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The performance of dye-sensitized solar cells (DSCs) critically depends on the efficiency of electron transport within the TiO 2 -dye-electrolyte interface. To improve the efficiency of the electron transfer the conventional structure of the working electrode (WE) based on TiO 2 nanoparticles (NPs) was replaced with TiO 2 nanotubes (NTs). Sol-gel method was used to prepare undoped and Nb-doped TiO 2 NPs and TiO 2 NTs. The crystallinity and morphology of the WEs were characterized using XRD, SEM and TEM techniques. XPS and PL measurements revealed a higher concentration of oxygen-related defects at the surface of NPs-based electrodes compared to that based on NTs. Replacement of the conventional NPs-based TiO 2 WE with alternative led to a 15% increase in power conversion efficiency (PCE) of the DSCs. The effect is attributed to the more efficient transfer of charge carriers in the NTs-based electrodes due to lower defect concentration. The suggestion was confirmed experimentally by electrical impedance spectroscopy measurements when we observed the higher recombination resistance at the TiO 2 NTs-electrolyte interface compared to that at the TiO 2 NPs-electrolyte interface. Moreover, Nb-doping of the TiO 2 structures yields an additional 14% PCE increase. The application of Nb-doped TiO 2 NTs as photo-electrode enables the fabrication of a DSC with an efficiency of 8.1%, which is 35% higher than that of a cell using a TiO 2 NPs. Finally, NTs-based DSCs have demonstrated a 65% increase in the PCE value, when light intensity was decreased from 1000 to 10 W/m 2 making such kind device be promising alternative indoor PV applications when the intensity of incident light is low., Competing Interests: The authors declare no conflict of interest

Solid oxide fuel cells produce electricity directly by oxidizing methane, which is the most attractive natural gas fuel, and metal nanocatalysts are a promising means of overcoming the poor catalytic activity of conventional ceramic electrodes. However, the lack of thermal and chemical stability of nanocatalysts is a major bottleneck in the effort to ensure the lifetime of metal-decorated electrodes for methane oxidation. Here, for the first time, this issue is addressed by encapsulating metal nanoparticles with gas-permeable inorganic shells. Pt particles approximately 10 nm in size are dispersed on the surface of a porous La 0.75 Sr 0.25 Cr 0.5 Mn 0.5 O 3 (LSCM) electrode via wet infiltration and are then coated with an ultrathin Al 2 O 3 layer via atomic layer deposition. The Al 2 O 3 overcoat, despite being an insulator, significantly enhances the immunity to carbon coking and provides high activity for the electrochemical oxidation of methane, thereby reducing the reaction impedance of the Pt-decorated electrode by more than 2 orders of magnitude and making the electrode activity of the Pt-decorated sample at 650 °C comparable with those reported at 800 °C for pristine LSCM electrodes. These observations provide a new perspective on strategies to lower the operation temperature, which has long been a challenge related to hydrocarbon-fueled solid oxide fuel cells.

The interaction of silver nitrate with star-shaped poly(2-ethyl-2-oxazoline) and poly(2-isopropyl-2-oxazoline) containing central thiacalix[4]arene cores, which proceeds under visible light in aqueous solutions at ambient temperature, was studied. It was found that this process led to the formation of stable colloidal solutions of silver nanoparticles. The kinetics of the formation of the nanoparticles was investigated by the observation of a time-dependent increase in the intensity of the plasmon resonance peak that is related to the nanoparticles and appears in the range of 400 to 700 nm. According to the data of electron and X-ray spectroscopy, scanning and transmission electron microscopy, X-ray diffraction analysis, and dynamic light scattering, the radius of the obtained silver nanoparticles is equal to 30 nm. In addition, the flow birefringence experiments showed that solutions of nanoparticles have high optical shear coefficients.

In animals that experience interactions with conspecifics while young, social interactions appear to be a necessary prerequisite for typical behaviour. Eusocial insects have large colonies where individuals experience a large number of social interactions with nest mates during all life stages, making them excellent candidates for understanding the effects of social isolation on brain development and behaviour. Here, we used the honey bee Apis mellifera to study the effect of social isolation and group size on reward perception and discrimination learning and memory. We confined day--old adult workers into three different size groups (1, 8 or 32 bees) for 6 days during a critical period associated with adult behavioural maturation. We quantified their sucrose responsiveness, their ability to use and remember olfactory cues to discriminate between sucrose and salt (i.e. discrimination learning), and four biogenic amines in the brain. We found that the smaller the group size, the more responsive a worker was to the sucrose reward. Honey bees raised in groups of 32 performed the best in the learning trials and had the highest levels of dopamine. We found no effect of group size on memory. The observed group size effect on learning but not memory supports the hypothesis that social interactions modulate learning through the dopaminergic system., Competing Interests: Competing interestsThe authors declare no competing or financial interests., (© 2019. Published by The Company of Biologists Ltd.)

The yellow-banded bumblebee Bombus terricola was common in North America but has recently declined and is now on the IUCN Red List of threatened species. The causes of B. terricola' s decline are not well understood. Our objectives were to create a partial genome and then use this to estimate population data of conservation interest, and to determine whether genes showing signs of recent selection suggest a specific cause of decline. First, we generated a draft partial genome (contig set) for B. terricola , sequenced using Pacific Biosciences RS II at an average depth of 35×. Second, we sequenced the individual genomes of 22 bumblebee gynes from Ontario and Quebec using Illumina HiSeq 2500, each at an average depth of 20×, which were used to improve the PacBio genome calls and for population genetic analyses. The latter revealed that several samples had long runs of homozygosity, and individuals had high inbreeding coefficient F, consistent with low effective population size. Our data suggest that B. terricola 's effective population size has decreased orders of magnitude from pre-Holocene levels. We carried out tests of selection to identify genes that may have played a role in ameliorating environmental stressors underlying B. terricola' s decline. Several immune-related genes have signatures of recent positive selection, which is consistent with the pathogen-spillover hypothesis for B. terricola 's decline. The new B. terricola contig set can help solve the mystery of bumblebee decline by enabling functional genomics research to directly assess the health of pollinators and identify the stressors causing declines.

The hydrosols of chitin nanocrystals (ChN) are promising as modifiers of properties, drug delivery systems, and media. The purpose of this work is to clarify the mechanisms for regulating processes of stability and structure formation occurring in the ChN hydrosols under the influence of varying ionic strength. ChN were isolated from the crab shell; ChN hydrosols are obtained with different concentrations of the dispersed phase. The structure and morphology of the particles was studied by atomic force microscopy and X-ray diffraction. Hydrosols were studied by rotational viscometry, dynamic light scattering, and photometry in the presence of KCl with concentration up to 200mM. The experimental results of finding the rapid coagulation threshold are compared with calculated ones performed with the use of the modified DLVO theory. It is established that in the range of electrolyte concentrations 30∼75mM, the optical and rheological properties of the ChN hydrosols undergo crucial changes. At an electrolyte concentration of 20∼150mM, particles coagulate at a secondary potential minimum; the parallel orientation of the particles is energetically more advantageous. In systems with a higher concentration of electrolyte, there is no potential barrier; rapid barrier-free coagulation is observed, with the formation of stronger coagulation contacts and the formation of stable gels., (Copyright © 2017 Elsevier Ltd. All rights reserved.)

CO 2 splitting via thermo-chemical or reactive redox has emerged as a novel and promising carbon-neutral energy solution. Its performance depends critically on the properties of the oxygen carriers (OC). Ceria is recognized as one of the most promising OC candidates, because of its fast chemistry, high ionic diffusivity, and large oxygen storage capacity. The fundamental surface ion-incorporation pathways, along with the role of surface defects and the adsorbates remain largely unknown. This study presents a detailed kinetics study of CO 2 splitting using CeO 2 and Ce 0.5 Zr 0.5 O 2 (CZO) in the temperature range 600-900 °C. Given our interest in fuel-assisted reduction, we limit our study to relatively lower temperatures to avoid excessive sintering and the need for high temperature heat. Compared to what has been reported previously, we observe higher splitting kinetics, resulting from the utilization of fine particles and well-controlled experiments which ensure a surface-limited-process. The peak rates with CZO are 85.9 μmole g -1 s -1 at 900 °C and 61.2 μmole g -1 s -1 at 700 °C, and those of CeO 2 are 70.6 μmole g -1 s -1 and 28.9 μmole g -1 s -1 . Kinetic models are developed to describe the ion incorporation dynamics, with consideration of CO 2 activation and the charge transfer reactions. CO 2 activation energy is found to be -120 kJ mole -1 for CZO, half of that for CeO 2 , while CO desorption energetics is analogous between the two samples with a value of ∼160 kJ mole -1 . The charge-transfer process is found to be the rate-limiting step for CO 2 splitting. The evolution of CO 3 2- with surface Ce 3+ is examined based on the modeled kinetics. We show that the concentration of CO 3 2- varies with Ce 3+ in a linear-flattened-decay pattern, resulting from a mismatch between the kinetics of the two reactions. Our study provides new insights into the significant role of surface defects and adsorbates in determining the splitting kinetics.

CH 3 NH 3 PbI 3 is one of the promising light sensitizers for perovskite photovoltaic cells, but a thick layer is required to enhance light absorption in the long-wavelength regime ranging from PbI 2 absorption edge (500 nm) to its optical band-gap edge (780 nm) in visible light. Meanwhile, the thick perovskite layer suppresses visible-light absorption in the short wavelengths below 500 nm and charge extraction capability of electron-hole pairs produced upon light absorption. Herein, we find that a new light scattering layer with the mixed cavities of sizes in 100 and 200 nm between transparent fluorine-doped tin oxide and mesoporous titanium dioxide electron transport layer enables full absorption of short-wavelength photons (λ < 500 nm) to the perovskite along with enhanced absorption of long-wavelength photons (500 nm < λ < 780 nm). Moreover, the light-driven electric field is proven to allow efficient charge extraction upon light absorption, thereby leading to the increased photocurrent density as well as the fill factor prompted by the slow recombination rate. Additionally, the photocurrent density of the cell with a light scattering layer of mixed cavities is stabilized due to suppressed charge accumulation. Consequently, this work provides a new route to realize broadband light harvesting of visible light for high-performance perovskite photovoltaic cells., (© 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Experiments linking neonicotinoids and declining bee health have been criticized for not simulating realistic exposure. Here we quantified the duration and magnitude of neonicotinoid exposure in Canada's corn-growing regions and used these data to design realistic experiments to investigate the effect of such insecticides on honey bees. Colonies near corn were naturally exposed to neonicotinoids for up to 4 months-the majority of the honey bee's active season. Realistic experiments showed that neonicotinoids increased worker mortality and were associated with declines in social immunity and increased queenlessness over time. We also discovered that the acute toxicity of neonicotinoids to honey bees doubles in the presence of a commonly encountered fungicide. Our work demonstrates that field-realistic exposure to neonicotinoids can reduce honey bee health in corn-growing regions., (Copyright © 2017 The Authors, some rights reserved; exclusive licensee American Association for the Advancement of Science. No claim to original U.S. Government Works.)

As Rosai-Dorfman Disease presents generally nonspecific symptoms, differential diagnosis can be of great learning curve for physicians. Additionally, RDD does not usually threaten life and spontaneous remission is frequently observed. However, unusually in our case the patient passed away within 1 month of confirmed diagnosis.

Segregation and phase separation of aliovalent dopants on perovskite oxide (ABO3) surfaces are detrimental to the performance of energy conversion systems such as solid oxide fuel/electrolysis cells and catalysts for thermochemical H2O and CO2 splitting. One key reason behind the instability of perovskite oxide surfaces is the electrostatic attraction of the negatively charged A-site dopants (for example, ) by the positively charged oxygen vacancies () enriched at the surface. Here we show that reducing the surface concentration improves the oxygen surface exchange kinetics and stability significantly, albeit contrary to the well-established understanding that surface oxygen vacancies facilitate reactions with O2 molecules. We take La0.8Sr0.2CoO3 (LSC) as a model perovskite oxide, and modify its surface with additive cations that are more and less reducible than Co on the B-site of LSC. By using ambient-pressure X-ray absorption and photoelectron spectroscopy, we proved that the dominant role of the less reducible cations is to suppress the enrichment and phase separation of Sr while reducing the concentration of and making the LSC more oxidized at its surface. Consequently, we found that these less reducible cations significantly improve stability, with up to 30 times faster oxygen exchange kinetics after 54 h in air at 530 °C achieved by Hf addition onto LSC. Finally, the results revealed a 'volcano' relation between the oxygen exchange kinetics and the oxygen vacancy formation enthalpy of the binary oxides of the additive cations. This volcano relation highlights the existence of an optimum surface oxygen vacancy concentration that balances the gain in oxygen exchange kinetics and the chemical stability loss.

The influence of the lattice strain on the kinetics of the oxygen reduction reaction (ORR) was investigated at the surface of Nd2NiO4+δ (NNO). Nanoscale dense NNO thin films with tensile, compressive and no strain along the c-axis were fabricated by pulsed laser deposition on single-crystalline Y0.08Zr0.92O2 substrates. The ORR kinetics on the NNO thin film cathodes was investigated by electrochemical impedance spectroscopy at 360-420 °C in air. The oxygen exchange kinetics on the NNO films with tensile strain along the c-axis was found to be 2-10 times faster than that on the films with compressive strain along the c-axis. A larger concentration of oxygen interstitials (δ) is found in the tensile NNO films compared to the films with no strain or compressive strain, deduced from the measured chemical capacitance. This is consistent with the increase in the distance between the NdO rock-salt layers observed by transmission electron microscopy. The surface structure of the nonstrained and tensile strained films remained stable upon annealing in air at 500 °C, while a significant morphology change accompanied by the enrichment of Nd was found at the surface of the films with compressive strain. The faster ORR kinetics on the tensile strained NNO films was attributed to the ability of these films to incorporate oxygen interstitials more easily, and to the better stability of the surface chemistry in comparison to the nonstrained or compressively strained films.

The degradation of the surface chemistry on perovskite (ABO3) oxides is a critical issue for their performance in energy conversion systems such as solid oxide fuel/electrolysis cells and in splitting of H2O and CO2 to produce fuels. This degradation is typically in the form of segregation and phase separation of dopant cations from the A-site, driven by elastic and electrostatic energy minimization and kinetic demixing. In this study, deposition of Ti at the surface was found to hinder the dopant segregation and the corresponding electrochemical degradation on a promising SOFC cathode material, La(0.8)Sr(0.2)CoO3 (LSC). The surface of the LSC films was modified by Ti (denoted as LSC-T) deposited from a TiCl4 solution. The LSC and LSC-T thin films were investigated by electrochemical impedance spectroscopy, nano-probe Auger electron spectroscopy, and X-ray photoelectron spectroscopy (XPS), upon annealing at 420-530 °C in air up to about 90 hours. The oxygen exchange coefficient, k(q), on LSC-T cathodes was found to be up to 8 times higher than that on LSC cathodes at 530 °C and retained its stability. Sr-rich insulating particles formed at the surface of the annealed LSC and LSC-T films, but with significantly less coverage of such particles on the LSC-T. From this result, it appears that modification of the LSC surface with Ti reduces the segregation of the blocking Sr-rich particles at the surface, and a larger area on LSC surface (with a higher Sr doping level in the lattice) is available for the oxygen reduction reaction. The stabilization of the LSC surface through Ti-deposition can open a new route for designing surface modifications on perovskite oxide electrodes for high temperature electro- and thermo-chemical applications.

Many animals have individual and social mechanisms for combating pathogens. Animals may exhibit short-term physiological tradeoffs between social and individual immunity because the latter is often energetically costly. Genetic tradeoffs between these two traits can also occur if mutations that enhance social immunity diminish individual immunity, or vice versa. Physiological tradeoffs between individual and social immunity have been previously documented in insects, but there has been no study of genetic tradeoffs involving these traits. There is strong evidence that some genes influence both innate immunity and behaviour in social insects--a prerequisite for genetic tradeoffs. Quantifying genetic tradeoffs is critical for understanding the evolution of immunity in social insects and for devising effective strategies for breeding disease-resistant pollinator populations. We conducted two experiments to test the hypothesis of a genetic tradeoff between social and individual immunity in the honey bee, Apis mellifera. First, we estimated the relative contribution of genetics to individual variation in innate immunity of honey bee workers, as only heritable traits can experience genetic tradeoffs. Second, we examined if worker bees with hygienic sisters have reduced individual innate immune response. We genotyped several hundred workers from two colonies and found that patriline genotype does not significantly influence the antimicrobial activity of a worker's hemolymph. Further, we did not find a negative correlation between hygienic behaviour and the average antimicrobial activity of a worker's hemolymph across 30 honey bee colonies. Taken together, our work indicates no genetic tradeoffs between hygienic behaviour and innate immunity in honey bees. Our work suggests that using artificial selection to increase hygienic behaviour of honey bee colonies is not expected to concurrently compromise individual innate immunity of worker bees.

Nitrogen is essential to reaction of (PNP)OsI (PNP is N(SiMe(2)CH(2)P(t)Bu(2))(2)) and Mg powder in THF, to give equimolar (PNP)OsH(N(2)) and hydrido carbene [((t)Bu(2)PCH(2)SiMe(2))N(SiMe(2)CH(2)P(t)Bu(CMe(2)CH)]OsH. This reaction is attributed to H(2) evolution from solid magnesium, rather than high energy H atom transfer between molecules, but relies also on the strong π-basicity of Os in favoring α-H migration from the metallated (t)Bu group on Os to form the second product, the hydrido carbene species. The path to two different products begins because the simple N(2) adduct of (PNP)OsI undergoes spontaneous heterolytic H-C splitting of the (t)Bu methyl group, to produce a secondary amine intermediate [((t)Bu(2)PCH(2)SiMe(2))N(H)(SiMe(2)CH(2)P(t)Bu(CMe(2)CH(2))]OsI(N(2)) which can then be dehydrohalogenated by Mg. The analogous reaction for (PNP)RuCl shows production of only (PNP)RuH(N(2)), with none of the hydride carbene dehydrogenation product. Comparative (Ru vs. Os) DFT calculations reveal the reaction steps where the Os analog is much more exothermic, accounting for certain reaction selectivities.

New genomic resources and genetic tools of the past few years have advanced the nematode genus Caenorhabditis as a model for comparative biology. However, understanding of natural genetic variation at molecular and phenotypic levels remains rudimentary for most species in this genus, and for C. briggsae in particular. Here we characterize phenotypic variation in C. briggsae's sensitivity to the potentially important and variable environmental toxin, ethanol, for globally diverse strains. We also quantify nucleotide variation in a new sample of 32 strains from four continents, including small islands, and for the closest-known relative of this species (C. sp. 9). We demonstrate that C. briggsae exhibits little heritable variation for the effects of ethanol on the norm of reaction for survival and reproduction. Moreover, C. briggsae does not differ significantly from C. elegans in our assays of its response to this substance that both species likely encounter regularly in habitats of rotting fruit and vegetation. However, we uncover drastically more molecular genetic variation than was known previously for this species, despite most strains, including all island strains, conforming to the broad biogeographic patterns described previously. Using patterns of sequence divergence between populations and between species, we estimate that the self-fertilizing mode of reproduction by hermaphrodites in C. briggsae likely evolved sometime between 0.9 and 10 million generations ago. These insights into C. briggsae's natural history and natural genetic variation greatly expand the potential of this organism as an emerging model for studies in molecular and quantitative genetics, the evolution of development, and ecological genetics.

Density functional theory calculations on the conformational preferences in the two fused five-membered rings of anionic N(SiR2CH2PR'2)2 chelated to RuX+ are compared to several experimental structures (X=halide). The calculations consider the structures of both singlet and triplet states and reveal that both the four tBu groups and the crowded juncture (N(SiMe2)2) of the two rings must be included computationally to understand the observed structures. Computational experiments with different substituents R and R' show the reality of N-->Ru pi donation. The cases where X=H and CH3 are also studied.

In laboratory experiments with batch cultures of thermophilic microorganisms isolated from urban heat supply systems, the growth of sulfate-reducing, iron-oxidizing, and iron-reducing bacteria was found to accelerate the corrosion rate of the steel-3 plates used in the pipelines. In the absence of bacteria and dissolved oxygen, minimal, corrosion was determined. The aforementioned microorganisms, as well as sulfur-oxidizing bacteria, were found to be widespread in water and corrosion deposits in low-alloy steel pipelines (both delivery and return) of the Moscow heat networks, as well as in the corrosion deposits on the steel-3 plates in a testing unit supplied with the network water. The microorganisms were found in samples with water pH ranging from 8.1 to 9.6 and a temperature lower than 90 degrees C. Magnetite, lepidocrocite, goethite, X-ray amorphous ferric oxide were the corrosion products identified on the steel-3 plates, as well as siderite, aragonite, and S0. The effect of microbiological processes on the rate of electrochemical corrosion was evaluated from the accumulation of corrosion deposits and from variation in total and local corrosion of the steel plates in a testing unit.

In comparison with allergens having protein fragments with a molecular weight not exceeding 110 kD, allergoids have been found to consist of larger fragments with a molecular weight of 10-150 kD. Allergoids have less charged components than initial allergens and less antigenic components. Allergoids retain their capacity for stimulating the production of antibodies, specific to all antigenic components.