Search

In this study, the influence of the anodic porous transport layer (PTL) on the performance of a proton exchange membrane (PEM) electrolysis laboratory test cell was investigated up to a current density of 5 A*cm−2. Operation parameters such as water volume flow rate (0.2-0.8 l*min−1), temperature (40-80 °C) and pressure (1-30 barg) have been varied to study their influence on the polarisation curve. Special attention has been paid to the appearance of mass transport losses (MTL) and their dependency on the operation parameters. Two stack designs that are commercially in use - one with and one without flow channels underneath the PTL - were tested and evaluated. Fundamental differences in performance have been observed between the two cell designs. Operation parameters only show impact on performance for the configuration without flow channels. Here, MTL were observed in several cases already for current densities around and above 1.0 A*cm−2. An increase in pressure, temperature or water flow rate reduces MTL for these configurations.

We report the synthesis of 9 new half squaraine (HfSQ) dyes; 5 containing a benzothiazole moiety and 4 containing an indolenine moiety. X-ray single crystal structural and characterisation data have been correlated with device data to understand the widely reported but poorly understood influence of S heteroatoms on DSC device performance. The S heteroatom in these new dyes has also been used as an atomic probe of the dye–TiO2 interface to dye binding and orientation. Thus, for the first time, using the S heteroatom probe, angle-resolved X-ray photoelectron (AR-XPS) data have shown these dyes sit horizontally at the dye–TiO2 interface confirmed by DFT computer modelling of novel and analogous HfSQ dyes with a benzoindole backbone.

Protists play a fundamental role in all ecosystems, but we are still far from estimating the total diversity of many lineages, in particular in highly diverse environments, such as freshwater. Here, we survey the protist diversity of the Parana River using metabarcoding, and we applied an approach that includes sequence similarity and phylogeny to evaluate the degree of genetic novelty of the protists' communities against the sequences described in the reference database PR2 . We observed that ~28% of the amplicon sequence variants were classified as novel according to their similarity with sequences from the reference database; most of them were related to heterotrophic groups traditionally overlooked in freshwater systems. This lack of knowledge extended to those groups within the green algae (Archaeplastida) that are well documented such as Mamiellophyceae, and also to the less studied Pedinophyceae, for which we found sequences representing novel deep-branching clusters. Among the groups with potential novel protists, Bicosoecida (Stramenopiles) were the best represented, followed by Codosiga (Opisthokonta), and the Perkinsea (Alveolata). This illustrates the lack of knowledge on freshwater planktonic protists and also the need for isolation and/or cultivation of new organisms to better understand their role in ecosystem functioning.

The behavior of polar metal organic molecules, chloroaluminum phthalocyanine (ClAlPc), upon ultraviolet (UV) irradiation was investigated to evaluate the stability of the adsorption process on the Ag(111) thin film and bulk crystal. Photoelectron spectroscopy (PES) was mainly employed to measure the molecular energy states (MES) and vacuum level (VL) shift for 1-ML ClAlPc in the Cl-down configuration. A consistent trend was observed showing that ClAlPc in the Cl-down configuration is energetically more stable on the Ag thin-film surface than on the corresponding surface of the Ag bulk crystal. The intermediate adsorption state in tilted configuration during the irradiation impinging is identified by large positive VL shifts and broad spectra line shapes to infer a flipping mechanism from Cl-down to Cl-up configuration. Strain on the Ag thin films from the underlying lattice-mismatched Ge(111) substrate is considered to cause enlarged hollow sites on the Ag(111) thin-films, that anchor the Cl-down configuration more tightly on the thin-film surfaces, as confirmed by density functional theory (DFT) calculations.

Sphagnum-dominated ecosystem plays major roles as carbon sinks at the global level. Associated microbial communities, in particular, eukaryotes, play significant roles in nutrient fixation and turnover. In order to understand better the ecological processes driven by these organisms, the first step is to characterise these associated organisms. We characterised the taxonomic diversity, and from this, inferred the functional diversity of microeukaryotes in Sphagnum mosses in tropical, subtropical and temperate climatic zones through an environmental DNA diversity metabarcoding survey of the V9 region of the gene coding for the RNA of the small subunit of the ribosomes (SSU rRNA). As microbial processes are strongly driven by temperatures, we hypothesised that saprotrophy would be highest in warm regions, whereas mixotrophy, an optimal strategy in oligotrophic environments, would peak under colder climates. Phylotype richness was higher in tropical and subtropical climatic zones than in the temperate region, mostly due to a higher diversity of animal parasites (i.e. Apicomplexa). Decomposers, and especially opportunistic yeasts and moulds, were more abundant under warmer climates, while mixotrophic organisms were more abundant under temperate climates. The dominance of decomposers, suggesting a higher heterotrophic activity under warmer climates, is coherent with the generally observed faster nutrient cycling at lower latitudes; this phenomenon is likely enhanced by higher inputs of nutrients most probably brought in the system by Metazoa, such as arthropods. Fil: Singer, David. Universidade de Sao Paulo; Brasil. Universite de Neuchatel; Suiza Fil: Metz, Sebastián Darío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Unrein, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Shimano, Satoshi. Hosei University; Japón Fil: Mazei, Yuri. Universidad Estatal de Moscú ; Rusia Fil: Mitchell, Edward A. D.. Jardin Botanique de Neuchâtel; Suiza Fil: Lara Pandis, Enrique Miguel. Consejo Superior de Investigaciones Científicas. Real Jardín Botánico; España

The growing societal and political focus on the use of environmentally friendly technologies has led to an ever-increasing interest in electrolysis technologies in the scientific communities. This development is reflected by the plethora of candidate catalysts for the hydrogen and oxygen evolution reactions, as well as the CO2 reduction reaction, reported in the literature. However, almost none of them entered the stage of application yet. Likewise, the reports on process engineering inadequately address the utilization of these catalysts, as well as electrode and cell concepts, that might be suitable for the market. Evidently, a closer collaboration between chemists and engineers from industry and academia is desirable to speed up the development of these disruptive technologies. Herein, we elucidate the critical parameters and highlight the necessary aspects to accelerate the development of industrially relevant catalysts capable of fulfilling the forthcoming challenges related to energy conversion and storage. The aim of this Perspective, composed by industrial and academic partners, is to critically question current undertakings and to encourage researchers to strike interdisciplinary research pathways. CA extern und CA Segets

How diversity is structured has been a central goal of microbial ecology. In freshwater ecosystems, selection has been found to be the main driver shaping bacterial communities. However, its relative importance compared with other processes (dispersal, drift, diversification) may depend on spatial heterogeneity and the dispersal rates within a metacommunity. Still, a decrease in the role of selection is expected with increasing dispersal homogenization. Here, we investigate the main ecological processes modulating bacterial assembly in contrasting scenarios of environmental heterogeneity. We carried out a spatiotemporal survey in the floodplain system of the Parana River. The bacterioplankton metacommunity was studied using both statistical inferences based on phylogenetic and taxa turnover as well as co-occurrence networks. We found that selection was the main process determining community assembly even at both extremes of environmental heterogeneity and homogeneity, challenging the general view that the strength of selection is weakened due to dispersal homogenization. The ecological processes acting on the community also determined the connectedness of bacterial networks associations. Heterogeneous selection promoted more interconnected networks increasing β-diversity. Finally, spatiotemporal heterogeneity was an important factor determining the number and identity of the most highly connected taxa in the system. Integrating all these empirical evidences, we propose a new conceptual model that elucidates how the environmental heterogeneity determines the action of the ecological processes shaping the bacterial metacommunity.

Accurately modeling the electronic structure of materials is a persistent challenge to high-throughput screening. A promising means of balancing accuracy against computational cost is non-self-consistent calculations with hybrid density-functional theory, where the electronic band energies are evaluated using a hybrid functional from orbitals obtained with a less demanding (semi)local functional. We have quantified the performance of this technique for predicting the physical properties of 16 tetrahedral semiconductors with bandgaps from 0.2 to 5.5 eV. Provided the base functional predicts a nonmetallic electronic structure, bandgaps within 5% of the PBE0 and HSE06 gaps can be obtained with an order of magnitude reduction in computing time. The positions of the valence and conduction band extrema and the Fermi level are well reproduced, enabling calculation of the band dispersion, density of states, and dielectric properties using Fermi's Golden Rule. While the error in the non-self-consistent total energies is ∼50 meV atom-1, the energy-volume curves are reproduced accurately enough to obtain the equilibrium volume and bulk modulus with minimal error. We also test the dielectric-dependent scPBE0 functional and obtain bandgaps and dielectric constants to within 2.5% of the self-consistent results, which amounts to a significant improvement over self-consistent PBE0 for a similar computational cost. We identify cases where the non-self-consistent approach is expected to perform poorly and demonstrate that partial self-consistency provides a practical and efficient workaround. Finally, we perform proof-of-concept calculations on CoO and NiO to demonstrate the applicability of the technique to strongly correlated open-shell transition-metal oxides.

Ceratium furcoides is an invasive freshwater dinoflagellate that in the last three decades has expanded its geographic distribution in South America, being recently found in Paraná River floodplain (Argentina). Despite growing concern about the presence and impacts of this invader, information regarding genetic diversity in the Southern Hemisphere is missing. This work constitutes the first phylogenetic characterization of Ceratium populations of South America, particularly, from the Paraná system. After taxonomic identification as C. furcoides based on morphological traits, two sequencing-based approaches were applied using the ribosomal 18S gene: Sanger sequencing to isolated individuals and high-throughput amplicon sequencing (HTS) to environmental DNA. The sequence of C. furcoides obtained shared 100% identity to Asian sequences, and formed a highly supported clade in the constructed reference phylogenetic tree. HTS helped to recover low-frequency genetic variants suggesting the presence of different population of C. furcoides, and to alert potential invasion in its early stages. Fil: Accattatis, Victoria. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina Fil: Piccini, Claudia. Instituto de Investigaciones Biológicas "Clemente Estable"; Uruguay Fil: Huber, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina Fil: Metz, Sebastián Darío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Rueda, Eva Carolina. Consejo Nacional de Investigaciones Científicas y Técnicas; Argentina. Universidad Nacional del Litoral. Facultad de Humanidades y Ciencias; Argentina Fil: Devercelli, Melina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Santa Fe. Instituto Nacional de Limnología. Universidad Nacional del Litoral. Instituto Nacional de Limnología; Argentina

Determining which processes take place in the spatial distribution of bacterioplankton metacommunities has been a central goal of microbial ecology. In freshwater ecosystems, selection has been spotted as the main driver shaping bacterial community. However, its relative importance compared with others processes (dispersal, drift, diversification) may depend on spatial heterogeneity and dispersal rates within a metacommunity. Still, a decrease in the role of selection is expected with increasing dispersal homogenization. Here, we investigate the main ecological processes modulating the bacterial assembly in contrasting scenarios of environmental heterogeneity. We carried out a spatiotemporal survey in the floodplain system of Paraná River. The bacterioplankton metacommunity was studied by a step-forward analysis combining different statistical inferences based on the phylogenetic and taxa turnover as well as co-occurrence networks. We found that selection was the main process even at both extremes of environmental heterogeneity and homogeneity, challenging the general view that the strength of selection is weakened due to dispersal homogenization. The ecological processes acting on the community also determined the complexity and randomness of bacterial networks. The heterogeneous selection promoted greater network complexity increasing the β-diversity, and bacterial associations were more random with the increasing influence of stochasticity. Finally, the spatiotemporal heterogeneity was an important factor determining the number and identity of keystone taxa in the system. Integrating all these empirical evidences we propose a new conceptual model that elucidates how the environmental heterogeneity guides the action of ecological processes shaping the bacterial metacommunity.

Hybrid Monte Carlo and adaptive kinetic Monte Carlo calculations have been performed to examine the thermodynamic equilibrium and kinetic properties of a double sided {111} terminated 10 mol% gadolinium doped ceria system. Hybrid Monte Carlo simulations demonstrate that both the concentration of gadolinium ions and oxygen vacancies are enhanced at the surface compared to the bulk. We do not observe the formation of any domain structures at the surface by gadolinium ions. The calculated average activation energy for oxygen transitions from the surface layer is reduced to 0.36 eV, compared to the bulk value of 0.50 eV. Consequently, the ionic conductivity in the surface layers is approximately twice that of the bulk which can be attributed to the surface structure. The adaptive kinetic Monte Carlo simulations found numerous multi-atom concerted diffusion mechanisms spanning large distances which would not have been accounted for in a typical list based kinetic Monte Carlo approach. The taken combined approach is essential to fully understand these complex materials.

cited By 0; International audience; A series of new hybrid donor-acceptor materials based on hexabenzocoronenes (HBC) functionalized with electron donors is investigated by combining a variety of quantum mechanical and molecular dynamic methodologies for use in organic photovoltaic (OPV) devices. Segments of a low band gap alternating copolymer constructed of benzo[1,2-b;3,4-b]dithiophene and thieno[3,4-c]pyrrole-4,6-dione were attached to the conjugated HBC core. The copolymer was chosen for its known high performance in OPVs, and both moieties were singled out due to their exceptional resistance to photo-oxidation, an important requirement for such applications. The macromolecular topology of these systems are expected to induce supra-molecular columns, such as those common to discotic liquid crystals, conducive to the effective percolation of electrons in OPV devices. A challenge with these systems, that of the mixing of the electronic structures of the donor and acceptor moieties that result in excitonic losses and charge recombination, was diminished by trialling a range of linking units. It was found possible to propose ideal donor-acceptor structures with enhanced charge dissociations and transfers in the π-stacking direction for use in OPV and other organic electronic devices.

Antimicrobial peptides (AMPs) are widely occurring host defense agents of interest as one route for addressing the growing problem of multidrug-resistant pathogens. Understanding the mechanisms behind their antipathogen activity is instrumental in designing new AMPs. Herein, we present an all-atom molecular dynamics and free energy study on cecropin B (CB) and its constituent domains. We find a cooperative mechanism in which CB inserts into an anionic model membrane with its amphipathic N-terminal segment, supported by the hydrophobic C-terminal segment of a second peptide. The two peptides interact via a Glu···Lys salt bridge and together sustain a pore in the membrane. Using a modified membrane composition, we demonstrate that when the lower leaflet is overall neutral, insertion of the cationic segment is retarded and thus this mode of action is membrane specific. The observed mode of action utilizes a flexible hinge, a common structural motif among AMPs, which allows CB to insert into the membrane using either or both termini. Data from both unbiased trajectories and enhanced sampling simulations indicate that a requirement for CB to be an effective AMP is the interaction of its hydrophobic C-terminal segment with the membrane. Simulations of these segments in isolation reveal their aggregation in the membrane and a different mechanism of supporting pore formation. Together, our results show the complex interaction of different structural motifs of AMPs and, in particular, a potential role for electronegative side chains in an overall cationic AMP.

The mechanism of the copper(I)-mediated reductive disproportionation reaction of NO to form N2O was investigated for five different 3,5-substituted tris(pyrazolyl)borate copper complexes (CuTpR1,R2) by means of DFT calculations. A thorough search of the potential surface was performed, using the B3LYP functional with the def2-SVP basis set for optimization purposes and def2-TZVP single-point calculations for constructing the potential energy surface for two of these complexes. The results can be condensed into six competing reaction mechanisms, two of which were more closely investigated using full def2-TZVP optimized potential and free energies. The results consistently predict the same mechanism to have the lowest overall barrier. For all five different complexes, this is found to be in good agreement with the experimental reaction barriers. The key intermediate for the transition from the N-bound reactant to the O-bound product contains a stable (NO)3 unit with one N–Cu and one O–Cu bond, which was not...

Fil: Huber, Maria Paula. Consejo Nacional de Investigaciones Cientificas y Tecnicas. Centro Cientifico Tecnologico Conicet - La Plata. Instituto de Investigaciones Biotecnologicas. Instituto de Investigaciones Biotecnologicas "Dr. Raul Alfonsin" (sede Chascomus). Universidad Nacional de San Martin. Instituto de Investigaciones Biotecnologicas. Instituto de Investigaciones Biotecnologicas "Dr. Raul Alfonsin" (sede Chascomus); Argentina

Photosynthetic picoeukaryotes (PPE) are key components of primary production in marine and freshwater ecosystems. In contrast with those of marine environments, freshwater PPE groups have received little attention. In this work, we used flow cytometry cell sorting, microscopy and metabarcoding to investigate the composition of small photosynthetic eukaryote communities from six eutrophic shallow lakes in South America, Argentina. We compared the total molecular diversity obtained from PPE sorted populations as well as from filtered total plankton samples (FTP). Most reads obtained from sorted populations belonged to the classes: Trebouxiophyceae, Chlorophyceae and Bacillariophyceae. We retrieved sequences from non-photosynthetic groups, such as Chytridiomycetes and Ichthyosporea which contain a number of described parasites, indicating that these organisms were probably in association with the autotrophic cells sorted. Dominant groups among sorted PPEs were poorly represented in FTP and their richness was on average lower than in the sorted samples. A significant number of operational taxonomic units (OTUs) were exclusively found in sorting samples, emphasizing that sequences from FTP underestimate the diversity of PPE. Moreover, 22% of the OTUs found among the dominant groups had a low similarity (

Trebouxiophyceae are a ubiquitous class of Chlorophyta encountered in aquatic and terrestrial environments. Most taxa are photosynthetic, and many acts as photobionts in symbiotic relationships, while others are free-living. Trebouxiophyceae have also been widely investigated for their use for biotechnological applications. In this work, we aimed at obtaining a comprehensive image of their diversity by compiling the information of 435 freshwater, soil and marine environmental DNA samples surveyed with Illumina sequencing technology in order to search for the most relevant environments for bioprospecting. Freshwater and soil were most diverse and shared more than half of all operational taxonomic units (OTUs), however, their communities were significantly distinct. Oceans hosted the highest genetic novelty, and did not share any OTUs with the other environments; also, marine samples host more diversity in warm waters. Symbiotic genera usually found in lichens such as Trebouxia, Myrmecia and Symbiochloris were also abundantly detected in the ocean, suggesting either free-living lifestyles or unknown symbiotic relationships with marine planktonic organisms. Altogether, our study opens the way to new prospection for trebouxiophycean strains, especially in understudied environments like the ocean., EL wishes to acknowledge the program ‘Atracción de talentos de la Comunidad de Madrid’ (grant 2017-T1/AMB-5210 4) and Swiss National Fund project SNF 31003A_163254 for funding. The project was funding by the ANPCyT ‘Agencia Nacional de Promoción Científica y Tecnológica’ (PICT-2014-1290; PICT-2016-1079). The Swiss NSF (P2NEP3_178543) to D.S.

The tin sulfides and selenides have a range of applications spanning photovoltaics and thermoelectrics to photocatalysts and photodetectors. However, significant challenges remain to widespread use, including electrical and chemical incompatibilities between SnS and device contact materials and the environmental toxicity of selenium. Solid solutions of isostructural sulfide and selenide phases could provide scope for optimizing physical properties against sustainability requirements, but this has not been comprehensively explored. This work presents a detailed modeling study of the Pnma and rocksalt Sn(S1-x Se x ), Sn(S1-x Se x )2, and Sn2(S1-x Se x )3 solid solutions. All four show an energetically favorable and homogenous mixing at all compositions, but rocksalt Sn(S1-x Se x ) and Sn2(S1-x Se x )3 are predicted to be metastable and accessible only under certain synthesis conditions. Alloying leads to a predictable variation of the bandgap, density of states, and optical properties with composition, allowing SnS2 to be "tuned down" to the ideal Shockley-Queisser bandgap of 1.34 eV. The impact of forming the solid solutions on the lattice dynamics is also investigated, providing insight into the enhanced performance of Sn(S1-x Se x ) solid solutions for thermoelectric applications. These results demonstrate that alloying affords facile and precise control over the electronic, optical, and vibrational properties, allowing material performance for optoelectronic applications to be optimized alongside a variety of practical considerations.

17 pages, 5 figures, 3 tables, supplemental material https://doi.org/10.1128/AEM.02659-18.-- Data availability.All sequences generated in this study can be accessed through European Nucleotide Archive (ENA) under the study accession number PRJEB27291 and accession numbers ERR2639355 to ERR2639364, High-throughput sequencing (HTS) of the 16S rRNA gene has been used successfully to describe the structure and dynamics of microbial communities. Picocyanobacteria are important members of bacterioplankton communities, and, so far, they have predominantly been targeted using universal bacterial primers, providing a limited resolution of the picocyanobacterial community structure and dynamics. To increase such resolution, the study of a particular target group is best approached with the use of specific primers. Here, we aimed to design and evaluate specific primers for aquatic picocyanobacterial genera to be used with high-throughput sequencing. Since the various regions of the 16S rRNA gene have different degrees of conservation in different bacterial groups, we therefore first determined which hypervariable region of the 16S rRNA gene provides the highest taxonomic and phylogenetic resolution for the genera Synechococcus, Prochlorococcus, and Cyanobium. An in silico analysis showed that the V5, V6, and V7 hypervariable regions appear to be the most informative for this group. We then designed primers flanking these hypervariable regions and tested them in natural marine and freshwater communities. We successfully detected that most (97%) of the obtained reads could be assigned to picocyanobacterial genera. We defined operational taxonomic units as exact sequence variants (zero-radius operational taxonomic units [zOTUs]), which allowed us to detect higher genetic diversity and infer ecologically relevant information about picocyanobacterial community composition and dynamics in different aquatic systems. Our results open the door to future studies investigating picocyanobacterial diversity in aquatic systems, This study was supported by the Argentinean Network for the Assessment and Monitoring of Pampean Shallow Lakes (PAMPA2–CONICET), the ANPCyT (PICT-2014-1290 and PICT-2016-1079), and by MAGGY (grant CTM2017-87736-R) to S. G. Acinas and REMEI (grant CTM2015-70340-R) to J. M. Gasol from the Spanish Ministry of Economy and Competitiveness (MINECO)

Solid oxide fuel cells are an important class of energy conversion devices in the search to replace fossil fuels. Their electrodes’ materials mostly belong to the perovskite family, which in their versatile composition are numerous; here we focus on the perovskite LaCoxFe1−xO3 and examine its electronic structure for x ≤ 0.5 using density functional theory with a plane wave basis and pseudopotentials. The resulting lattice parameters show good agreement with experiment, and the Mulliken and Bader charges show that iron and cobalt mostly remain as Fe3+ and Co3+ throughout an increasing Co:Fe ratio. The charge and spin magnitudes of oxygen ions is determined by their local, cation neighbors with the largest charge and spin magnitudes found on oxygen ions sandwiched between two Fe ions. Density of states and partial density of states analyses reveal that increasing the ratio of Co to Fe in oxygen stoichiometric materials decreases their relative, semi-conducting nature toward insulating, by virtue of the decrease in the number of (conducting) O–Fe–O bonds and the increase in (insulating) O–Co–O bonds. The appearance of an intermediate spin state of Co and examination of its PDOS confirms the hypothesis that Co–O, d–p hybridization is a necessary factor for its occurrence.

Glyphosate-based herbicides are the most commonly used herbicide worldwide. Although glyphosate is known to be toxic to aquatic organisms, it can also have stimulatory effects on small-size (ø2 µm) cyanobacteria (Pcy) able to metabolize and degrade glyphosate and AMPA. Several previous experimental studies in micro- and mesocosms reported increases of Pcy abundance in response to glyphosate additions, but comparable field evidence is presently unavailable. We surveyed a large geographical area in order to collect information on Pcy abundance from lakes within the Pampa region (with over three decades of glyphosate usage) and lakes from Patagonia (with virtually no history of glyphosate usage). Fifty-two Pampean lakes and 24 Patagonian lakes were surveyed. We used three indicators of glyphosate impact: herbicide concentration, the presence of phosphonate metabolism genes (responsible for glyphosate and AMPA degradation) in environmental DNA samples, and descriptors of land use in the surrounding area of each lake. We addressed three questions: (1) is there field evidence of stimulatory effects of glyphosate on picocyanobacteria abundance? (2) is the magnitude of the effects of glyphosate in natural systems comparable to that reported under controlled experimental conditions? and (3), how do the effects of glyphosate compare to the effects of other potential environmental drivers of Pcy biomass? The collected evidence is consistent with the hypothesis that long-term agricultural practices relying on glyphosate-based technologies had important effects on freshwater microbial communities, particularly by promoting increases in picocyanobacteria abundance.

The flagellated protozoan parasite Trichomonas vaginalis is the etiologic agent of trichomoniasis, the most common non-viral sexually transmitted infection worldwide. As an obligate extracellular pathogen, adherence to epithelial cells is critical for parasite survival within the human host and a better understanding of this process is a prerequisite for the development of therapies to combat infection. In this sense, recent work has shown S-acylation as a key modification that regulates pathogenesis in different protozoan parasites. However, there are no reports indicating whether this post-translational modification is a mechanism operating in T. vaginalis. In order to study the extent and function of S-acylation in T. vaginalis biology, we undertook a proteomic study to profile the full scope of S-acylated proteins in this parasite and reported the identification of 363 proteins involved in a variety of biological processes such as protein transport, pathogenesis related and signaling, among others. Importantly, treatment of parasites with the palmitoylation inhibitor 2-bromopalmitate causes a significant decrease in parasite: Parasite aggregation as well as adherence to host cells suggesting that palmitoylation could be modifying proteins that are key regulators of Trichomonas vaginalis pathogenesis. Fil: Nievas, Yésica Romina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Vashisht, Ajay A.. University of California; Estados Unidos Fil: Corvi, Maria Martha. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Metz, Sebastián Darío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Johnson, Patricia J. University of California; Estados Unidos Fil: Wohlschlegel, James A.. University of California; Estados Unidos Fil: de Miguel, Natalia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina

Dye-sensitized solar cells (DSCs) have been the subject of wide-ranging studies for many years because of their potential for large-scale manufacturing using roll-to-roll processing allied to their use of earth abundant raw materials. Two main challenges exist for DSC devices to achieve this goal; uplifting device efficiency from the 12 to 14% currently achieved for laboratory-scale ‘hero’ cells and replacement of the widely-used liquid electrolytes which can limit device lifetimes. To increase device efficiency requires optimized dye injection and regeneration, most likely from multiple dyes while replacement of liquid electrolytes requires solid charge transporters (most likely hole transport materials – HTMs). While theoretical and experimental work have both been widely applied to different aspects of DSC research, these approaches are most effective when working in tandem. In this context, this perspective paper considers the key parameters which influence electron transfer processes in DSC devices using one or more dye molecules and how modelling and experimental approaches can work together to optimize electron injection and dye regeneration., Graphical Abstract This paper provides a perspective that theory and experiment are best used in tandem to study DSC devices

Clay–polymer nanocomposite materials have gained much attention owing to their low weight ratio of filler to reinforcement properties, delivering lightweight yet resilient materials with excellent barrier properties to gas diffusion. An important process in their production is clay exfoliation, as maximum reinforcement and improvement of barrier properties occur when the clay mineral platelets are fully separated and dispersed through the polymer matrix with a preferred orientation. In this study we examine clay swelling—the first step leading to exfoliation—using molecular dynamics to generate solvation energetics, swelling curves, and atomic density profiles of three types of clay minerals—montmorillonite, vermiculite, and hectorite—with interlayer Na+ cations and/or three quaternary ammonium surfactants in water and ethanol. Analysis based on the provided simulations can help to distinguish between favorable and unfavorable swelling profiles of mineral/surfactant/solvent systems and therefore guide fur...

The mechanism of the copper(I)-mediated reductive disproportionation reaction of NO to form N

We analyzed the interplay between neutral and deterministic processes in maintaining contrasting alternative bacterioplankton communities through time in highly productive shallow lakes and evaluated the relevance of these processes when a regime shift from a clear to a turbid state occurred. We observed that local assembly is ruled primary deterministically, via local habitat filtering, with a secondary role of stochastic processes. We also found a hierarchy in the environmental sorting: while an unusual Verrucomicrobia dominance characterizes the three systems, local conditions limit within-bacterial community membership to closely phylogenetically related and ecologically similar taxa. These results indicate that bacterial abilities to establish in these lakes are strongly determined by their traits, and point toward special physiological adaptations to persist when these systems undergo a regime shift. Altogether, these results hint to a divergence in function among these alternative communities, mediated by major shifts in bacterial community trait structure, particularly regarding carbon use. Fil: Llames, Maria Eugenia del Rosario. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Huber, Maria Paula. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Metz, Sebastián Darío. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina Fil: Unrein, Fernando. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús). Universidad Nacional de San Martín. Instituto de Investigaciones Biotecnológicas. Instituto de Investigaciones Biotecnológicas "Dr. Raúl Alfonsín" (sede Chascomús); Argentina

Organic molecules with a permanent electric dipole moment have been widely used as a template for further growth of molecular layers in device structures. Key properties of the resulting organic films such as energy level alignment (ELA), work function, and injection/collection barrier are linked to the magnitude and direction of the dipole moment at the interface. Using angle-resolved photoemission spectroscopy (ARPES), we have systematically investigated the coverage-dependent work function and spectral line shapes of occupied molecular energy states (MESs) of chloroaluminium-phthalocyanine (ClAlPc) grown on Ag(111). We demonstrate that the dipole orientation of the first ClAlPc layer can be controlled by adjusting the deposition rate and postannealing conditions, and we find that the ELA at the interface differs by $\ensuremath{\sim}0.4\phantom{\rule{0.16em}{0ex}}\mathrm{eV}$ between the Cl up and down configurations of the adsorbed ClAlPc molecules. These observations are rationalized by density functional theory (DFT) calculations based on a realistic model of the ClAlPc/Ag(111) interface, which reveal that the different orientations of the ClAlPc dipole layer lead to different charge-transfer channels between the adsorbed ClAlPc and Ag(111) substrate. Our findings provide a useful framework toward method development for ELA tuning.

Pfadabhangiges Verhalten bei Direktinvestitionsentscheidungen, das in ineffizienten Handeln von einzelnen Unternehmen oder von Unternehmenspopulationen resultieren kann, spielt insbesondere in der empirischen Forschung eine untergeordnete Rolle, obwohl zahlreiche Arbeiten des Internationalen Managements dynamisch zeitliche und raumliche Interaktionseffekte beschreiben, die ein solches Verhalten begrunden konnen. Ziel dieser Studie ist es, empirisch zu untersuchen, welche Relevanz unterschiedliche Interaktionseffekte fur die Direktinvestitionsentscheidung haben und inwiefern diese zu einem pfadabhangigen Verhalten fuhren. Hierzu schatzen wir dynamisch raumliche Paneldaten-Regressionsmodelle fur deutsche Direktinvestitionen (1994–2010) und die Ergebnisse zeigen, dass das Direktinvestitionsverhalten deutscher Unternehmen einer pfadabhangigen Prozesslogik folgt. So konvergiert der Entwicklungsprozess von Direktinvestitionsbestanden zwar innerhalb eines Gastlandes langfristig gegen ein Gleichgewicht, jedoch divergieren zwischen verschiedenen Landergruppen die Bestande, da diese aufgrund dynamisch zeitlicher Effekte unterschiedlichen Wachstumspfaden folgen. Weiterhin werden erstmalig explizit interorganisationale Interaktionseffekte nachgewiesen, welche in Landergruppen mit geringer anfanglicher Direktinvestitionsintensitat oder geringem Entwicklungsniveau einen signifikant positiven Einfluss auf deutsche Direktinvestitionen ausuben. Auch zeigt sich, dass Interaktionseffekte zwischen Gastlandern bestehen, die zu einem raumlichen pfadabhangigen Expansionsprozess fuhren konnen.

Das Forschungsfeld des Internationalen Managements ist gepragt durch eine Vielzahl von Partialtheorien. Zahlreiche dieser Theorien verstehen die Internationalisierung als dynamischen Prozess, unterscheiden sich jedoch hinsichtlich der Erklarungsfaktoren. Einigen beschreiben den Internationalisierungsprozess als inkremental durch die Unternehmensvergangenheit gepragt, andere heben die Bedeutung externer Faktoren hervor und wieder andere berucksichtigen beide Erklarungsansatze. Um diese unterschiedlichen Betrachtungsebenen zu integrieren wird im vorliegenden Beitrag ein mehrdimensionales coevolutionares Modell entwickelt. In diesem Kontext wird aus pfadabhangigkeitstheoretischer Perspektive untersucht, welche unternehmensinternen und -externen Faktoren auf die Entscheidungstrager bei der Internationalisierung wirken, wobei explizit zwischen initialen Internationalisierungsentscheidungen und solchen wahrend des laufenden Internationalisierungsprozesses unterschieden wird, mit dem Ziel ein ganzheitliches Bild der Relevanz pfadabhangigkeitstheoretischer Uberlegungen fur den Internationalisierungsprozess von Unternehmen zu erlangen.

In diesem Beitrag wird die Entwicklung von Routinen und organisationalen Fahigkeiten aus pfadtheoretischer Perspektive untersucht. Ein Hauptaugenmerk wird auf die Entstehungsphase und die den weiteren Verlauf bestimmenden Mechanismen gelegt. Die Analyse anhand typischer pfadabhangigkeitstheoretischer Merkmale zeigt dabei die hohe Relevanz pfadtheoretischer Uberlegungen in diesem Themenfeld. Es wird dargelegt, dass die Entwicklung von Routinen und organisationalen Fahigkeiten durch zahlreiche positive Ruckkopplungseffekte gepragt ist und dass diese nicht unabhangig voneinander wirken, sondern Wechselwirkungen zwischen diesen bestehen. Dieses Zusammenspiel verschiedener Ruckkopplungseffekte liefert einen Erklarungsbeitrag dazu, inwiefern Routinen zu organisationalen Fahigkeiten emergieren konnen. Ein weiteres Ergebnis ist, dass pfadabhangige Entwicklungen nicht nur innerhalb eines einzelnen Prozesses wirken, sondern verschiedene Prozesse aufgrund paralleler und sequentieller Interdependenzen in Verbindung stehen; letztere sind insbesondere auch fur die Entwicklung dynamischer Fahigkeiten von Bedeutung. Zusammenfassend konnen pfadabhangigkeitstheoretische Uberlegungen als Untersuchungsgrundlage dienen, unternehmensweite zu Inflexibilitat fuhrende Entwicklungen zu erklaren.

Im vorliegenden Beitrag wird die auslandische Standortwahl von Unternehmen untersucht, wobei letztere als Teile einer Unternehmenspopulation verstanden werden. Im Mittelpunkt steht die Fragestellung, welche Auswirkungen das Handeln von Populationsmitgliedern untereinander auf die Internationalisierungsaktivitaten einzelner Unternehmen hat. Die folgende Analyse zeigt, dass komplexe nicht-lineare Wirkungszusammenhange zwischen den verschiedenen Akteuren bestehen, welche einen pfadabhangigen Internationalisierungsprozess von Unternehmenspopulationen begrunden. Dieser begunstigt eine Ballung von Direktinvestitionsbestanden in bestimmten Landern und kann zu temporar ineffizienten Allokationen von Direktinvestitionsbestanden fuhren. Andererseits besteht gerade fur wenig entwickelte Lander, welche uber ein geringes Direktinvestitionsniveau verfugen, die Chance, durch investitionsfordernde Masnahmen einen Prozess zu initiieren, welcher sich durch einen wechselseitigen selbstverstarkenden Effekt einerseits zwischen auslandischen Unternehmen und andererseits zwischen diesen und den landerspezifischen Determinanten auszeichnet.

DL_MESO is a parallel mesoscale simulation package capable of dissipative particle dynamics and the lattice Boltzmann equation method. It has been developed at Daresbury Laboratory for the United Kingdom Collaborative Computational Project known as CCP5. Capable of addressing industrially relevant tasks, but written to support academic research, it has a wide range of applications and scales to thousands of processors on high-performance computing platforms yet runs efficiently on smaller commodity clusters and single processor personal computers. This article serves as a guide to a variety of users, describing the functionality, performance and structure of this simulation package. Representative examples highlighting the capabilities of DL_MESO are given for each of the two methodologies available. Future directions for the package are discussed towards the end of the article.

ChemShell is a modular computational chemistry package with a particular focus on hybrid quantum mechanical/molecular mechanical (QM/MM) simulations. A core set of chemical data handling modules and scripted interfaces to a large number of quantum chemistry and molecular modeling packages underpin a flexible QM/MM scheme. ChemShell has been used in the study of small molecules, molecular crystals, biological macromolecules such as enzymes, framework materials including zeolites, ionic solids, and surfaces. We outline the range of QM/MM coupling schemes and supporting functions for system setup, geometry optimization, and transition-state location (including those from the open-source DL-FIND optimization library). We discuss recently implemented features allowing a more efficient treatment of long range electrostatic interactions, X-ray based quantum refinement of crystal structures, free energy methods, and excited-state calculations. ChemShell has been ported to a range of parallel computers and we describe a number of options including parallel execution based on the message-passing capabilities of the interfaced packages and task-farming for applications in which a number of individual QM, MM, or QM/MM calculations can performed simultaneously. We exemplify each of the features by brief reference to published applications.