-up throughout two consecutive seasons (seven evaluation moments). Performance (100m freestyle), anthropometric, kinematic, hydrodynamic and efficiency features were evaluated. A gender and skill-level effect was observed. Boys improved in a higher amount (%) comparing to girls. Overall, swimmers in skill-level 2 (both genders) presented a higher intra-individual variability. Performance and anthropometrics showed a significant inter-individual variability in most moments, but hydrodynamics, kinematics and efficiency did not. Within each skill-level hydrodynamics, kinematics and efficiency were the variables that showed a high inter-individual variability. As a gender and skill-level effect was noticed in an age-group of young swimmers, coaches and practitioners should put the focus in specific and customized training plans for each skill-level of swimmers...

"Análise longitudinal da variabilidade intra- e inter-individual da performance e fatores determinantes em nadadores jovens." O objetivo principal do estudo foi acompanhar a variabilidade intra- e inter-individual da performance e dos seus fatores determinantes de nadadores jovens durante duas temporadas competitivas. Trinta nadadores jovens (14 nadadores: 12.33±0.65 anos; 16 nadadoras: 11.15±0.55 anos) foram avaliados ao longo das duas épocas (7 momentos de avaliação). Foi avaliada a performance (100m livres), e variáveis antropométricas, cinemáticas, hidrodinâmicas e de eficiência. Foi observado um efeito do sexo e do nível competitivo. Os nadadores melhoraram em maior quantidade (%) do que as nadadoras. Os nadadores no nível competitivo 2 (ambos os sexos) apresentaram uma intra-variabilidade superior. A performance e as variáveis antropométricas apresentaram uma inter-variabilidade significativa na maior parte dos momentos de avaliação, ao contrário das variáveis hidrodinâmicas, cinemáticas e de eficiência. Dentro de cada nível competitivo as variáveis hidrodinâmicas, cinemáticas e de eficiência foram as que apresentaram uma variabilidade inter-individual superior. Como foi verificado um efeito do sexo e do nível competitivo, treinadores e praticantes devem colocar o foco em treinos específicos e personalizados para cada grupo de nadadores de acordo com o nível competitivo...

"Análisis longitudinal de la variabilidade intra- y inter-individual del rendimiento y sus determinantes en nadadores jóvenes." El objetivo principal del estudio fue el seguimiento de la variabilidad intra- e inter-individual del rendimiento y sus factores determinantes de nadadores jóvenes en dos temporadas competitivas. Treinta nadadores jóvenes (14 niños: 12.33±0.65 años; 16 niñas: 11.15±0.55 años) fueron seguidos a lo largo de dos temporadas competitivas (7 momentos de evaluación). Se evaluó el rendimiento (100m estilo libre), e características antropométricas, cinemáticas, hidrodinámicas e la eficiencia. Se observó un efecto del sexo e del nivel de habilidad. Los niños mejoraron en una cantidad superior (%) en comparación con las niñas. En general, los nadadores de nivel de habilidad 2 (los dos sexos) presentaron una mayor variabilidad intra-individual. El rendimiento y la antropometría mostraron una variabilidad inter-individual significativa en la mayoría de los momentos, lo mismo no ocurrió con la hidrodinámica, la cinemática y la eficiencia. Dentro de cada nivel de habilidad, la hidrodinámica, la cinemática y la eficiencia fueron las variables que mostraron una alta variabilidad inter-individual. Como se ha observado un efecto de sexo e nivel de habilidad, entrenadores y practicantes deben poner el foco en los planes de formación específicos y personalizados para cada nivel de habilidad de los nadadores...

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Graphane, hydrogenated graphene, can be patterned into electronic devices by selectively removing hydrogen atoms. The most simple of such devices is the so-called nanoroad, analogous to the graphene nanoribbon, where confinement-and the opening of a gap-is obtained without the need for breaking the carbon bonds. In this work we address the electronic transport properties of such systems considering different hydrogen impurities within the conduction channel. We show, using a combination of density functional theory and non-equilibrium Green's functions, that hydrogen leads to significant changes in the transport properties and in some cases to current polarization.

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Carbon nanotubes have been at the forefront of nanotechnology, leading not only to a better understanding of the basic properties of charge transport in one dimensional materials, but also to the perspective of a variety of possible applications, including highly sensitive sensors. Practical issues, however, have led to the use of bundles of nanotubes in devices, instead of isolated single nanotubes. From a theoretical perspective, the understanding of charge transport in such bundles, and how it is affected by the adsorption of molecules, has been very limited, one of the reasons being the sheer size of the calculations. A frequent option has been the extrapolation of knowledge gained from single tubes to the properties of bundles. In the present work we show that such procedure is not correct, and that there are qualitative differences in the effects caused by molecules on the charge transport in bundles versus isolated nanotubes. Using a combination of density functional theory and recursive Green's function techniques we show that the adsorption of molecules randomly distributed onto the walls of carbon nanotube bundles leads to changes in the charge density and consequently to significant alterations in the conductance even in pristine tubes. We show that this effect is driven by confinement which is not present in isolated nanotubes. Furthermore, a low concentration of dopants randomly adsorbed along a two-hundred nm long bundle drives a change in the transport regime; from ballistic to diffusive, which can account for the high sensitivity to different molecules.

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The respiration of metal oxides by the bacterium Geobacter sulfurreducens requires the assembly of a small peptide (the GS pilin) into conductive filaments termed pili. We gained insights into the contribution of the GS pilin to the pilus conductivity by developing a homology model and performing molecular dynamics simulations of the pilin peptide in vacuo and in solution. The results were consistent with a predominantly helical peptide containing the conserved α-helix region required for pilin assembly but carrying a short carboxy-terminal random-coiled segment rather than the large globular head of other bacterial pilins. The electronic structure of the pilin was also explored from first principles and revealed a biphasic charge distribution along the pilin and a low electronic HOMO-LUMO gap, even in a wet environment. The low electronic band gap was the result of strong electrostatic fields generated by the alignment of the peptide bond dipoles in the pilin's α-helix and by charges from ions in solution and amino acids in the protein. The electronic structure also revealed some level of orbital delocalization in regions of the pilin containing aromatic amino acids and in spatial regions of high resonance where the HOMO and LUMO states are, which could provide an optimal environment for the hopping of electrons under thermal fluctuations. Hence, the structural and electronic features of the pilin revealed in these studies support the notion of a pilin peptide environment optimized for electron conduction.

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BACKGROUND: The association between physical activity and quality of life in stroke survivors has not been analyzed within a framework related to the human development index. This study aimed to identify differences in physical activity level and in the quality of life of stroke survivors in two cities differing in economic aspects of the human development index. METHODS: Two groups of subjects who had suffered a stroke at least a year prior to testing and showed hemiplegia or hemiparesis were studied: a group from Belo Horizonte (BH) with 48 people (51.5 ± 8.7 years) and one from Montes Claros (MC) with 29 subjects (55.4 ± 8.1 years). Subsequently, regardless of location, the groups were divided into Active and Insufficiently Active so their difference in terms of quality of life could be analyzed. RESULTS: There were no significant differences between BH and MCG when it came to four dimensions of physical health that were evaluated (physical functioning, physical aspect, pain and health status) or in the following four dimensions of mental health status (vitality, social aspect, emotional aspect and mental health). However, significantly higher mean values were found in Active when compared with Insufficiently Active individuals in various measures of physical health (physical functioning 56.2 ± 4.4 vs. 47.4 ± 6.9; physical aspect 66.5 ± 6.5 vs. 59.1 ± 6.7; pain 55.9 ± 6.2 vs. 47.7 ± 6.0; health status 67.2 ± 4.2 vs. 56.6 ± 7.8) (arbitrary units), and mental health (vitality 60.9 ± 6.8 vs. 54.1 ± 7.2; social aspect 60.4 ± 7.1 vs. 54.2 ± 7.4; emotional aspect 64.0 ± 5.5 vs. 58.1 ± 6.9; mental health status 66.2 ± 5.5 vs. 58.4 ± 7.5) (arbitrary units). CONCLUSIONS: Despite the difference between the cities concerning HDI values, no significant differences in quality of life were found between BH and MCG. However, the Active group showed significantly better results, confirming the importance of active lifestyle to enhance quality of life in stroke survivors.

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The use of the spin of the electron as the ultimate logic bit-in what has been dubbed spintronics-can lead to a novel way of thinking about information flow. At the same time single-layer graphene has been the subject of intense research due to its potential application in nanoscale electronics. While defects can significantly alter the electronic properties of nanoscopic systems, the lack of control can lead to seemingly deleterious effects arising from the random arrangement of such impurities. Here we demonstrate, using ab initio density functional theory and non-equilibrium Green's functions calculations, that it is possible to obtain perfect spin selectivity in doped graphene nanoribbons to produce a perfect spin filter. We show that initially unpolarized electrons entering the system give rise to 100% polarization of the current due to random disorder. This effect is explained in terms of different localization lengths for each spin channel which leads to a new mechanism for the spin filtering effect that is disorder-driven.

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Here we present a parametrized tight-binding (TB) model to calculate the band structure of single-wall carbon nanotubes (SWNTs). On the basis of ab initio calculations we fit the band structure of nanotubes of different radii with results obtained with an orthogonal TB model to third neighbors, which includes the effects of orbital hybridization by means of a reduced set of parameters. The functional form for the dependence of these parameters on the radius of the tubes can be used to interpolate appropriate TB parameters for different SWNTs and to study the effects of curvature on their electronic properties. Additionally, we have shown that the model gives an appropriate description of the optical spectra of SWNTs, which can be useful for a proper assignation of SWNTs' specific chirality from optical absorption experiments.

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This study examined the association between fat-free mass (FFM) and muscle strength with bone mineral density (BMD), and compared the BMD values between sarcopenic and nonsarcopenic older women. After the exclusion criteria were applied, a total of 246 volunteers (age: 66.51+/-6.37 yr) participated in the analysis. Subjects underwent FFM and BMD evaluation by dual-energy X-ray absorptiometry and quadriceps strength by an isokinetic dynamometer. To address the potential for confounding by height, FFM values were considered relative to body height squared. For fat mass correction, fat-adjusted FFM was calculated. Individuals were classified as sarcopenic if their appendicular FFM was less than 5.45 kg/m2. All the evaluated FFM indexes were significantly correlated with the measured BMD sites. Sarcopenic individuals presented significantly lower whole body and trochanter BMD, and were significantly more prone to have low BMD. Muscle strength was also correlated with BMD sites; however, when it was expressed relative to body weight, the significance disappeared. Nevertheless, volunteers with low relative strength had higher risk of having low trochanter BMD. It can be concluded, in older women, that FFM is significantly correlated with BMD independently of height and fat mass. Muscle strength was also correlated with BMD, although the correlation was weaker when corrected for body weight. Finally, sarcopenic elderly women were more likely to have low BMD and muscle strength.

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The introduction of high-permittivity gate dielectric materials into complementary metal oxide semiconductor technology has reopened the interest in Ge as a channel material mainly due to its high hole mobility. Since HfO(2) and ZrO(2) are two of the most promising dielectric candidates, it is important to investigate if Hf and Zr may diffuse into the Ge channel. Therefore, using ab initio density functional theory calculations, we have studied substitutional and interstitial Hf and Zr impurities in c-Ge,looking for neutral defects. We find that (i) substitutional Zr and Hf defects are energetically more favorable than interstitial defects; (ii) under oxygen-rich conditions, neither Zr nor Hf migration towards the channel is likely to occur; (iii) either under Hf- or Zr-rich conditions it is very likely, particularly for Zr, that defects will be incorporated in the channel.

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The presence of certain kinds of defects at the edges of monohydrogenated zigzag graphene nanoribbons changes dramatically the charge transport properties inducing a spin-polarized conductance. Using an approach based on density functional theory and nonequilibrium Green's function formalism to calculate the transmittance, we classify the defects in different classes depending on their distinct transport properties: (i) sigma-defects, which do not affect the transmittance close to the Fermi energy (EF); and (ii) pi-defects, which cause a spin polarization of the transmittance and that can be further divided into either electron or hole defects if the spin transport polarization results in larger transmittance for the up or down spin channel, respectively.

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The fact that the resistance of propagating electrons in solids depends on their spin orientation has led to a new field called spintronics. With the parallel advances in nanoscience, it is now possible to talk about nanospintronics. Many works have focused on the study of charge transport along nanosystems, such as carbon nanotubes, graphene nanoribbons, or metallic nanowires, and spin dependent transport properties at this scale may lead to new behaviors due to the manipulation of a small number of spins. Metal nanowires have been studied as electric contacts where atomic and molecular insertions can be constructed. Here we describe what might be considered the ultimate spin device, namely, a Au thin nanowire with one Co atom bridging its two sides. We show that this system has strong spin dependent transport properties and that its local symmetry can dramatically change them, leading to a significant spin polarized conductance.

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Using a combination of density functional theory and recursive Green's functions techniques, we present a full description of a large scale sensor, accounting for disorder and different coverages. Here, we use this method to demonstrate the functionality of nitrogen-rich carbon nanotubes as ammonia sensors as an example. We show how the molecules one wishes to detect bind to the most relevant defects on the nanotube, describe how these interactions lead to changes in the electronic transport properties of each isolated defect, and demonstrate that there are significative resistance changes even in the presence of disorder, elucidating how a realistic nanosensor works.

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Several experimental groups have achieved effective n- and p-type doping of silicon nanowires (SiNWs). However, theoretical analyses on ultrathin SiNWs suggest that dopants tend to segregate to their surfaces, where they would combine with defects such as dangling bonds (DB), becoming electronically inactive. Using fully ab initio calculations, we show that the differences in formation energies among surface and core substitutional sites decrease rapidly as the diameters of the wires increase, indicating that the dopants will be uniformly distributed. Moreover, occurrence of the electronically inactive impurity/DB complex rapidly becomes less frequent for NWs of larger diameters. We also show that the high confinement in the ultrathin SiNWs causes the impurity levels to be deeper than in the silicon bulk, but our results indicate that for NWs of diameters larger than approximately 3 nm the impurity levels recover bulk characteristics. Finally, we show that different surfaces will lead to different dopant properties in the gap.

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We investigate, using ab initio molecular dynamics simulations, the effect of temperature on the stability of pure, C and H doped, atomically thin gold nanowires. We show how thermal fluctuations lead to local instabilities that result in the rupture of the nanowires, and how appropriate impurities may help to stabilize these wires. We also show that when light impurity atoms, such as hydrogen, are incorporated in the Au nanowires, quantum effects will affect the nuclear dynamical evolution.

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We report a spin polarized density functional theory study of the electronic and transport properties of graphene nanoribbons doped with boron atoms. We considered hydrogen terminated graphene (nano)ribbons with width up to 3.2 nm. The substitutional boron atoms at the nanoribbon edges (sites of lower energy) suppress the metallic bands near the Fermi level, giving rise to a semiconducting system. These substitutional boron atoms act as scattering centers for the electronic transport along the nanoribbons. We find that the electronic scattering process is spin-anisotropic; namely, the spin-down (up) transmittance channels are weakly (strongly) reduced by the presence of boron atoms. Such anisotropic character can be controlled by the width of the nanoribbon; thus, the spin-up and spin-down transmittance can be tuned along the boron-doped nanoribbons.