Hysteresis in phase volumes, compositions and interfacial roughness in model OPV-small-molecule/polymer thin-films.

Domain morphology and composition, and the structure of interfaces between domains are key factors in the performance and stability of organic photovoltaics (OPVs) fabricated from polymer/small-molecule blends. In this study, we investigate the evolution of composition, phase-volume and interfacial roughness in model polymer/small-molecule bilayers, in response to thermal annealing. Polystyrene/fullerene mixing is studied as a function of annealing temperature, using in situ neutron reflectivity, in thin-film bilayer samples comprising pure component or mixed layers. Remarkably, we discover that thermal annealing at temperatures around or above the reported glass transition temperatures, Tg, of the components can result in extensive mass-transfer between layers, that has the superficial appearance of equilibration, but leaves the layer compositions, thicknesses, and/or the interfacial composition profile in a non-equilibrium state. This is not merely a case of slow kinetics near Tg, as subsequent heating to higher temperatures, followed by cooling, reveals pronounced hysteresis in these systems. This has important implications for the measurement of equilibrium compositions in polymer/small-molecule mixtures for OPV applications, and for device stability during operation.

Effects of calcium ammonium nitrate fed to dairy cows on nutrient intake and digestibility, milk quality, microbial protein synthesis, and ruminal fermentation parameters.

We evaluated the effects of supplemental calcium ammonium nitrate (CAN) fed to dairy cows on dry matter (DM) intake, nutrient digestibility, milk quality, microbial protein synthesis, and ruminal fermentation. Six multiparous Holstein cows at 106 ± 14.8 d in milk, with 551 ± 21.8 kg of body weight were used in a replicated 3 × 3 Latin square design. Experimental period lasted 21 d, with 14 d for an adaptation phase and 7 d for sampling and data collection. Cows were randomly assigned to receive the following treatments: URE, 12 g of urea/kg of DM as a control group; CAN15, 15 g of CAN/kg of DM; and CAN30, 30 g of CAN/kg of DM. Supplemental CAN reduced DM intake (URE 19.0 vs. CAN15 18.9 vs. CAN30 16.5 kg/d). No treatment effects were observed for apparent digestibility of DM, organic matter, crude protein, ether extract, and neutral detergent fiber; however, CAN supplementation linearly increased nonfiber carbohydrate digestibility. Milk yield was not affected by treatments (average = 23.1 kg/d), whereas energy-corrected milk (ECM) and 3.5% fat-corrected milk (FCM) decreased as the levels of CAN increased. Nitrate residue in milk increased linearly (URE 0.30 vs. CAN15 0.33 vs. CAN30 0.38 mg/L); however, treatments did not affect nitrite concentration (average: 0.042 mg/L). Milk fat concentration was decreased (URE 3.39 vs. CAN15 3.35 vs. CAN30 2.94%), and the proportion of saturated fatty acids was suppressed by CAN supplementation. No treatment effects were observed on the reducing power and thiobarbituric acid reactive substances of milk, whereas conjugated dienes increased linearly (URE 47.6 vs. CAN15 52.7 vs. CAN30 63.4 mmol/g of fat) with CAN supplementation. Treatments had no effect on microbial protein synthesis; however, molar proportion of ruminal acetate and acetate-to-propionate ratio increased with CAN supplementation. Based on the results observed, supplementing CAN at 30 g/kg of DM should not be recommended as an optimal dose because it lowered DM intake along with ECM and 3.5% FCM, although no major changes were observed on milk quality and ruminal fermentation.

Rapid encoding of musical tones discovered in whole-brain connectivity.

Information encoding has received a wide neuroscientific attention, but the underlying rapid spatiotemporal brain dynamics remain largely unknown. Here, we investigated the rapid brain mechanisms for encoding of sounds forming a complex temporal sequence. Specifically, we used magnetoencephalography (MEG) to record the brain activity of 68 participants while they listened to a highly structured musical prelude. Functional connectivity analyses performed using phase synchronisation and graph theoretical measures showed a large network of brain areas recruited during encoding of sounds, comprising primary and secondary auditory cortices, frontal operculum, insula, hippocampus and basal ganglia. Moreover, our results highlighted the rapid transition of brain activity from primary auditory cortex to higher order association areas including insula and superior temporal pole within a whole-brain network, occurring during the first 220 ms of the encoding process. Further, we discovered that individual differences along cognitive abilities and musicianship modulated the degree centrality of the brain areas implicated in the encoding process. Indeed, participants with higher musical expertise presented a stronger centrality of superior temporal gyrus and insula, while individuals with high working memory abilities showed a stronger centrality of frontal operculum. In conclusion, our study revealed the rapid unfolding of brain network dynamics responsible for the encoding of sounds and their relationship with individual differences, showing a complex picture which extends beyond the well-known involvement of auditory areas. Indeed, our results expanded our understanding of the general mechanisms underlying auditory pattern encoding in the human brain.

Microfluidic solvent extraction of poly(vinyl alcohol) droplets: effect of polymer structure on particle and capsule formation.

We investigate the formation of poly(vinyl alcohol) microparticles by the selective extraction of aqueous polymer solution droplets, templated by microfluidics and subsequently immersed in a non-solvent bath. The role of polymer molecular mass (18-105 kg mol-1), degree of hydrolysis (88-99%) and thus solubility, and initial solution concentration (0.01-10% w/w) are quantified. Monodisperse droplets with radii ranging from 50 to 500 µm were produced at a flow-focusing junction with carrier phase hexadecane and extracted into ethyl acetate. Solvent exchange and extraction result in droplet shrinkage, demixing, coarsening and phase-inversion, yielding polymer microparticles with well-defined dimensions and internal microstructure. Polymer concentration, varied from below the overlap concentration c* to above the concentrated crossover c**, as estimated by viscosity measurements, was found to have the largest impact on the final particle size and extraction timescale, while polymer mass and hydrolysis played a secondary role. These results are consistent with the observation that the average polymer concentration upon solidification greatly exceeds c**, and that the internal microparticle porosity is largely unchanged. However, reducing the initial polymer concentration to well below c* (approximately 100×) and increasing droplet size yields thin-walled (100's of nm) capsules which controllably crumple upon extraction. The symmetry of the process can be readily broken by imposing extraction conditions at an impermeable surface, yielding large, buckled, cavity morphologies. Based on these results, we establish robust design criteria for polymer capsules and particles, demonstrated here for poly(vinyl alcohol), with well-defined shape, dimensions and internal microstructure.

Endemic species may have complex histories: within-refugium phylogeography of an endangered Iberian vole.

Glacial refugia protected and promoted biodiversity during the Pleistocene, not only at a broader scale, but also for many endemics that contracted and expanded their ranges within refugial areas. Understanding the evolutionary history of refugial endemics is especially important in the case of endangered species to recognize the origins of their genetic structure and thus produce better informed conservation practices. The Iberian Peninsula is an important European glacial refugium, rich in endemics of conservation concern, including small mammals, such as the Cabrera vole (Microtus cabrerae). This near-threatened rodent is characterized by an unusual suite of genetic, life history and ecological traits, being restricted to isolated geographic nuclei in fast-disappearing Mediterranean subhumid herbaceous habitats. To reconstruct the evolutionary history of the Cabrera vole, we studied sequence variation at mitochondrial, autosomal and sex-linked loci, using invasive and noninvasive samples. Despite low overall mitochondrial and nuclear nucleotide diversities, we observed two main well-supported mitochondrial lineages, west and east. Phylogeographic modelling in the context of the Cabrera vole's detailed fossil record supports a demographic scenario of isolation of two populations during the Last Glacial Maximum from a single focus in the southern part of the Iberian Peninsula. In addition, our data suggest subsequent divergence within the east, and secondary contact and introgression of the expanding western population, during the late Holocene. This work emphasizes that refugial endemics may have a phylogeographic history as rich as that of more widespread species, and conservation of such endemics includes the preservation of that genetic legacy.

Impact of solution phase behaviour and external fields on thin film morphology: PCBM and RRa-P3HT model system.

We report the impact of the ternary solution phase behaviour on the film morphology and crystallization of a model polymer:fullerene system. We employ UV-Vis absorption spectroscopy, combined with sequential filtration and dilution, to establish the phase diagram for regio-random poly(3-hexylthiophene-2,5-diyl) and phenyl-C61-butyric acid methyl ester (PCBM) in chlorobenzene. Films are systematically cast from one- and two-phase regions decoupling homogeneous and heterogenous nucleation, and the role of pre-formed aggregates from solutions. Increasing annealing temperature from 120 to 200 °C reveals a highly non-monotonic nucleation profile with a maximum at 170 °C, while the crystal growth rate increases monotonically. UV ozonolysis is employed to vary substrate energy, and found to increase nucleation rate and to promote a binary crystallization process. As previously found, exposure to light, under an inert atmosphere, effectively suppresses homogeneous nucleation; however, it has a considerably smaller effect on heterogeneous nucleation, either from solution aggregates or substrate-driven. Our results establish a quantitative link between solution thermodynamics, crystallization and provide insight into morphological design based on processing parameters in a proxy organic photovoltaic system.

Diversity and genetic structure of the native Brazil nut tree (Bertholletia excelsa Bonpl.) population.

The present study was carried out in a native Brazil nut tree population (Bertholletia excelsa Bonpl., Lecythidaceae) to assess its genetic diversity and structure. Ten microsatellite markers were used to genotype 198 adult trees (B. excelsa). The population presented high genetic diversity and inbreeding absence rates. The empirical Bayesian method showed three distinct groups in the structure of this population. Molecular analysis of variance showed 98% variability within groups, and 2% between groups. The genetic divergence (FST) indicated little difference between groups; thus, suggesting efficient gene flow between the analyzed B. excelsa adult trees.

Prevalence of Leptospira antibodies in wild boars (Sus scrofa) from Northern Portugal: risk factor analysis.

Leptospirosis is a zoonosis of worldwide distribution, caused by infection with pathogenic spirochaetes of the genus Leptospira. The wild boar (Sus scrofa), an important hunting species in Europe, seems to play a significant role in the epidemiological cycle of leptospirosis. A total of 101 serum samples from wild boar hunted in Northern Portugal were analysed for leptospiral antibodies detection by microscopic agglutination test. Sera were collected during hunting seasons (2011-2013) and tested with 17 different pathogenic serovars of Leptospira. Antibodies against nine serovars were detected in 66 (65·4%) of these sera. Serovars Tarassovi and Altodouro exhibited the highest seroreactivity rates (23·8% and 16·8%, respectively), followed by Autumnalis (7·9%) and Bratislava (6·9%). Age and district of origin were found to be risk factors for the presence of leptospiral antibodies in contrast to gender. From a One Health perspective, this study revealed that wild boar should be considered as a potential source of leptospirosis dissemination for humans and animal species (domestic and wild) in shared environments, particularly in the Trás-os-Montes region.

Partitioning the grapevine growing season in the Douro Valley of Portugal: accumulated heat better than calendar dates.

Temperature and water status profiles during the growing season are the most important factors influencing the ripening of wine grapes. To model weather influences on the quality and productivity of the vintages, it is necessary to partition the growing season into smaller growth intervals in which weather variables are evaluated. A significant part of past and ongoing research on the relationships between weather and wine quality uses calendar-defined intervals to partition the growing season. The phenology of grapevines is not determined by calendar dates but by several factors such as accumulated heat. To examine the accuracy of different approaches, this work analyzed the difference in average temperature and accumulated precipitation using growth intervals with boundaries defined by means of estimated historical phenological dates and intervals defined by means of accumulated heat or average calendar dates of the Douro Valley of Portugal. The results show that in situations where there is an absence of historical phenological dates and/or no available data that makes the estimation of those dates possible, it is more accurate to use grapevine heat requirements than calendar dates to define growth interval boundaries. Additionally, we analyzed the ability of the length of growth intervals with boundaries based on grapevine heat requirements to differentiate the best from the worst vintage years with the results showing that vintage quality is strongly related to the phenological events. Finally, we analyzed the variability of growth interval lengths in the Douro Valley during 1980-2009 with the results showing a tendency for earlier grapevine physiology.

More than a feeling: Effects of competitive asymmetry on human emotions.

Competitive interactions have important effects on human emotions. Both victory and defeat can evoke a wide range of emotional reactions, including joy, pride, anger, fear, sadness and shame. However, little is known about what determines this variety of contestants' affective responses. Therefore, the purpose of this study was to evaluate the effects of competitive asymmetry, a common and ecologically relevant feature of animal conflicts, on human emotional responses to winning or losing a contest. To test this hypothesis, we conducted two experiments, the first with high school students (n = 331) and the second with young athletes (n = 73), in which we manipulated the outcomes of successive matches in a non-athletic competition. Thus, by inducing the competitors' scores, ranging from closer to more decisive outcomes, we were able to define the degree of competitive asymmetry in victory and defeat conditions. We then assessed participants' emotional responses to a set of affective stimuli. In the defeat condition, we found in both studies an increase in the occurrence of anger and fear due to more symmetric contests. There were also more frequent reports of shame following more decisive defeats (Experiment 1) and of pride following closer victories (Experiment 2), which were seen neither for sadness nor joy in any of the studies. Supporting our hypothesis, emotional reactions triggered by asymmetries among contestants were consistent with the behavioral patterns commonly seen in symmetric and asymmetric animal conflict, such as dominance/aggressive and defensive/escape behaviors.

Assessing the agreement between the pneumatic and the flow-centrifuge method for estimating xylem safety in temperate diffuse-porous tree species.

The increasing frequency of global change-type droughts has created a need for fast, accurate and widely applicable techniques for estimating xylem embolism resistance to improve forecasts of future forest changes. We used data from 12 diffuse-porous temperate tree species covering a wide range of xylem safety to compare the pneumatic and flow-centrifuge method, two rapid methods used for constructing xylem vulnerability curves. We evaluated the agreement between parameters estimated with both methods and the sensitivity of pneumatic measurements to the duration of air discharge (AD) measurements. There was close agreement between xylem water potentials at 50% air discharged (PAD), estimated with the Pneumatron, and 50% loss of hydraulic conductivity (PLC), estimated with the flow-centrifuge method (mean signed deviation: 0.12 MPa, Pearson correlation: 0.96 after 15 s of gas extraction). However, the relationship between the estimated slopes was more variable, resulting in lower agreement in the xylem water potential at 12% and 88% PAD/PLC. The agreement between the two methods was not affected by species-specific vessel length distributions. All pneumatic parameters were sensitive to AD time. Overall agreement was highest at relatively short AD times, with an optimum at 16 s. Our results highlight the value of the Pneumatron as an easy and reliable tool to estimate 50% embolism thresholds for a wide range of diffuse-porous temperate angiosperms. Further, our study provides a set of useful metrics for methodological comparisons of vulnerability curves in terms of systematic and random deviations, as well as overall agreement.

Functional graph alterations in schizophrenia: a result from a global anatomic decoupling?

During rest, the brain exhibits slow hemodynamic fluctuations (<0.1 Hz) that are correlated across spatially segregated brain regions, defining functional networks. Resting-state functional networks of people with schizophrenia were found to have graph properties that differ from those of control subjects. Namely, functional graphs from patients exhibit reduced small-worldness, increased hierarchy, lower clustering, improved efficiency and greater robustness. Notably, most of these parameters correlate with patients' cognitive performance.To test if a brain-wide coupling deficit could be at the origin of such network reorganization, we use a model of resting-state activity where the coupling strength can be manipulated. For a range of coupling values, the simulated functional graphs obtained were characterized using graph theory.For a coupling range, simulated graphs shared properties of healthy resting-state functional graphs. On decreasing the coupling strength, the resultant functional graphs exhibited a topological reorganization, in the same way as described in schizophrenia.This work shows how complex functional graph alterations reported in schizophrenia can be accounted for by a decrease in the structural coupling strength. These results are corroborated by reports of lower white matter density in schizophrenia.

Mn substitution in the topological metal Zr2Te2P.

Results are reported for Mn intercalated Zr2Te2P, where x-ray diffraction , energy dispersive spectroscopy, and transmission electron microscopy measurements reveal that the van der Waals bonded Te-Te layers are partially filled by Zr and Mn ions. This leads to the chemical formulas Zr0.07Zr2Te2P and Mn0.06Zr0.03Zr2Te2P for the parent and substituted compounds, respectively. The impact of the Mn ions is seen in the anisotropic magnetic susceptibility, where Curie-Weiss fits to the data indicate that the Mn ions are in the divalent state. Heat capacity and electrical transport measurements reveal metallic behavior, but the electronic coefficient of the heat capacity (γMn≈ 36.6 mJ (mol·K2)-1) is enhanced by comparison to that of the parent compound. Magnetic ordering is seen atTM≈4 K, where heat capacity measurements additionally show that the phase transition is broad, likely due to the disordered Mn distribution. This transition also strongly reduces the electronic scattering seen in the normalized electrical resistance. These results show that Mn substitution simultaneously introduces magnetic interactions and tunes the electronic state, which improves prospects for inducing novel behavior in Zr2Te2P and the broader family of ternary tetradymites.

Integrating ecosystem services into sustainable landscape management: A collaborative approach.

The Paiva River is considered one of the least polluted rivers in Europe and its watershed has a high conservation value. However, the Paiva River basin suffers pressures related with recurrent disturbances in land use, such as forest fires, agricultural activities, urbanization and pressures that affect the natural hydromorphological conditions and the continuity of watercourses. Blue and Green Infrastructures (BGINs) emerge to improve biodiversity, sustainability and the supply of ecosystem services while improving socioeconomic aspects. Thus, this article aims to identify priority areas in the basin, for intervention with these infrastructures. For that, a spatial multicriteria decision analysis (MDCA) was carried out according to several data related to the Paiva River Basin. As local politicians and responsible entities for the natural resources management are the main experts on the problems and their possible solutions at the local level, they were involved in this decision-making model. Therefore, these specialized stakeholders did the weighting assignment according to the most or least importance of the same for the work. The map of priority locations to implement BGINs was obtained in the sequel. To the top 5 priority areas, stakeholders attributed the best solutions based on nature. The most recommended BGINs were recovery/maintenance of riparian vegetation and conservation and reforestation of the native forest, both presented in four of the five areas, and introduction of fuel management strips presented in three of the five areas. Thus, we concluded that it is extremely important to include the communities and the competent entities of nature and environment management in scientific projects related to conservation, forming a synergy that makes it possible to combine scientific knowledge with local experience acquired in the field. This project uses a very flexible methodology of local data and can be a great example to be implemented in other hydrographic basins anywhere in the world.

A dual high-energy radiography platform with 15 µm resolution at the National Ignition Facility.

To study matter at extreme densities and pressures, we need mega laser facilities such as the National Ignition Facility as well as creative methods to make observations during timescales of a billionth of a second. To facilitate this, we developed a platform and diagnostic to characterize a new point-projection radiography configuration using two micro-wires irradiated by a short pulse laser system that provides a large field of view with up to 3.6 ns separation between images. We used tungsten-carbide solid spheres as reference objects and inferred characteristics of the back-lighter source using a forward-fitting algorithm. The resolution of the system is inferred to be 15 µm (using 12.5 µm diameter wires). The bremsstrahlung temperature of the source is 70-300 keV, depending on laser energy and coupling efficiency. By adding the images recorded on multiple stacked image plates, the signal-to-noise of the system is nearly doubled. The imaging characterization technique described here can be adapted to most point-projection platforms where the resolution, spectral contrast, and signal-to-noise are important.

Diabetes and other glucose metabolism abnormalities in Mexican Zapotec and Mixe Indians.

AIMS: Aboriginal populations are experiencing an explosive rise in the prevalence of Type 2 diabetes. The purpose of this study was to estimate the prevalence of diabetes and other glucose metabolism abnormalities in Mexican Zapotec and Mixe Indians and to determine their association with known risk factors. METHODS: A cross-sectional study was conducted in the southern Mexican state of Oaxaca. Two communities of Zapotec population and three of Mixe population were randomly chosen. Mexican Indians>or=35 years old were invited to participate; 394 Zapotec and 730 Mixe Indians participated. Diabetes and other glucose metabolism abnormalities were diagnosed using standard World Health Organization criteria after an oral glucose tolerance test. Prevalence and odds ratio (OR) were estimated with 95% confidence intervals (95% CI). RESULTS: The crude prevalence of diabetes was 8.19% (95% CI 6.7-9.9%) and the age- and sex-adjusted prevalence was 8.27%, significantly higher among Zapotec (8.71%) than among Mixe Indians (6.90%). The prevalence of impaired glucose tolerance was 9.9% and 4.7% of the studied subjects had impaired fasting glucose. The main risk factors related to the occurrence of diabetes were a family history of diabetes (OR 4.1; 95% CI 1.9-8.8), obesity (OR 3.0; 95% CI 1.6-5.6), hypertension (OR 2.6; 95% CI 1.5-4.7) and a high-risk waist-hip ratio (4.6; 95% CI 1.2-17.7). CONCLUSIONS: The prevalence of diabetes is high in this population, the highest so far reported in Mexican Indians. Mexico's health system faces a huge challenge to avert the advanced spread of diabetes in this susceptible population.

Nonviral gene delivery to mesenchymal stem cells using cationic liposomes for gene and cell therapy.

Mesenchymal stem cells (MSCs) hold a great promise for application in several therapies due to their unique biological characteristics. In order to harness their full potential in cell-or gene-based therapies it might be advantageous to enhance some of their features through gene delivery strategies. Accordingly, we are interested in developing an efficient and safe methodology to genetically engineer human bone marrow MSC (BM MSC), enhancing their therapeutic efficacy in Regenerative Medicine. The plasmid DNA delivery was optimized using a cationic liposome-based reagent. Transfection efficiencies ranged from approximately 2% to approximately 35%, resulting from using a Lipid/DNA ratio of 1.25 with a transgene expression of 7 days. Importantly, the number of plasmid copies in different cell passages was quantified for the first time and approximately 20,000 plasmid copies/cell were obtained independently of cell passage. As transfected MSC have shown high viabilities (>90%) and recoveries (>52%) while maintaining their multipotency, this might be an advantageous transfection strategy when the goal is to express a therapeutic gene in a safe and transient way.

Optimization of gene delivery to HEK293T cells by microporation using a central composite design methodology.

Microporation is an efficient method for delivering plasmid DNA molecules into cultured cells. Herein, we present the optimization of gene delivery by microporation using a Central Composite Design methodology. It was given relevance not only to the transfection efficiency but also to the cell recovery. Different amounts of DNA (1 and 3 µg) mainly affected cell viabilities and cell recoveries, which decrease from 93 to 76% and from 47 to 25% respectively, when higher DNA quantity is used. With this work we suggest an easy methodology to improve transfection of mammalian cells underlining the feasibility to achieve 60% of gene delivery efficiencies whilst recovering 50% of cells, with 90% of viability.

Chronic hepatitis C treatment in a cystic fibrosis patient in the pulmonary pre-transplant stage.

The standard treatment of chronic hepatitis C, pegylated interferon and ribavirin (pegI/R), has many limitations in both effectiveness and secondary effects, which makes it unsuitable or even contraindicated for some patients. In hepatitis C virus-infected cystic fibrosis patients this treatment could increase respiratory infections with subsequent pulmonary function deterioration. On the contrary, hepatitis C virus (HCV) infection may make lung transplant (LT) unfeasible. We present the case of a cystic fibrosis-young man diagnosed with HCV infection during LT assessment who was treated with pegI/R. In spite of the lung function worsening and respiratory infections, he managed to complete treatment and even sustained virological response (SVR). At present he is on LT waiting list.