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Rapid Synthesis of Sub-10nm Hexagonal NaYF4-Based Upconverting Nanoparticles using Therminol((R))66
(2018)
We report a simple one-pot method for the rapid preparation of sub-10nm pure hexagonal (-phase) NaYF4-based upconverting nanoparticles (UCNPs). Using Therminol((R))66 as a co-solvent, monodisperse UCNPs could be obtained in unusually short reaction times. By varying the reaction time and reaction temperature, it was possible to control precisely the particle size and crystalline phase of the UCNPs. The upconversion (UC) luminescence properties of the nanocrystals were tuned by varying the concentrations of the dopants (Nd3+ and Yb3+ sensitizer ions and Er3+ activator ions). The size and phase-purity of the as-synthesized core and core-shell nanocrystals were assessed by using complementary transmission electron microscopy, dynamic light scattering, X-ray diffraction, and small-angle X-ray scattering studies. In-depth photophysical evaluation of the UCNPs was pursued by using steady-state and time-resolved luminescence spectroscopy. An enhancement in the UC intensity was observed if the nanocrystals, doped with optimized concentrations of lanthanide sensitizer/activator ions, were further coated with an inert/active shell. This was attributed to the suppression of surface-related luminescence quenching effects.
Effective communication among sympatric species is often instrumental for behavioural isolation, where the failure to successfully discriminate between potential mates could lead to less fit hybrid offspring. Discrimination between con- and heterospecifics tends to occur more often in the sex that invests more in offspring production, i.e. females, but males may also mediate reproductive isolation. In this study, we show that among two Campylomormyrus Africanweakly electric fish species, males preferentially associate with conspecific females during choice tests using live fish as stimuli, i.e. when all sensory modalities potentially used for communication were present. We then conducted playback experiments to determine whether the species-specific electric organ discharge (EOD) used for electrocommunication serves as the cue for this conspecific association preference. Interestingly, only C. compressirostris males associated significantly more with the conspecific EOD waveform when playback stimuli were provided, while no such association preference was observed in C. tamandua males. Given our results, the EOD appears to serve, in part, as a male-mediated pre-zygotic isolation mechanism among sympatric species. However, the failure of C. tamandua males to discriminate between con- and heterospecific playback discharges suggests that multiple modalities may be necessary for species recognition in some African weakly electric fish species.
Germination, a crucial phase in the life cycle of a plant, can be significantly influenced by competition and facilitation. The aim of this study was to test whether differences in cover of surrounding vegetation can lead to population differentiation in germination behaviour of an annual grassland species, and if so, whether such a differentiation can be found in the native as well as in the introduced range. We used maternal progeny of Erodium cicutarium previously propagated under uniform conditions that had been collected in multiple populations in the native and two introduced ranges, in populations representing extremes in terms of mean and variability of the cover of surrounding vegetation. In the first experiment, we tested the effect of germination temperature and mean cover at the source site on germination, and found interlinked effects of these factors. In seeds from one of the introduced ranges (California), we found indication for a 2-fold dormancy, hindering germination at high temperatures even if physical dormancy was broken and water was available. This behaviour was less strong in high cover populations, indicating cross-generational facilitating effects of dense vegetation. In the second experiment, we tested whether spatial variation in cover of surrounding vegetation has an effect on the proportion of dormant seeds. Contrary to our expectations, we found that across source regions, high variance in cover was associated with higher proportions of seeds germinating directly after storage. In all three regions, germination seemed to match the local environment in terms of climate and vegetation cover. We suggest that this is due to a combined effect of introduction of preadapted genotypes and local evolutionary processes.
Arsenic-containing hydrocarbons (AsHCs), a subgroup of arsenolipids (AsLs) occurring in fish and edible algae, possess a substantial neurotoxic potential in fully differentiated human brain cells. Previous in vivo studies indicating that AsHCs cross the blood–brain barrier of the fruit fly Drosophila melanogaster raised the question whether AsLs could also cross the vertebrate blood–brain barrier (BBB). In the present study, we investigated the impact of several representatives of AsLs (AsHC 332, AsHC 360, AsHC 444, and two arsenic-containing fatty acids, AsFA 362 and AsFA 388) as well as of their metabolites (thio/oxo-dimethylpropionic acid, dimethylarsinic acid) on porcine brain capillary endothelial cells (PBCECs, in vitro model for the blood–brain barrier). AsHCs exerted the strongest cytotoxic effects of all investigated arsenicals as they were up to fivefold more potent than the toxic reference species arsenite (iAsIII). In our in vitro BBB-model, we observed a slight transfer of AsHC 332 across the BBB after 6 h at concentrations that do not affect the barrier integrity. Furthermore, incubation with AsHCs for 72 h led to a disruption of the barrier at sub-cytotoxic concentrations. The subsequent immunocytochemical staining of three tight junction proteins revealed a significant impact on the cell membrane. Because AsHCs enhance the permeability of the in vitro blood–brain barrier, a similar behavior in an in vivo system cannot be excluded. Consequently, AsHCs might facilitate the transfer of accompanying foodborne toxicants into the brain.
Understanding and reducing complex systems pharmacology models based on a novel input-response index
(2018)
A growing understanding of complex processes in biology has led to large-scale mechanistic models of pharmacologically relevant processes. These models are increasingly used to study the response of the system to a given input or stimulus, e.g., after drug administration. Understanding the input–response relationship, however, is often a challenging task due to the complexity of the interactions between its constituents as well as the size of the models. An approach that quantifies the importance of the different constituents for a given input–output relationship and allows to reduce the dynamics to its essential features is therefore highly desirable. In this article, we present a novel state- and time-dependent quantity called the input–response index that quantifies the importance of state variables for a given input–response relationship at a particular time. It is based on the concept of time-bounded controllability and observability, and defined with respect to a reference dynamics. In application to the brown snake venom–fibrinogen (Fg) network, the input–response indices give insight into the coordinated action of specific coagulation factors and about those factors that contribute only little to the response. We demonstrate how the indices can be used to reduce large-scale models in a two-step procedure: (i) elimination of states whose dynamics have only minor impact on the input–response relationship, and (ii) proper lumping of the remaining (lower order) model. In application to the brown snake venom–fibrinogen network, this resulted in a reduction from 62 to 8 state variables in the first step, and a further reduction to 5 state variables in the second step. We further illustrate that the sequence, in which a recursive algorithm eliminates and/or lumps state variables, has an impact on the final reduced model. The input–response indices are particularly suited to determine an informed sequence, since they are based on the dynamics of the original system. In summary, the novel measure of importance provides a powerful tool for analysing the complex dynamics of large-scale systems and a means for very efficient model order reduction of nonlinear systems.
Reducing uncertainties about carbon cycling is important in the Arctic where rapid environmental changes contribute to enhanced mobilization of carbon. Here we quantify soil organic carbon (SOC) contents of permafrost soils along the Yukon Coastal Plain and determine the annual fluxes from coastal erosion. Different terrain units were assessed based on surficial geology, morphology, and ground ice conditions. To account for the volume of wedge ice and massive ice in a unit, SOC contents were reduced by 19% and sediment contents by 16%. The SOC content in a 1m(2) column of soil varied according to the height of the bluff, ranging from 30 to 662kg, with a mean value of 183kg. Forty-four per cent of the SOC was within the top 1m of soil and values varied based on surficial materials, ranging from 30 to 53kg C/m(3), with a mean of 41kg. Eighty per cent of the shoreline was erosive with a mean annual rate of change of -0.7m/yr. This resulted in a SOC flux per meter of shoreline of 132kg C/m/yr, and a total flux for the entire 282km of the Yukon coast of 35.5 x 10(6) kg C/yr (0.036 Tg C/yr). The mean flux of sediment per meter of shoreline was 5.3 x 10(3) kg/m/yr, with a total flux of 1,832 x 10(6)kg/yr (1.832 Tg/yr). Sedimentation rates indicate that approximately 13% of the eroded carbon was sequestered in nearshore sediments, where the overwhelming majority of organic carbon was of terrestrial origin. Plain Language Summary The oceans help slow the buildup of carbon dioxide (CO2) because they absorb much of this greenhouse gas. However, if carbon from other sources is added to the oceans, it can affect their ability to absorb atmospheric CO2. Our study examines the organic carbon added to the Canadian Beaufort Sea from eroding permafrost along the Yukon coast, a region quite vulnerable to erosion. Understanding carbon cycling in this area is important because environmental changes in the Arctic such as longer open water seasons, rising sea levels, and warmer air, water and soil temperatures are likely to increase coastal erosion and, thus, carbon fluxes to the sea. We measured the carbon in different types of permafrost soils and applied corrections to account for the volume taken up by various types of ground ice. By determining how quickly the shoreline is eroding, we assessed how much organic carbon is being transferred to the ocean each year. Our results show that 36 x 10(6) kg of carbon is added annually from this section of the coast. If we extrapolate these results to other coastal areas along the Canadian Beaufort Sea, the flux of organic carbon is nearly 3 times what was previously thought.
Previous thermomechanical modeling studies indicated that variations in the temperature and strength of the crystalline crust might be responsible for the juxtaposition of domains with thin-skinned and thick-skinned crustal deformation along strike the foreland of the central Andes. However, there is no evidence supporting this hypothesis from data-integrative models. We aim to derive the density structure of the lithosphere by means of integrated 3-D density modeling, in order to provide a new basis for discussions of compositional variations within the crust and for future thermal and rheological modeling studies. Therefore, we utilize available geological and geophysical data to obtain a structural and density model of the uppermost 200km of the Earth. The derived model is consistent with the observed Bouguer gravity field. Our results indicate that the crystalline crust in northern Argentina can be represented by a lighter upper crust (2,800kg/m(3)) and a denser lower crust (3,100kg/m(3)). We find new evidence for high bulk crustal densities >3,000kg/m(3) in the northern Pampia terrane. These could originate from subducted Puncoviscana wackes or pelites that ponded to the base of the crystalline crust in the late Proterozoic or indicate increasing bulk content of mafic material. The precise composition of the northern foreland crust, whether mafic or felsic, has significant implications for further thermomechanical models and the rheological behavior of the lithosphere. A detailed sensitivity analysis of the input parameters indicates that the model results are robust with respect to the given uncertainties of the input data.
In catastrophe risk modeling, a defensible estimation of impact severity and its likelihood of occurrence to a portfolio of assets can only be made through a rigorous treatment of uncertainty and the consideration of multiple alternative models. This approach, however, requires repeating lengthy calculations multiple times. To limit the demand on computational time and resources, a frequent practice in the industry is to estimate the distribution of earthquake-induced portfolio losses using a simulated catalog of events from a single representative mean ground motion hazard model for the region. This simplified approach is faster but may provide biased estimates of the likelihood of occurrence of the large and infrequent losses that drive many risk mitigation decisions. Investigation through case studies of different portfolios of assets located in the San Francisco Bay Region shows the potential for both a bias in the mean loss estimates and an underestimation of their central 70% interpercentile. We propose a simplified and computationally practical approach that reduces the bias in the mean portfolio loss estimates. This approach does not improve the estimate of the interpercentile range, however, a quantity of no direct practical use.
Phytochemical investigation of the CH2Cl2/MeOH (1:1) extract of the roots of Lannea rivae (Chiov) Sacleux (Anacardiaceae) led to the isolation of a new alkenyl cyclohexenone derivative: (4R,6S)-4,6-dihydroxy-6-((Z)-nonadec-14′-en-1-yl)cyclohex-2-en-1-one (1), and a new alkenyl cyclohexanol derivative: (2S*,4R*,5S*)-2,4,5-trihydroxy-2-((Z)-nonadec-14′-en-1-yl)cyclohexanone (2) along with four known compounds, namely epicatechin gallate, taraxerol, taraxerone and β-sitosterol; while the stem bark afforded two known compounds, daucosterol and lupeol. Similar investigation of the roots of Lannea schweinfurthii (Engl.) Engl. led to the isolation of four known compounds: 3-((E)-nonadec-16′-enyl)phenol, 1-((E)-heptadec-14′-enyl)cyclohex-4-ene-1,3-diol, catechin, and 1-((E)-pentadec-12′-enyl)cyclohex-4-ene-1,3-diol. The structures of the isolated compounds were determined by NMR spectroscopy and mass spectrometry. The absolute configuration of compound 1 was established by quantum chemical ECD calculations. In an antibacterial activity assay using the microbroth kinetic method, compound 1 showed moderate activity against Escherichia coli while compound 2 exhibited moderate activity against Staphylococcus aureus. Compound 1 also showed moderate activity against E. coli using the disc diffusion method. The roots extract of L. rivae was notably cytotoxic against both the DU-145 prostate cancer cell line and the Vero mammalian cell line (CC50 = 5.24 and 5.20 μg/mL, respectively). Compound 1 was also strongly cytotoxic against the DU-145 cell line (CC50 = 0.55 μg/mL) but showed no observable cytotoxicity (CC50 > 100 μg/mL) against the Vero cell line. The roots extract of L. rivae and L. schweinfurthii, epicatechin gallate as well as compound 1 exhibited inhibition of carageenan-induced inflammation.
Mimicking non-verbal emotional expressions and empathy development in simulated consultations
(2018)
Objective: To explore the feasibility of applying an experimental design to study the relationship between non-verbal emotions and empathy development in simulated consultations.
Method: In video-recorded simulated consultations, twenty clinicians were randomly allocated to either an experimental group (instructed to mimic non-verbal emotions of a simulated patient, SP) or a control group (no such instruction). Baseline empathy scores were obtained before consultation, relational empathy was rated by SP after consultation. Multilevel logistic regression modelled the probability of mimicry occurrence, controlling for baseline empathy and clinical experience. ANCOVA compared group differences on relational empathy and consultation smoothness.
Results: Instructed mimicry lasted longer than spontaneous mimicry. Mimicry was marginally related to improved relational empathy. SP felt being treated more like a whole person during consultations with spontaneous mimicry. Clinicians who displayed spontaneous mimicry felt consultations went more smoothly.
Conclusion: The experimental approach improved our understanding of how non-verbal emotional mimicry contributed to relational empathy development during consultations. Further work should ascertain the potential of instructed mimicry to enhance empathy development.
Practice implications: Understanding how non-verbal emotional mimicry impacts on patients’ perceived clinician empathy during consultations may inform training and intervention programme development.
Participatory design (PD) in HCI has been successfully applied to vulnerable groups, but further research is still needed on forced migrants. We report on a month-long case study with a group of about 25 young forced migrants (YFMs), where we applied and adapted strategies from PD and participatory research (PR). We gained insights into the benefits and drawbacks of combining PD and PR concepts in this particular scenario. The PD+PR approach supported intercultural collaborations between YFMs and young members of the host community. It also enabled communication across language barriers by using visual and “didactic reduction” resources. On a theoretical level, the experiences we gained allowed us to reflect on the role of “safe spaces” for participation and the need for further discussing it in PD. Our results can benefit researchers who take part in technology-related participatory processes with YFMs.
Retrieval of water constituents from hyperspectral in-situ measurements under variable cloud cover
(2018)
Remote sensing and field spectroscopy of natural waters is typically performed under clear skies, low wind speeds and low solar zenith angles. Such measurements can also be made, in principle, under clouds and mixed skies using airborne or in-situ measurements; however, variable illumination conditions pose a challenge to data analysis. In the present case study, we evaluated the inversion of hyperspectral in-situ measurements for water constituent retrieval acquired under variable cloud cover. First, we studied the retrieval of Chlorophyll-a (Chl-a) concentration and colored dissolved organic matter (CDOM) absorption from in-water irradiance measurements. Then, we evaluated the errors in the retrievals of the concentration of total suspended matter (TSM), Chl-a and the absorption coefficient of CDOM from above-water reflectance measurements due to highly variable reflections at the water surface. In order to approximate cloud reflections, we extended a recent three-component surface reflectance model for cloudless atmospheres by a constant offset and compared different surface reflectance correction procedures. Our findings suggest that in-water irradiance measurements may be used for the analysis of absorbing compounds even under highly variable weather conditions. The extended surface reflectance model proved to contribute to the analysis of above-water reflectance measurements with respect to Chl-a and TSM. Results indicate the potential of this approach for all-weather monitoring.
The increasing availability of earth observations necessitates mathematical methods to optimally combine such data with hydrologic models. Several algorithms exist for such purposes, under the umbrella of data assimilation (DA). However, DA methods are often applied in a suboptimal fashion for complex real-world problems, due largely to several practical implementation issues. One such issue is error characterization, which is known to be critical for a successful assimilation. Mischaracterized errors lead to suboptimal forecasts, and in the worst case, to degraded estimates even compared to the no assimilation case. Model uncertainty characterization has received little attention relative to other aspects of DA science. Traditional methods rely on subjective, ad hoc tuning factors or parametric distribution assumptions that may not always be applicable. We propose a novel data-driven approach (named SDMU) to model uncertainty characterization for DA studies where (1) the system states are partially observed and (2) minimal prior knowledge of the model error processes is available, except that the errors display state dependence. It includes an approach for estimating the uncertainty in hidden model states, with the end goal of improving predictions of observed variables. The SDMU is therefore suited to DA studies where the observed variables are of primary interest. Its efficacy is demonstrated through a synthetic case study with low-dimensional chaotic dynamics and a real hydrologic experiment for one-day-ahead streamflow forecasting. In both experiments, the proposed method leads to substantial improvements in the hidden states and observed system outputs over a standard method involving perturbation with Gaussian noise.
Students' achievement emotions are critical in their academic development. Therefore, teachers need to create an emotionally positive learning environment. In the light of this, the present study investigated the connection between students' enjoyment, anxiety, boredom and, in the first case, students' academic self-concept and, in the second, teachers' diagnostic skills. The third part of our study examined whether this link would be moderated by students' academic self-concept. Our sample comprised N = 1803 eighth-grade students who reported their achievement emotions and evaluated the diagnostic skills of both their German and mathematics teachers. Hierarchical models indicated that students experience more enjoyment and less anxiety and boredom if teachers exhibit better diagnostic skills. The role of teachers' diagnostic skills in relation to students' emotions was in part moderated by the students' self-concept. These results are discussed in terms of their implications for effective teaching.
We propose an alternative procedure for the capture of the hard‐rock regional kappa (κ0ref). In our approach, we make use of a potential link between the well‐known κ parameter and the properties of coda waves. In our analysis, we consider near‐distance records of four crustal earthquakes of local magnitude 3.7–4.9 that occurred in four regions of France in different geological contexts: the crystalline axial chain of Pyrenees to the southwest, the large sedimentary basin to the southeast, the Alpine range to the east, and the extensional Rhine graben to the northeast. Each earthquake has been recorded at a pair of nearby soft‐ and hard‐rock station sites. The high‐frequency (16–32 Hz) spectral amplitudes of the coda window (carefully selected on the time series of the accelerograms) confirm an exponential decrease, which we quantify by κAHcoda and call “kappa of coda.” It is found that κAHcoda is independent of the soil type but shows significant regional variations. κ measurements (Anderson and Hough, 1984) over the coda window (κAHcoda) and full time series (κAH) show strong correlation at hard‐rock sites. This suggests that κAHcoda can provide a new proxy to estimate the regional hard rock κ0ref (Ktenidou et al., 2015). Theoretical analysis is also presented to relate the regional κAHcoda and coda quality factor Qc, which quantifies the average attenuation properties of the crust (both scattering and absorption). It allows interpreting κAHcoda as the time spent by the waves in the medium, weighted by its attenuation properties. This theoretical analysis also shows that the classical κ measurement should be frequency dependent; this was confirmed by the spectra of the observed records.
Even before formal schooling, children map numbers onto space in a directional manner. The origin of this preliterate spatial–numerical association is still debated. We investigated the role of enculturation for shaping the directionality of the association between numbers and space, focusing on counting behavior in 3- to 5-year-old preliterate children. Two studies provide evidence that, after observing reading from storybooks (left-to-right or right-to-left reading) children change their counting direction in line with the direction of observed reading. Just observing visuospatial directional movements had no such effect on counting direction. Complementarily, we document that book illustrations, prevalent in children’s cultures, exhibit directionality that conforms to the direction of a culture’s written language. We propose that shared book reading activates spatiotemporal representations of order in young children, which in turn affect their spatial representation of numbers.
Blockchain technology offers a sizable promise to rethink the way interorganizational business processes are managed because of its potential to realize execution without a central party serving as a single point of trust (and failure). To stimulate research on this promise and the limits thereof, in this article, we outline the challenges and opportunities of blockchain for business process management (BPM). We first reflect how blockchains could be used in the context of the established BPM lifecycle and second how they might become relevant beyond. We conclude our discourse with a summary of seven research directions for investigating the application of blockchain technology in the context of BPM.
Heg1 and Ccm1/2 proteins control endocardial mechanosensitivity during zebrafish valvulogenesis
(2018)
Endothelial cells respond to different levels of fluid shear stress through adaptations of their mechanosensitivity. Currently, we lack a good understanding of how this contributes to sculpting of the cardiovascular system. Cerebral cavernous malformation (CCM) is an inherited vascular disease that occurs when a second somatic mutation causes a loss of CCM1/KRIT1, CCM2, or CCM3 proteins. Here, we demonstrate that zebrafish Krit1 regulates the formation of cardiac valves. Expression of heg1, which encodes a binding partner of Krit1, is positively regulated by blood-flow. In turn, Heg1 stabilizes levels of Krit1 protein, and both Heg1 and Krit1 dampen expression levels of klf2a, a major mechanosensitive gene. Conversely, loss of Krit1 results in increased expression of klf2a and notch1b throughout the endocardium and prevents cardiac valve leaflet formation. Hence, the correct balance of blood-flow-dependent induction and Krit1 protein mediated repression of klf2a and notch1b ultimately shapes cardiac valve leaflet morphology.
Sortase A (SrtA) from Staphylococcus aureus has been often used for ligating a protein with other natural or synthetic compounds in recent years. Here we show that SrtA-mediated ligation (SML) is universally applicable for the linkage of two purely artificial building blocks. Silica nanoparticles (NPs), poly(ethylene glycol) and poly(N-isopropyl acrylamide) are chosen as synthetic building blocks. As a proof of concept, NP-polymer, NP-NP, and polymer-polymer structures are formed by SrtA catalysis. Therefore, the building blocks are equipped with the recognition sequence needed for SrtA reaction-the conserved peptide LPETG-and a pentaglycine motif. The successful formation of the reaction products is shown by means of transmission electron microscopy (TEM), matrix assisted laser desorption ionization-time of flight mass spectrometry (MALDI-ToF MS), and dynamic light scattering (DLS). The sortase catalyzed linkage of artificial building blocks sets the stage for the development of a new approach to link synthetic structures in cases where their synthesis by established chemical methods is complicated.
An original set of experimental and modeling tools is used to quantify the yield of each of the physical processes leading to photocurrent generation in organic bulk heterojunction solar cells, enabling evaluation of materials and processing condition beyond the trivial comparison of device performances. Transient absorption spectroscopy, “the” technique to monitor all intermediate states over the entire relevant timescale, is combined with time-delayed collection field experiments, transfer matrix simulations, spectral deconvolution, and parametrization of the charge carrier recombination by a two-pool model, allowing quantification of densities of excitons and charges and extrapolation of their kinetics to device-relevant conditions. Photon absorption, charge transfer, charge separation, and charge extraction are all quantified for two recently developed wide-bandgap donor polymers: poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-difluorothiophene) (PBDT[2F]T) and its nonfluorinated counterpart poly(4,8-bis((2-ethylhexyl)oxy)benzo[1,2-b:4,5-b′]dithiophene-3,4-thiophene) (PBDT[2H]T) combined with PC71BM in bulk heterojunctions. The product of these yields is shown to agree well with the devices' external quantum efficiency. This methodology elucidates in the specific case studied here the origin of improved photocurrents obtained when using PBDT[2F]T instead of PBDT[2H]T as well as upon using solvent additives. Furthermore, a higher charge transfer (CT)-state energy is shown to lead to significantly lower energy losses (resulting in higher VOC) during charge generation compared to P3HT:PCBM.
In this study transmission X-ray microscopy (TXM) was tested as a method to investigate the chemistry and structure of corroded silicate glasses at the nanometer scale. Three different silicate glasses were altered in static corrosion experiments for 1-336 hours at temperatures between 60 degrees C and 85 degrees C using a 25% HCl solution. Thin lamellas were cut perpendicular to the surface of corroded glass monoliths and were analysed with conventional TEM as well as with TXM. By recording optical density profiles at photon energies around the Na and O K-edges, the shape of the corrosion rim/pristine glass interfaces and the thickness of the corrosion rims has been determined. Na and O near-edge X-ray absorption fine-structure spectra (NEXAFS) were obtained without inducing irradiation damage and have been used to detect chemical changes in the corrosion rims. Spatially resolved NEXAFS spectra at the O K-edge provided insight to structural changes in the corrosion layer on the atomic scale. By comparison to O K-edge spectra of silicate minerals and (hydrous) albite glass as well as to O K-edge NEXAFS of model structures simulated with ab initio calculations, evidence is provided that changes of the fine structure at the O K-edge are assigned to the formation of siloxane groups in the corrosion rim.
Low-achieving students are at risk of experiencing a pattern of emotional, motivational, and cognitive deficits called school-related helplessness if they attribute their low achievement to low aptitude. Teachers' beliefs about the causes of students' low achievement are important sources of attributional information for students. In a sample of 2117 German ninth-graders attending the lowest track, 118 math and 129 German-language teachers, we tested whether teachers' beliefs about the extent to which aptitude causes achievement moderated the achievement-helplessness relation in students and whether there were differences between math and German. Multilevel analyses revealed that low prior achievement predicted higher helplessness in both subjects but the effect was stronger in math than in German. Teachers' beliefs amplified the achievement-helplessness relation in math but not in German. Results are discussed regarding domain-specific epistemological beliefs, and implications for research and practice are derived.
We obtain a generalized diffusion equation in modified or Riemann-Liouville form from continuous time random walk theory. The waiting time probability density function and mean squared displacement for different forms of the equation are explicitly calculated. We show examples of generalized diffusion equations in normal or Caputo form that encode the same probability distribution functions as those obtained from the generalized diffusion equation in modified form. The obtained equations are general and many known fractional diffusion equations are included as special cases.
Efficient Li utilization is generally considered to be a prerequisite for developing next-generation energy storage systems (ESSs). However, uncontrolled growth of Li microstructures (LmSs) during electrochemical cycling has prevented its practical commercialization. Herein, we attempt to understand the correlation of morphological evolution of Li electrodes with degrading electrochemical performances of Li/LiCoO2 and Li/S systems by synchrotron X-ray phase contrast tomography technique. It was found that the continuous transformation of the initial dense Li bulk to a porous lithium interface (PL1) structure intimately correlates with the gradually degrading overall cell performance of these two systems. Additionally, the formation mechanism of the PLI and its correlation with previously reported inwardly growing LmS and the lithium-reacted region have been intensively discussed. The information that we gain herein is complementary to previous investigations and may provide general insights into understanding of degradation mechanisms of Li metal anodes and also provide highly needed guidelines for effective design of reliable next-generation Li metal-based ESSs.
(5R,6S)-6-Acetoxy-5-hexadecanolide (MOP) is the oviposition pheromone of the mosquito Cx. quinquefasciatus, a vector of pathogens causing a variety of tropical diseases. We describe and evaluate herein three syntheses of MOP starting from mannitol-derived (3R,4R)-hexa-1,5-diene-3,4-diol. This C-2-symmetric building block is elaborated through bidirectional olefin metathesis reactions into 6-epi-MOP, which was converted into MOP via Mitsunobu inversion. The shortest of the three routes makes use of two sequential cross-metathesis reactions and an assisted tandem catalytic olefin reduction, induced by an in situ conversion of a Ru-carbene to a Ru-hydride.
We investigate synchronization of coupled organ pipes. Synchronization and reflection in the organ lead to undesired weakening of the sound in special cases. Recent experiments have shown that sound interaction is highly complex and nonlinear, however, we show that two delay-coupled Van-der-Pol oscillators appear to be a good model for the occurring dynamical phenomena. Here the coupling is realized as distance-dependent, or time-delayed, equivalently. Analytically, we investigate the synchronization frequency and bifurcation scenarios which occur at the boundaries of the Arnold tongues. We successfully compare our results to experimental data.
Arctic tundra ecosystems have experienced unprecedented change associated with climate warming over recent decades. Across the Pan-Arctic, vegetation productivity and surface greenness have trended positively over the period of satellite observation. However, since 2011 these trends have slowed considerably, showing signs of browning in many regions. It is unclear what factors are driving this change and which regions/landforms will be most sensitive to future browning. Here we provide evidence linking decadal patterns in arctic greening and browning with regional climate change and local permafrost-driven landscape heterogeneity. We analyzed the spatial variability of decadal-scale trends in surface greenness across the Arctic Coastal Plain of northern Alaska (similar to 60,000 km(2)) using the Landsat archive (1999-2014), in combination with novel 30 m classifications of polygonal tundra and regional watersheds, finding landscape heterogeneity and regional climate change to be the most important factors controlling historical greenness trends. Browning was linked to increased temperature and precipitation, with the exception of young landforms (developed following lake drainage), which will likely continue to green. Spatiotemporal model forecasting suggests carbon uptake potential to be reduced in response to warmer and/or wetter climatic conditions, potentially increasing the net loss of carbon to the atmosphere, at a greater degree than previously expected.
SmB6 is predicted to be the first member of the intersection of topological insulators and Kondo insulators, strongly correlated materials in which the Fermi level lies in the gap of a many-body resonance that forms by hybridization between localized and itinerant states. While robust, surface-only conductivity at low temperature and the observation of surface states at the expected high symmetry points appear to confirm this prediction, we find both surface states at the (100) surface to be topologically trivial. We find the (Gamma) over bar state to appear Rashba split and explain the prominent (X) over bar state by a surface shift of the many-body resonance. We propose that the latter mechanism, which applies to several crystal terminations, can explain the unusual surface conductivity. While additional, as yet unobserved topological surface states cannot be excluded, our results show that a firm connection between the two material classes is still outstanding.
The power spectral density (PSD) of any time-dependent stochastic processX (t) is ameaningful feature of its spectral content. In its text-book definition, the PSD is the Fourier transform of the covariance function of X-t over an infinitely large observation timeT, that is, it is defined as an ensemble-averaged property taken in the limitT -> infinity. Alegitimate question is what information on the PSD can be reliably obtained from single-trajectory experiments, if one goes beyond the standard definition and analyzes the PSD of a single trajectory recorded for a finite observation timeT. In quest for this answer, for a d-dimensional Brownian motion (BM) we calculate the probability density function of a single-trajectory PSD for arbitrary frequency f, finite observation time T and arbitrary number k of projections of the trajectory on different axes. We show analytically that the scaling exponent for the frequency-dependence of the PSD specific to an ensemble of BM trajectories can be already obtained from a single trajectory, while the numerical amplitude in the relation between the ensemble-averaged and single-trajectory PSDs is afluctuating property which varies from realization to realization. The distribution of this amplitude is calculated exactly and is discussed in detail. Our results are confirmed by numerical simulations and single-particle tracking experiments, with remarkably good agreement. In addition we consider a truncated Wiener representation of BM, and the case of a discrete-time lattice random walk. We highlight some differences in the behavior of a single-trajectory PSD for BM and for the two latter situations. The framework developed herein will allow for meaningful physical analysis of experimental stochastic trajectories.
This study analyzes the influence of local and regional climatic factors on the stable isotopic composition of rainfall in the Vietnamese Mekong Delta (VMD) as part of the Asian monsoon region. It is based on 1.5 years of weekly rainfall samples. In the first step, the isotopic composition of the samples is analyzed by local meteoric water lines (LMWLs) and single-factor linear correlations. Additionally, the contribution of several regional and local factors is quantified by multiple linear regression (MLR) of all possible factor combinations and by relative importance analysis. This approach is novel for the interpretation of isotopic records and enables an objective quantification of the explained variance in isotopic records for individual factors. In this study, the local factors are extracted from local climate records, while the regional factors are derived from atmospheric backward trajectories of water particles. The regional factors, i.e., precipitation, temperature, relative humidity and the length of backward trajectories, are combined with equivalent local climatic parameters to explain the response variables delta O-18, delta H-2, and d-excess of precipitation at the station of measurement. The results indicate that (i) MLR can better explain the isotopic variation in precipitation (R-2 = 0.8) compared to single-factor linear regression (R-2 = 0.3); (ii) the isotopic variation in precipitation is controlled dominantly by regional moisture regimes (similar to 70 %) compared to local climatic conditions (similar to 30 %); (iii) the most important climatic parameter during the rainy season is the precipitation amount along the trajectories of air mass movement; (iv) the influence of local precipitation amount and temperature is not sig-nificant during the rainy season, unlike the regional precipitation amount effect; (v) secondary fractionation processes (e.g., sub-cloud evaporation) can be identified through the d-excess and take place mainly in the dry season, either locally for delta O-18 and delta H-2, or along the air mass trajectories for d-excess. The analysis shows that regional and local factors vary in importance over the seasons and that the source regions and transport pathways, and particularly the climatic conditions along the pathways, have a large influence on the isotopic composition of rainfall. Although the general results have been reported qualitatively in previous studies (proving the validity of the approach), the proposed method provides quantitative estimates of the controlling factors, both for the whole data set and for distinct seasons. Therefore, it is argued that the approach constitutes an advancement in the statistical analysis of isotopic records in rainfall that can supplement or precede more complex studies utilizing atmospheric models. Due to its relative simplicity, the method can be easily transferred to other regions, or extended with other factors. The results illustrate that the interpretation of the isotopic composition of precipitation as a recorder of local climatic conditions, as for example performed for paleorecords of water isotopes, may not be adequate in the southern part of the Indochinese Peninsula, and likely neither in other regions affected by monsoon processes. However, the presented approach could open a pathway towards better and seasonally differentiated reconstruction of paleoclimates based on isotopic records.
Iron sulfur (Fe-S) clusters and the molybdenum cofactor (Moco) are present at enzyme sites, where the active metal facilitates electron transfer. Such enzyme systems are soluble in the mitochondrial matrix, cytosol and nucleus, or embedded in the inner mitochondrial membrane, but virtually absent from the cell secretory pathway. They are of ancient evolutionary origin supporting respiration, DNA replication, transcription, translation, the biosynthesis of steroids, heme, catabolism of purines, hydroxylation of xenobiotics, and cellular sulfur metabolism. Here, Fe-S cluster and Moco biosynthesis in Drosophila melanogaster is reviewed and the multiple biochemical and physiological functions of known Fe-S and Moco enzymes are described. We show that RNA interference of Mocs3 disrupts Moco biosynthesis and the circadian clock. Fe-S-dependent mitochondrial respiration is discussed in the context of germ line and somatic development, stem cell differentiation and aging. The subcellular compartmentalization of the Fe-S and Moco assembly machinery components and their connections to iron sensing mechanisms and intermediary metabolism are emphasized. A biochemically active Fe-S core complex of heterologously expressed fly Nfs1, Isd11, IscU, and human frataxin is presented. Based on the recent demonstration that copper displaces the Fe-S cluster of yeast and human ferredoxin, an explanation for why high dietary copper leads to cytoplasmic iron deficiency in flies is proposed. Another proposal that exosomes contribute to the transport of xanthine dehydrogenase from peripheral tissues to the eye pigment cells is put forward, where the Vps16a subunit of the HOPS complex may have a specialized role in concentrating this enzyme within pigment granules. Finally, we formulate a hypothesis that (i) mitochondrial superoxide mobilizes iron from the Fe-S clusters in aconitase and succinate dehydrogenase; (ii) increased iron transiently displaces manganese on superoxide dismutase, which may function as a mitochondrial iron sensor since it is inactivated by iron; (iii) with the Krebs cycle thus disrupted, citrate is exported to the cytosol for fatty acid synthesis, while succinyl-CoA and the iron are used for heme biosynthesis; (iv) as iron is used for heme biosynthesis its concentration in the matrix drops allowing for manganese to reactivate superoxide dismutase and Fe-S cluster biosynthesis to reestablish the Krebs cycle.
The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. The computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure. Published by AIP Publishing.
X-ray free-electron lasers (XFELs) and table-top sources of x-rays based upon high harmonic generation (HHG) have revolutionized the field of ultrafast x-ray atomic and molecular physics, largely due to an explosive growth in capabilities in the past decade. XFELs now provide unprecedented intensity (10(20) W cm(-2)) of x-rays at wavelengths down to similar to 1 Angstrom, and HHG provides unprecedented time resolution (similar to 50 attoseconds) and a correspondingly large coherent bandwidth at longer wavelengths. For context, timescales can be referenced to the Bohr orbital period in hydrogen atom of 150 attoseconds and the hydrogen-molecule vibrational period of 8 femtoseconds; wavelength scales can be referenced to the chemically significant carbon K-edge at a photon energy of similar to 280 eV (44 Angstroms) and the bond length in methane of similar to 1 Angstrom. With these modern x-ray sources one now has the ability to focus on individual atoms, even when embedded in a complex molecule, and view electronic and nuclear motion on their intrinsic scales (attoseconds and Angstroms). These sources have enabled coherent diffractive imaging, where one can image non-crystalline objects in three dimensions on ultrafast timescales, potentially with atomic resolution. The unprecedented intensity available with XFELs has opened new fields of multiphoton and nonlinear x-ray physics where behavior of matter under extreme conditions can be explored. The unprecedented time resolution and pulse synchronization provided by HHG sources has kindled fundamental investigations of time delays in photoionization, charge migration in molecules, and dynamics near conical intersections that are foundational to AMO physics and chemistry. This roadmap coincides with the year when three new XFEL facilities, operating at Angstrom wavelengths, opened for users (European XFEL, Swiss-FEL and PAL-FEL in Korea) almost doubling the present worldwide number of XFELs, and documents the remarkable progress in HHG capabilities since its discovery roughly 30 years ago, showcasing experiments in AMO physics and other applications. Here we capture the perspectives of 17 leading groups and organize the contributions into four categories: ultrafast molecular dynamics, multidimensional x-ray spectroscopies; high-intensity x-ray phenomena; attosecond x-ray science.
Sub-seasonal thaw slump mass wasting is not consistently energy limited at the landscape scale
(2018)
Predicting future thaw slump activity requires a sound understanding of the atmospheric drivers and geomorphic controls on mass wasting across a range of timescales. On sub-seasonal timescales, sparse measurements indicate that mass wasting at active slumps is often limited by the energy available for melting ground ice, but other factors such as rainfall or the formation of an insulating veneer may also be relevant. To study the sub-seasonal drivers, we derive topographic changes from single-pass radar interferometric data acquired by the TanDEM-X satellites. The estimated elevation changes at 12m resolution complement the commonly observed planimetric retreat rates by providing information on volume losses. Their high vertical precision (around 30 cm), frequent observations (11 days) and large coverage (5000 km(2)) allow us to track mass wasting as drivers such as the available energy change during the summer of 2015 in two study regions. We find that thaw slumps in the Tuktoyaktuk coastlands, Canada, are not energy limited in June, as they undergo limited mass wasting (height loss of around 0 cm day 1) despite the ample available energy, suggesting the widespread presence of early season insulating snow or debris veneer. Later in summer, height losses generally increase (around 3 cm day 1), but they do so in distinct ways. For many slumps, mass wasting tracks the available energy, a temporal pattern that is also observed at coastal yedoma cliffs on the Bykovsky Peninsula, Russia. However, the other two common temporal trajectories are asynchronous with the available energy, as they track strong precipitation events or show a sudden speed-up in late August respectively. The observed temporal patterns are poorly related to slump characteristics like the headwall height. The contrasting temporal behaviour of nearby thaw slumps highlights the importance of complex local and temporally varying controls on mass wasting.
The luminescence of Lanthanide(Ill) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and.Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(Ill) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K <= T <= 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M <= 1 <= 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.
Organic bulk heterojunction (BHJ) solar cells require energetic offsets between the donor and acceptor to obtain high short-circuit currents (J(SC)) and fill factors (FF). However, it is necessary to reduce the energetic offsets to achieve high open-circuit voltages (V-OC). Recently, reports have highlighted BHJ blends that are pushing at the accepted limits of energetic offsets necessary for high efficiency. Unfortunately, most of these BHJs have modest FF values. How the energetic offset impacts the solar cell characteristics thus remains poorly understood. Here, a comprehensive characterization of the losses in a polymer:fullerene BHJ blend, PIPCP:phenyl-C61-butyric acid methyl ester (PC61BM), that achieves a high V-OC (0.9 V) with very low energy losses (E-loss = 0.52 eV) from the energy of absorbed photons, a respectable J(SC) (13 mA cm(-2)), but a limited FF (54%) is reported. Despite the low energetic offset, the system does not suffer from field-dependent generation and instead it is characterized by very fast nongeminate recombination and the presence of shallow traps. The charge-carrier losses are attributed to suboptimal morphology due to high miscibility between PIPCP and PC61BM. These results hold promise that given the appropriate morphology, the J(SC), V-OC, and FF can all be improved, even with very low energetic offsets.
The spatial magnetic properties, through-space NMR shieldings (TSNMRS), of the typically anti-aromatic cyclopentadienyl cation, cyclobutadiene, pentalene, s-indacene and of substituted/annelated analogues of the latter structures have been calculated using the CIAO perturbation method employing the nucleus independent chemical shift (NICS) concept and visualized as iso-chemical-shielding surfaces (ICSS) of various size and direction. The TSNMRS values were employed to visualize and quantify the dia(para) magnetic ring current effects in the studied compounds. The interplay of dia(para)magnetic ring current effects due to substitution/annelation caused by heavy exo-cyclic n,pi-electron delocalization can be qualified.
Global patterns of declining temperature variability from the Last Glacial Maximum to the Holocene
(2018)
Changes in climate variability are as important for society to address as are changes in mean climate(1). Contrasting temperature variability during the Last Glacial Maximum and the Holocene can provide insights into the relationship between the mean state of the climate and its variability(2,3). However, although glacial-interglacial changes in variability have been quantified for Greenland(2), a global view remains elusive. Here we use a network of marine and terrestrial temperature proxies to show that temperature variability decreased globally by a factor of four as the climate warmed by 3-8 degrees Celsius from the Last Glacial Maximum (around 21,000 years ago) to the Holocene epoch (the past 11,500 years). This decrease had a clear zonal pattern, with little change in the tropics (by a factor of only 1.6-2.8) and greater change in the mid-latitudes of both hemispheres (by a factor of 3.3-14). By contrast, Greenland ice-core records show a reduction in temperature variability by a factor of 73, suggesting influences beyond local temperature or a decoupling of atmospheric and global surface temperature variability for Greenland. The overall pattern of reduced variability can be explained by changes in the meridional temperature gradient, a mechanism that points to further decreases in temperature variability in a warmer future.
We report on light-induced deformation of colloidal spheres consisting of azobenzene-containing polymers. The colloids of the size between 60 nm and 2 mu m in diameter were drop casted on a glass surface and irradiated with linearly polarized light. It was found that colloidal particles can be deformed up to ca. 6 times of their initial diameter. The maximum degree of deformation depends on the irradiation wavelength and intensity, as well as on colloidal particles size. On the basis of recently proposed theory by Toshchevikov et al. [J. Phys. Chem. Lett. 2017, 8, 1094], we calculated the optomechanical stresses (ca. 100 MPa) needed for such giant deformations and compared them with the experimental results.
Modulating the Molybdenum Coordination Sphere of Escherichia coli Trimethylamie N-Oxide Reductase
(2018)
The well-studied enterobacterium Escherichia coli present in the human gut can reduce trimethylamine N-oxide (TMAO) to trimethylamine during anaerobic respiration. The TMAO reductase TorA is a monomeric, bis-molybdopterin guanine dinucleotide (bis-MGD) cofactor-containing enzyme that belongs to the dimethyl sulfoxide reductase family of molybdoenzymes. We report on a system for the in vitro reconstitution of TorA with molybdenum cofactors (Moco) from different sources. Higher TMAO reductase activities for TorA were obtained when using Moco sources containing a sulfido ligand at the molybdenum atom. For the first time, we were able to isolate functional bis-MGD from Rhodobacter capsulatus formate dehydrogenase (FDH), which remained intact in its isolated state and after insertion into apo-TorA yielded a highly active enzyme. Combined characterizations of the reconstituted TorA enzymes by electron paramagnetic resonance spectroscopy and direct electrochemistry emphasize that TorA activity can be modified by changes in the Mo coordination sphere. The combination of these results together with studies of amino acid exchanges at the active site led us to propose a novel model for binding of the substrate to the molybdenum atom of TorA.
Genome-wide association studies of birth weight have focused on fetal genetics, whereas relatively little is known about the role of maternal genetic variation. We aimed to identify maternal genetic variants associated with birth weight that could highlight potentially relevant maternal determinants of fetal growth. We meta-analysed data on up to 8.7 million SNPs in up to 86 577 women of European descent from the Early Growth Genetics (EGG) Consortium and the UK Biobank. We used structural equation modelling (SEM) and analyses of mother-child pairs to quantify the separate maternal and fetal genetic effects. Maternal SNPs at 10 loci (MTNR1B, HMGA2, SH2B3, KCNAB1, L3MBTL3, GCK, EBF1, TCF7L2, ACTL9, CYP3A7) were associated with offspring birth weight at P< 5 x 10(-8). In SEM analyses, at least 7 of the 10 associations were consistent with effects of the maternal genotype acting via the intrauterine environment, rather than via effects of shared alleles with the fetus. Variants, or correlated proxies, at many of the loci had been previously associated with adult traits, including fasting glucose (MTNR1B, GCK and TCF7L2) and sex hormone levels (CYP3A7), and one (EBF1) with gestational duration. The identified associations indicate that genetic effects on maternal glucose, cytochrome P450 activity and gestational duration, and potentially on maternal blood pressure and immune function, are relevant for fetal growth. Further characterization of these associations in mechanistic and causal analyses will enhance understanding of the potentially modifiable maternal determinants of fetal growth, with the goal of reducing the morbidity and mortality associated with low and high birth weights.
For attributing hydrological changes to anthropogenic climate change, catchment models are driven by climate model output. A widespread approach to bridge the spatial gap between global climate and hydrological catchment models is to use a weather generator conditioned on weather patterns (WPs). This approach assumes that changes in local climate are characterized by between-type changes of patterns. In this study we test this assumption by analyzing a previously developed WP classification for the Rhine basin, which is based on dynamic and thermodynamic variables. We quantify changes in pattern characteristics and associated climatic properties. The amount of between- and within-type changes is investigated by comparing observed trends to trends resulting solely from WP occurrence. To overcome uncertainties in trend detection resulting from the selected time period, all possible periods in 1901-2010 with a minimum length of 31 years are analyzed. Increasing frequency is found for some patterns associated with high precipitation, although the trend sign highly depends on the considered period. Trends and interannual variations of WP frequencies are related to the long-term variability of large-scale circulation modes. Long-term WP internal warming is evident for summer patterns and enhanced warming for spring/autumn patterns since the 1970s. Observed trends in temperature and partly in precipitation are mainly associated with frequency changes of specific WPs, but some amount of within-type changes remains. The classification can be used for downscaling of past changes considering this limitation, but the inclusion of thermodynamic variables into the classification impedes the downscaling of future climate projections.
Multiblock-like amphiphilic polyurethanes constituted by poly(ethylene oxide) and biosourced betulin are designed for antifouling and synthesized by a convenient organocatalytic route comprising tandem chain-growth and step-growth polymerizations. The doping density of betulin (D-B) in the polymer chain structure is readily varied by a mixed-initiator strategy. The spin-coated polymer films exhibit unique nanophase separation and protein resistance behaviors. Higher D-B leads to enhanced surface hydrophobicity and, unexpectedly, improved protein resistance. It is found that the surface holds molecular-level heterogeneity when D-B is substantially high due to restricted phase separation; therefore, broad-spectrum protein resistance is achieved despite considerable surface hydrophobicity. As D-B decreases, the distance between adjacent betulin units increases so that hydrophobic nanodomains are formed, which provide enough landing areas for relatively small-sized proteins to adsorb on the surface.
Aims. To gain a realistic picture of the donor star in Vela X-1, we constructed a hydrodynamically consistent atmosphere model describing the wind stratification while properly reproducing the observed donor spectrum. To investigate how X-ray illumination affects the stellar wind, we calculated additional models for different X-ray luminosity regimes. Methods. We used the recently updated version of the Potsdam Wolf-Rayet code to consistently solve the hydrodynamic equation together with the statistical equations and the radiative transfer. Results. The wind flow in Vela X-1 is driven by ions from various elements, with Fe III and S III leading in the outer wind. The model-predicted mass-loss rate is in line with earlier empirical studies. The mass-loss rate is almost unaffected by the presence of the accreting NS in the wind. The terminal wind velocity is confirmed at u(infinity) approximate to 600 km s(-1). On the other hand, the wind velocity in the inner region where the NS is located is only approximate to 100 km s(-1), which is not expected on the basis of a standard beta-velocity law. In models with an enhanced level of X-rays, the velocity field in the outer wind can be altered. If the X-ray flux is too high, the acceleration breaks down because the ionization increases. Conclusions. Accounting for radiation hydrodynamics, our Vela X-1 donor atmosphere model reveals a low wind speed at the NS location, and it provides quantitative information on wind driving in this important HMXB.
Ice-rich yedoma-dominated landscapes store considerable amounts of organic carbon (C) and nitrogen (N) and are vulnerable to degradation under climate warming. We investigate the C and N pools in two thermokarst-affected yedoma landscapes - on Sobo-Sise Island and on Bykovsky Peninsula in the north of eastern Siberia. Soil cores up to 3m depth were collected along geomorphic gradients and analysed for organic C and N contents. A high vertical sampling density in the profiles allowed the calculation of C and N stocks for short soil column intervals and enhanced understanding of within-core parameter variability. Profile-level C and N stocks were scaled to the landscape level based on landform classifications from 5 m resolution, multispectral RapidEye satellite imagery. Mean landscape C and N storage in the first metre of soil for Sobo-Sise Island is estimated to be 20.2 kg C m(-2) and 1.8 kg N m(-2) and for Bykovsky Peninsula 25.9 kg C m(-2) and 2.2 kg N m(-2). Radiocarbon dating demonstrates the Holocene age of thermokarst basin deposits but also suggests the presence of thick Holoceneage cover layers which can reach up to 2 m on top of intact yedoma landforms. Reconstructed sedimentation rates of 0.10-0.57 mm yr(-1) suggest sustained mineral soil accumulation across all investigated landforms. Both yedoma and thermokarst landforms are characterized by limited accumulation of organic soil layers (peat). We further estimate that an active layer deepening of about 100 cm will increase organic C availability in a seasonally thawed state in the two study areas by similar to 5.8 Tg (13.2 kg C m(-2)). Our study demonstrates the importance of increasing the number of C and N storage inventories in ice-rich yedoma and thermokarst environments in order to account for high variability of permafrost and thermokarst environments in pan-permafrost soil C and N pool estimates.
Recovering genomics clusters of secondary metabolites from lakes using genome-resolved metagenomics
(2018)
Metagenomic approaches became increasingly popular in the past decades due to decreasing costs of DNA sequencing and bioinformatics development. So far, however, the recovery of long genes coding for secondary metabolites still represents a big challenge. Often, the quality of metagenome assemblies is poor, especially in environments with a high microbial diversity where sequence coverage is low and complexity of natural communities high. Recently, new and improved algorithms for binning environmental reads and contigs have been developed to overcome such limitations. Some of these algorithms use a similarity detection approach to classify the obtained reads into taxonomical units and to assemble draft genomes. This approach, however, is quite limited since it can classify exclusively sequences similar to those available (and well classified) in the databases. In this work, we used draft genomes from Lake Stechlin, north-eastern Germany, recovered by MetaBat, an efficient binning tool that integrates empirical probabilistic distances of genome abundance, and tetranucleotide frequency for accurate metagenome binning. These genomes were screened for secondary metabolism genes, such as polyketide synthases (PKS) and non-ribosomal peptide synthases (NRPS), using the Anti-SMASH and NAPDOS workflows. With this approach we were able to identify 243 secondary metabolite clusters from 121 genomes recovered from our lake samples. A total of 18 NRPS, 19 PKS, and 3 hybrid PKS/NRPS clusters were found. In addition, it was possible to predict the partial structure of several secondary metabolite clusters allowing for taxonomical classifications and phylogenetic inferences. Our approach revealed a high potential to recover and study secondary metabolites genes from any aquatic ecosystem.
The Leading Arm (LA) of the Magellanic Stream is a vast debris field of H I clouds connecting the Milky Way and the Magellanic Clouds. It represents an example of active gas accretion onto the Galaxy. Previously, only one chemical abundance measurement had been made in the LA. Here we present chemical abundance measurements using Hubble Space Telescope/Cosmic Origins Spectrograph and Green Bank Telescope spectra of four AGN sightlines passing through the LA and three nearby sightlines that may trace outer fragments of the LA. We find low oxygen abundances, ranging from 4.0+(2.0)(2.0)% 12.6(4.1)(6.0)% solar, in the confirmed LA directions, with the lowest values found in the region known as LA III, farthest from the LMC. These abundances are substantially lower than the single previous measurement, S/H = 35 +/- 7% solar, but are in agreement with those reported in the SMC filament of the trailing Stream, supporting a common origin in the SMC (not the LMC) for the majority of the LA and trailing Stream. This provides important constraints for models of the formation of the Magellanic System. Finally, two of the three nearby sightlines show high-velocity clouds with H I columns, kinematics, and oxygen abundances consistent with LA membership. This suggests that the LA is larger than traditionally thought, extending at least 20 degrees further to the Galactic northwest.
A prediction of the current paradigm of the hierarchical assembly of galaxies is the presence of supermassive dual black holes at separations of a few kpc or less. In this context, we report the detection of a narrow-line emitter within the extended Ly alpha nebula (similar to 120 kpc diameter) of the luminous radio-quiet quasi-stellar object (QSO) LBQS 0302 0019 at z = 3 : 286. We identify several high-ionization narrow emission lines (He II, C IV, C III) associated with this point-like source, which we have named "Jil", which is only similar to 20 kpc (2 : 0 0 9) away from the QSO in projection. Emission-line diagnostics confirm that the source is likely powered by photoionization of an obscured active galactic nucleus (AGN) three orders of magnitude fainter than the QSO. The system represents the tightest unobscured/obscured dual AGN currently known at z > 3, highlighting the power of MUSE to detect these elusive systems.
Experimental studies on polysemy have come to contradictory conclusions on whether words with multiple senses are stored as separate or shared mental representations. The present study examined the semantic relatedness and semantic similarity of literal and non-literal (metonymic and metaphorical) senses of three word classes: nouns, verbs, and adjectives. Two methods were used: a psycholinguistic experiment and a distributional analysis of corpus data. In the experiment, participants were presented with 6-12 short phrases containing a polysemous word in literal, metonymic, or metaphorical senses and were asked to classify them so that phrases with the same perceived sense were grouped together. To investigate the impact of professional background on their decisions, participants were controlled for linguistic vs. non-linguistic education. For nouns and verbs, all participants preferred to group together phrases with literal and metonymic senses, but not any other pairs of senses. For adjectives, two pairs of senses were often grouped together: literal with metonymic, and metonymic with metaphorical. Participants with a linguistic background were more accurate than participants with non-linguistic backgrounds, although both groups shared principal patterns of sense classification. For the distributional analysis of corpus data, we used a semantic vector approach to quantify the similarity of phrases with literal, metonymic, and metaphorical senses in the corpora. We found that phrases with literal and metonymic senses had the highest degree of similarity for the three word classes, and that metonymic and metaphorical senses of adjectives had the highest degree of similarity among all word classes. These findings are in line with the experimental results. Overall, the results suggest that the mental representation of a polysemous word depends on its word class. In nouns and verbs, literal and metonymic senses are stored together, while metaphorical senses are stored separately; in adjectives, metonymic senses significantly overlap with both literal and metaphorical senses.
Pak choi (Brassica rapa subsp. chinensis) is rich in secondary metabolites and contains numerous antioxidants, including flavonoids; hydroxycinnamic acids; carotenoids; chlorophylls; and glucosinolates, which can be hydrolyzed to epithionitriles, nitriles, or isothiocyanates. Here, we investigate the effect of reduced exposure to ultraviolet B (UVB) and UV (UVA and UVB) light at four different developmental stages of pak choi. We found that both the plant morphology and secondary metabolite profiles were affected by reduced exposure to UVB and UV, depending on the plant’s developmental stage. In detail, mature 15- and 30-leaf plants had higher concentrations of flavonoids, hydroxycinnamic acids, carotenoids, and chlorophylls, whereas sprouts contained high concentrations of glucosinolates and their hydrolysis products. Dry weights and leaf areas increased as a result of reduced UVB and low UV. For the flavonoids and hydroxycinnamic acids in 30-leaf plants, less complex compounds were favored, for example, sinapic acid acylated kaempferol triglycoside instead of the corresponding tetraglycoside. Moreover, also in 30-leaf plants, zeaxanthin, a carotenoid linked to protection during photosynthesis, was increased under low UV conditions. Interestingly, most glucosinolates were not affected by reduced UVB and low UV conditions. However, this study underlines the importance of 4-(methylsulfinyl)butyl glucosinolate in response to UVA and UVB exposure. Further, reduced UVB and low UV conditions resulted in higher concentrations of glucosinolate-derived nitriles. In conclusion, exposure to low doses of UVB and UV from the early to late developmental stages did not result in overall lower concentrations of plant secondary metabolites.