In vitro evaluation of the cis-[Ru(phen)2(pPDIp)]2+⁎⁎ complex for antimicrobial photodynamic therapy against Sporothrix brasiliensis and Candida albicans.

BACKGROUND: Photodynamic therapy (PDT) activates a photosensitizer by visible light to generate cytotoxic oxygen species that lead to cell death. With proper illumination, PDT is often used in applications on superficial and sub-surface lesions. Sporotrichosis infection occurs by Sporothrix fungi which causes a skin wound, worsened by Candida albicans infections. This study investigated the photosensitizing efficiency of the Ru(phen)2(pPDIp)(PF6)2 complex, RupPDIp, against S. brasiliensis and C. albicans. MATERIAL AND METHODS: RupPDIp efficiency against these fungi was tested using 450 nm (blue light and 36 J/cm2) and 525 nm (green light, 25.2 J/cm2) at 0.05-20 µM concentrations. To ensure PDT effectiveness, control groups were tested in the absence and in the presence of RupPDIp under light irradiation and in the dark. RESULTS: RupPDIp eliminated both fungi at ≤5.0 µM. Green light showed the best results, eliminating S. brasiliensis and C. albicans colonies at RupPDIp 0.5 µM and 0.05 µM, respectively. CONCLUSION: RupPDIp is a promising photosensitizer in aPDT, eliminating 106 CFU/mL of both fungi at 450 nm and 525 nm, with lower light doses and concentrations when treated with the green light compared to the blue light.

Identifying and managing patient–ventilator asynchrony: An international survey / Identificación y manejo de la asincronía paciente-ventilador: encuesta internacional

Objective To describe the main factors associated with proper recognition and management of patient–ventilator asynchrony (PVA). Design An analytical cross-sectional study was carried out. Setting An international study conducted in 20 countries through an online survey. Participants Physicians, respiratory therapists, nurses and physiotherapists currently working in the Intensive Care Unit (ICU). Main variables of interest Univariate and multivariate logistic regression models were used to establish associations between all variables (profession, training in mechanical ventilation, type of training program, years of experience and ICU characteristics) and the ability of HCPs to correctly identify and manage 6 PVA. Results A total of 431 healthcare professionals answered a validated survey. The main factors associated to proper recognition of PVA were: specific training program in mechanical ventilation (MV) (OR 2.27; 95%CI 1.14–4.52; p=0.019), courses with more than 100h completed (OR 2.28; 95%CI 1.29–4.03; p=0.005), and the number of ICU beds (OR 1.037; 95%CI 1.01–1.06; p=0.005). The main factor influencing the management of PVA was the correct recognition of 6 PVAs (OR 118.98; 95%CI 35.25–401.58; p<0.001). Conclusion Identifying and managing PVA using ventilator waveform analysis is influenced by many factors, including specific training programs in MV, the number of ICU beds, and the number of recognized PVAs. (AU)

Objetivo Describir los factores asociados al correcto reconocimiento y manejo de la asincronía paciente-ventilador (APV). Diseño Estudio analítico transversal. Ámbito Estudio internacional realizado en 20 países mediante una encuesta a través de Internet. Participantes Médicos, terapeutas respiratorios, enfermeras/os y fisioterapeutas que trabajan actualmente en unidades de cuidados intensivos (UCI). Principales variables de interés Se utilizó un análisis uni y multivariado para describir la asociación entre todas las variables (profesión, formación en ventilación mecánica, tipo de programa de formación, años de experiencia y características de la UCI en la cual trabajan los profesionales) con la correcta identificación y manejo de 6 APV. Resultados Un total de 431 profesionales respondieron una encuesta validada previamente. Los factores asociados a una correcta identificación de 6 APV fueron: haber completado un programa de formación específico sobre ventilación mecánica (OR: 2,27; IC 95%: 1,14-4,52; p=0,019), programa de formación con más de 100h (OR: 2,28; IC 95%: 1,29-4,03; p=0,005) y el número de camas de UCI (OR: 1,037; IC 95%: 1,01-1,06; p=0,005). El principal factor asociado a un adecuado manejo de la APV fue la correcta identificación de 6 APV (OR: 118,98; IC 95%: 35,25-401,58; p<0,001). Conclusiones La identificación y el manejo de la asincronía paciente-ventilador, mediante el análisis de las curvas del ventilador está influenciada por programas de formación, específicos sobre ventilación mecánica, el número de camas de la UCI y el número de asincronías identificadas. (AU)

Identifying and managing patient-ventilator asynchrony: An international survey.

OBJECTIVE: To describe the main factors associated with proper recognition and management of patient-ventilator asynchrony (PVA). DESIGN: An analytical cross-sectional study was carried out. SETTING: An international study conducted in 20 countries through an online survey. PARTICIPANTS: Physicians, respiratory therapists, nurses and physiotherapists currently working in the Intensive Care Unit (ICU). MAIN VARIABLES OF INTEREST: Univariate and multivariate logistic regression models were used to establish associations between all variables (profession, training in mechanical ventilation, type of training program, years of experience and ICU characteristics) and the ability of HCPs to correctly identify and manage 6 PVA. RESULTS: A total of 431 healthcare professionals answered a validated survey. The main factors associated to proper recognition of PVA were: specific training program in mechanical ventilation (MV) (OR 2.27; 95%CI 1.14-4.52; p=0.019), courses with more than 100h completed (OR 2.28; 95%CI 1.29-4.03; p=0.005), and the number of ICU beds (OR 1.037; 95%CI 1.01-1.06; p=0.005). The main factor influencing the management of PVA was the correct recognition of 6 PVAs (OR 118.98; 95%CI 35.25-401.58; p<0.001). CONCLUSION: Identifying and managing PVA using ventilator waveform analysis is influenced by many factors, including specific training programs in MV, the number of ICU beds, and the number of recognized PVAs.

Immunophenotyping, plasticity tests and nanotagging of stem cells derived from adipose tissue of wild rodent agouti (Dasyprocta prymnolopha) / Imunofenotipagem, testes de plasticidade e marcação com nanocristais de céluas-tronco derivadas de tecido adiposo em cutias

There is a growing interest in the study of unspecialized mesenchymal stem cells, for there are still some discussions about their in vitro behavior. Regenerative medicine is a science undergoing improvement which develops treatments as cell therapy using somatic stem cells. In several studies, adipose tissue is presented as a source of multipotent adult cells that has several advantages over other tissue sources. This study aimed to characterize and evaluate the tagging of mesenchymal stem cells from the agoutis adipose tissue (Dasyprocta prymonolopha), with fluorescent intracytoplasmic nanocrystals. Fibroblast cells were observed, plastic adherent, with extended self-renewal, ability to form colonies, multipotency by differentiation into three lineages, population CD90 + and CD45 - expression, which issued high red fluorescence after the tagging with fluorescent nanocrystals by different paths and cryopreserved for future use. It is possible to conclude that mesenchymal stem cells from agouti adipose tissue have biological characteristics and in vitro behavior that demonstrate its potential for use in clinical tests.(AU)

Há um interesse crescente no estudo das células estaminais mesenquimais, não especializadas, pois ainda existem algumas discussões sobre seu comportamento in vitro. A medicina regenerativa é uma ciência em fase de crescimento que desenvolve tratamentos como terapia celular utilizando células estaminais somáticas. Em vários estudos, o tecido adiposo é apresentado como uma fonte de células adultas multipotentes que tem várias vantagens em relação a outras fontes de tecido. Este estudo teve como objetivo caracterizar e avaliar a marcação de células estaminais mesenquimais do tecido adiposo de cutias (Dasyprocta prymnolopha) com nanocristais intracitoplasmáticos fluorescentes. Observaram-se células fibroblásticas, aderentes ao plástico, com autorrenovação prolongada, capacidade de formar colônias, diferenciação em três linhagens, população CD90 + e expressão CD45, que emitiram alta fluorescência vermelha após a marcação com nanocristais fluorescentes por diferentes vias, e criopreservadas para uso futuro. É possível concluir que as células estaminais mesenquimais do tecido adiposo de cutias têm características biológicas e comportamentos in vitro que demonstram seu potencial para uso em testes clínicos.(AU)

Spin-orbit coupling prevents spin channel suppression of transition metal atoms on armchair graphene nanoribbons.

We investigate the spin-dependent electronic and transport properties of armchair graphene nanoribbons including spin-orbit coupling due to the presence of nickel and iridium adatoms by using ab initio calculations within the spin-polarized density functional theory and non-equilibrium Green's function formalism. Our results indicate that the intensity of the spin-flip precession is a direct consequence of the relaxed adsorption sites of the adatoms. We point out that d orbitals of Ni and Ir result in strong dependence on the spin-conserved and spin-flip transmission probabilities. In particular, we show that the presence of spin-orbit coupling can lead to an enhancement of the transmission probabilities especially around resonances arising due to weak coupling with specific orbitals.

Finite-size correction scheme for supercell calculations in Dirac-point two-dimensional materials.

Modern electronic structure calculations are predominantly implemented within the super cell representation in which unit cells are periodically arranged in space. Even in the case of non-crystalline materials, defect-embedded unit cells are commonly used to describe doped structures. However, this type of computation becomes prohibitively demanding when convergence rates are sufficiently slow and may require calculations with very large unit cells. Here we show that a hitherto unexplored feature displayed by several 2D materials may be used to achieve convergence in formation- and adsorption-energy calculations with relatively small unit-cell sizes. The generality of our method is illustrated with Density Functional Theory calculations for different 2D hosts doped with different impurities, all of which providing accuracy levels that would otherwise require enormously large unit cells. This approach provides an efficient route to calculating the physical properties of 2D systems in general but is particularly suitable for Dirac-point materials doped with impurities that break their sublattice symmetry.

Drought promotes increases in total mercury and methylmercury concentrations in fish from the lower Paraíba do Sul river, southeastern Brazil.

Bioaccumulation of mercury and methylmercury in fish represents a serious risk to human beings. Extreme climate events like droughts may increase the trophic transfer of contaminants and net methylation of mercury. The present study assessed the influence of the 2014 drought on total mercury and methylmercury levels in fish from the lower Paraiba do Sul river basin. Contaminant levels were compared for Pimelodus fur, Pachyurus adspersus, Pimelodella lateristriga, Oligosarcus hepsetus, and Crenicichla lacustris captured in five sites in 2013 (N = 212) and 2014 (N = 231). The results indicate that levels of contaminants were higher during the drought in most species. Rainfall was weakly and negatively correlated with total mercury levels in most of the species. The weak relationship between these two variables was due to the indirect influence of rainfall on mercury bioaccumulation. In summary, drought increased the levels of two contaminants in fish.

Early mobilization: Why, what for and how?

Early mobilization strategies in the intensive care unit may result in the prevention and reduction of polyneuromyopathy in the critical patient, improved quality of life, shortened ICU and hospital stay, and lesser mortality during hospitalization. However, it is well known that factors such as the protocol used, the population included in the studies, the timing of the strategy, the severity of the patients and different barriers directly influence the outcomes. This study examines the main protocols described in the literature and their associated results. The main techniques used were kinesitherapy, transfer and locomotion training, as well as neuromuscular electrical stimulation and cycle ergometry. Although two trials and a meta-analysis found no positive results with mobilization, programs that focus on specific populations, such as patients with weakness due to immobility and with preserved neuromuscular excitability can derive more positive effects from such treatment.

Two-dimensional exciton properties in monolayer semiconducting phosphorus allotropes.

Excitons play a key role in technological applications since they have a strong influence on determining the efficiency of photovoltaic devices. Recently, it has been shown that the allotropes of phosphorus possess an optical band gap that can be tuned over a wide range of values including the near-infrared and visible spectra, which would make them promising candidates for optoelectronic applications. In this work we carry out ab initio many-body perturbation theory calculations to study the excitonic effects on the optical properties of two-dimensional phosphorus allotropes: the case of blue and black monolayers. We elucidate the most relevant optical transitions, exciton binding energy spectrum as well as real-space exciton distribution, particularly focusing on the absorption spectrum dependence on the incident light polarization. In addition, based on our results, we use a set of effective hydrogenic models, in which the electron-hole Coulomb interaction is included to estimate exciton binding energies and radii. Our results show an excellent agreement between the many-body methodology and the effective models.

Edge phonons in black phosphorus.

Black phosphorus has recently emerged as a new layered crystal that, due to its peculiar and anisotropic crystalline and electronic band structures, may have important applications in electronics, optoelectronics and photonics. Despite the fact that the edges of layered crystals host a range of singular properties whose characterization and exploitation are of utmost importance for device development, the edges of black phosphorus remain poorly characterized. In this work, the atomic structure and behaviour of phonons near different black phosphorus edges are experimentally and theoretically studied using Raman spectroscopy and density functional theory calculations. Polarized Raman results show the appearance of new modes at the edges of the sample, and their spectra depend on the atomic structure of the edges (zigzag or armchair). Theoretical simulations confirm that the new modes are due to edge phonon states that are forbidden in the bulk, and originated from the lattice termination rearrangements.

Charge storage in oxygen deficient phases of TiO2: defect Physics without defects.

Defects in semiconductors can exhibit multiple charge states, which can be used for charge storage applications. Here we consider such charge storage in a series of oxygen deficient phases of TiO2, known as Magnéli phases. These Magnéli phases (TinO2n-1) present well-defined crystalline structures, i.e., their deviation from stoichiometry is accommodated by changes in space group as opposed to point defects. We show that these phases exhibit intermediate bands with an electronic quadruple donor transitions akin to interstitial Ti defect levels in rutile TiO2. Thus, the Magnéli phases behave as if they contained a very large pseudo-defect density: ½ per formula unit TinO2n-1. Depending on the Fermi Energy the whole material will become charged. These crystals are natural charge storage materials with a storage capacity that rivals the best known supercapacitors.

Anomalous Temperature Dependence of the Band Gap in Black Phosphorus.

Black phosphorus (BP) has gained renewed attention due to its singular anisotropic electronic and optical properties that might be exploited for a wide range of technological applications. In this respect, the thermal properties are particularly important both to predict its room temperature operation and to determine its thermoelectric potential. From this point of view, one of the most spectacular and poorly understood phenomena is indeed the BP temperature-induced band gap opening; when temperature is increased, the fundamental band gap increases instead of decreases. This anomalous thermal dependence has also been observed recently in its monolayer counterpart. In this work, based on ab initio calculations, we present an explanation for this long known and yet not fully explained effect. We show that it arises from a combination of harmonic and lattice thermal expansion contributions, which are in fact highly interwined. We clearly narrow down the mechanisms that cause this gap opening by identifying the peculiar atomic vibrations that drive the anomaly. The final picture we give explains both the BP anomalous band gap opening and the frequency increase with increasing volume (tension effect).

Multifunctional biosensors based on peptide-polyelectrolyte conjugates.

A novel enzymatic platform for the sensing of H2O2 and glucose that uses L,L-diphenylalanine micro/nanostructures (FF-MNSs) as an enzyme support is shown. This platform is obtained by the self-assembly of poly(allylamine hydrochloride) (PAH), FF-MNSs, and microperoxidase-11 (MP11) anchored onto the peptide matrix, in two different crystal structures of FF-MNSs: hexagonal (P61) and orthorhombic (P22121). The electroactive area of the electrodes increases in the presence of FF-MNSs. We also demonstrate via theoretical calculations that the valence band energy of the orthorhombic structure allows it to be doped, similarly to p-type semiconductors, where PAH acts as a doping agent for the orthorhombic peptide structure, decreasing the band-gap by around 1 eV, which results in a smaller charge transfer resistance. These results are consistent with electrochemical impedance spectroscopy measurements, which further elucidate the role of the band structure of the orthorhombic FF-MNSs in the conductivity and electron transfer rates of the hybrid material. An effective communication between the electrode and the active site of a glucose oxidase enzyme through MP11-protein complexes occurs, paving the way for FF-MNSs in the orthorhombic phase for the future development of bioelectronics sensing devices.

Optical spectrum of bottom-up graphene nanoribbons: towards efficient atom-thick excitonic solar cells.

Recently, atomically well-defined cove-shaped graphene nanoribbons have been obtained using bottom-up synthesis. These nanoribbons have an optical gap in the visible range of the spectrum which make them candidates for donor materials in photovoltaic devices. From the atomistic point of view, their electronic and optical properties are not clearly understood. Therefore, in this work we carry out ab-initio density functional theory calculations combine with many-body perturbation formalism to study their electronic and optical properties. Through the comparison with experimental measurements, we show that an accurate description of the nanoribbon's optical properties requires the inclusion of electron-hole correlation effects. The energy, binding energy and the corresponding excitonic transitions involved are analyzed. We found that in contrast to zigzag graphene nanoribbons, the excitonic peaks in the absorption spectrum are a consequence of a group of transitions involving the first and second conduction and valence bands. Finally, we estimate some relevant optical properties that strengthen the potential of these nanoribbons for acting as a donor materials in photovoltaic.

Electronic transport in patterned graphene nanoroads.

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.

Intrinsic stability of the smallest possible silver nanotube.

Recently, Lagos et al. [Nature Nanotech. 4, 149 (2009)] reported the discovery of the smallest possible Ag nanotube with a square cross section. Ab initio density functional theory calculations strongly support that the stability of these hollow structures is structurally intrinsic and not the result of contamination by light atoms. We also report the first experimental observation of the theoretically predicted corrugation of the hollow structure. Quantum conductance calculations predict a unique signature of 3.6 G0 for this new family of nanotubes.

Disorder-based graphene spintronics.

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.

Designing real nanotube-based gas sensors.

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.

Effect of the continuity of the pi conjugation on the conductance of ruthenium-octene-ruthenium molecular junctions.

The conductance of a family of ruthenium-octene-ruthenium molecular junctions with different pi conjugation are investigated using a fully self-consistent ab initio approach which combines the nonequilibrium Green's function formalism with density functional theory. Our calculations demonstrate that the continuity of the pi conjugation in the contact region as well as along the molecular backbone affects the junction conductance significantly, showing the advantage of using the ruthenium-carbon double bond as the linkage of conjugated organic molecules.

Modeling the effect of dispersed doping agents in carbon nanotubes.

Theoretical studies of how the electronic properties of a nanotube are affected by one isolated doping agent is commonly done by ab-initio electronic structure calculations. Although these calculations are essential to understand how the system responds to doping, they are by no means sufficient, since, in reality, a large disordered array of doping agents must be considered. It is then necessary to combine ab-initio techniques with less-computationally-demanding methods if one wishes to describe the real effect of doping on the electronic properties of nanotubes. Here we propose a method that makes use of ab-initio results for single impurities as an input to generate the parameters of the less-demanding tight-binding technique. The method is based on suitable sum rules for the Green functions of the impurity-free nanotubes and does not rely on any fitting scheme. The resulting parametrization allows us to describe disordered systems without losing the important contributions due to charge transfer and screening. Transport properties are subsequentially investigated.