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Inspired by the application of ultrasonic cavitation based mechanical force (CMF) to open small channels in natural soft materials (skin or tissue), it is explored whether an artificial polymer network can be created, in which shape-changes can be induced by CMF. This concept comprises an interconnected macroporous rhodium-phosphine (Rh-P) coordination polymer network, in which a CMF can reversibly dissociate the Rh-P microphases. In this way, the ligand exchange of Rh-P coordination bonds in the polymer network is accelerated, resulting in a topological rearrangement of molecular switches. This rearrangement of molecular switches enables the polymer network to release internal tension under ultrasound exposure, resulting in a CMF-induced shape-memory capability. The interconnected macroporous structure with thin pore walls is essential for allowing the CMF to effectively permeate throughout the polymer network. Potential applications of this CMF-induced shape-memory polymer can be mechanosensors or ultrasound controlled switches.
Imaging changes in molecular geometries on their natural femtosecond timescale with sub-Angstrom spatial precision is one of the critical challenges in the chemical sciences, as the nuclear geometry changes determine the molecular reactivity. For photoexcited molecules, the nuclear dynamics determine the photoenergy conversion path and efficiency. Here we report a gas-phase electron diffraction experiment using megaelectronvolt (MeV) electrons, where we captured the rotational wavepacket dynamics of nonadiabatically laser-aligned nitrogen molecules. We achieved a combination of 100 fs root-mean-squared temporal resolution and sub-Angstrom (0.76 angstrom) spatial resolution that makes it possible to resolve the position of the nuclei within the molecule. In addition, the diffraction patterns reveal the angular distribution of the molecules, which changes from prolate (aligned) to oblate (anti-aligned) in 300 fs. Our results demonstrate a significant and promising step towards making atomically resolved movies of molecular reactions.
We present results on ultrafast gas electron diffraction (UGED) experiments with femtosecond resolution using the MeV electron gun at SLAC National Accelerator Laboratory. UGED is a promising method to investigate molecular dynamics in the gas phase because electron pulses can probe the structure with a high spatial resolution. Until recently, however, it was not possible for UGED to reach the relevant timescale for the motion of the nuclei during a molecular reaction. Using MeV electron pulses has allowed us to overcome the main challenges in reaching femtosecond resolution, namely delivering short electron pulses on a gas target, overcoming the effect of velocity mismatch between pump laser pulses and the probe electron pulses, and maintaining a low timing jitter. At electron kinetic energies above 3 MeV, the velocity mismatch between laser and electron pulses becomes negligible. The relativistic electrons are also less susceptible to temporal broadening due to the Coulomb force. One of the challenges of diffraction with relativistic electrons is that the small de Broglie wavelength results in very small diffraction angles. In this paper we describe the new setup and its characterization, including capturing static diffraction patterns of molecules in the gas phase, finding time-zero with sub-picosecond accuracy and first time-resolved diffraction experiments. The new device can achieve a temporal resolution of 100 fs root-mean-square, and sub-angstrom spatial resolution. The collimation of the beam is sufficient to measure the diffraction pattern, and the transverse coherence is on the order of 2 nm. Currently, the temporal resolution is limited both by the pulse duration of the electron pulse on target and by the timing jitter, while the spatial resolution is limited by the average electron beam current and the signal-to-noise ratio of the detection system. We also discuss plans for improving both the temporal resolution and the spatial resolution.
Infants start learning the prosodic properties of their native language before 12 months, as shown by the emergence of a trochaic bias in English-learning infants between 6 and 9 months (Jusczyk et al., 1993), and in German-learning infants between 4 and 6 months (Huhle et al., 2009, 2014), while French-learning infants do not show a bias at 6 months (Hohle et al., 2009). This language-specific emergence of a trochaic bias is supported by the fact that English and German are languages with trochaic predominance in their lexicons, while French is a language with phrase-final lengthening but lacking lexical stress. We explored the emergence of a trochaic bias in bilingual French/German infants, to study whether the developmental trajectory would be similar to monolingual infants and whether amount of relative exposure to the two languages has an impact on the emergence of the bias. Accordingly, we replicated Hohle et al. (2009) with 24 bilingual 6-month-olds learning French and German simultaneously. All infants had been exposed to both languages for 30 to 70% of the time from birth. Using the Head Preference Procedure, infants were presented with two lists of stimuli, one made up of several occurrences of the pseudoword /GAba/ with word-initial stress (trochaic pattern), the second one made up of several occurrences of the pseudoword /gaBA/ with word-final stress (iambic pattern). The stimuli were recorded by a native German female speaker. Results revealed that these French/German bilingual 6-month olds have a trochaic bias (as evidenced by a preference to listen to the trochaic pattern). Hence, their listening preference is comparable to that of monolingual German-learning 6-month-olds, but differs from that of monolingual French-learning 6-month-olds who did not show any preference (Noble et al., 2009). Moreover, the size of the trochaic bias in the bilingual infants was not correlated with their amount of exposure to German. The present results thus establish that the development of a trochaic bias in simultaneous bilinguals is not delayed compared to monolingual German-learning infants (Hohle et al., 2009) and is rather independent of the amount of exposure to German relative to French.
Observing the motion of the nuclear wave packets during a molecular reaction, in both space and time, is crucial for understanding and controlling the outcome of photoinduced chemical reactions. We have imaged the motion of a vibrational wave packet in isolated iodine molecules using ultrafast electron diffraction with relativistic electrons. The time-varying interatomic distance was measured with a precision 0.07 angstrom and temporal resolution of 230 fs full width at half maximum. The method is not only sensitive to the position but also the shape of the nuclear wave packet.
The combination of high-performance liquid chromatography and electrospray ionization ion mobility spectrometry facilitates the two-dimensional separation of complex mixtures in the retention and drift time plane. The ion mobility spectrometer presented here was optimized for flow rates customarily used in high-performance liquid chromatography between 100 and 1500 mu L/min. The characterization of the system with respect to such parameters as the peak capacity of each time dimension and of the 2D spectrum was carried out based on a separation of a pesticide mixture containing 24 substances. While the total ion current chromatogram is coarsely resolved, exhibiting coelutions for a number of compounds, all substances can be separately detected in the 2D plane due to the orthogonality of the separations in retention and drift dimensions. Another major advantage of the ion mobility detector is the identification of substances based on their characteristic mobilities. Electrospray ionization allows the detection of substances lacking a chromophore. As an example, the separation of a mixture of 18 amino acids is presented. A software built upon the free mass spectrometry package OpenMS was developed for processing the extensive 2D data. The different processing steps are implemented as separate modules which can be arranged in a graphic workflow facilitating automated processing of data.
We analyze the spatiotemporal distribution of fault geometries from seismicity induced by fluid injection at The Geysers geothermal field. The consistency of these faults with the local stress field is investigated using (1) the fault instability coefficient I comparing the orientation of a fault with the optimal orientation for failure in the assumed stress field and (2) the misfit angle beta between slip vectors observed from focal mechanisms and predicted from stress tensor. A statistical approach is applied to calculate the most likely fault instabilities considering the uncertainties from focal mechanisms and stress inversion. We find that faults activated by fluid injection may display a broad range in orientations. About 72% of the analyzed seismicity occurs on faults with favorable orientation for failure with respect to the stress field. However, a number of events are observed either to occur on severely misoriented faults or to slip in a different orientation than predicted from stress field. These events mostly occur during periods of high injection rates and are located in proximity to the injection wells. From the stress inversion, the friction coefficient providing the largest overall instability is mu = 0.5. About 91% of the events are activated with an estimated excess pore pressure <10 MPa, in agreement with previous models considering the combined effect of thermal and poroelastic stress changes from fluid injection. Furthermore, high seismic activity and largest magnitudes occur on favorably oriented faults with large instability coefficients and low slip misfit angles.
The phenylidenepyridine (ppy) palladacycles [PdCl(ppy)(IMes)] (4) [IMes = 1,3-bis(mesityl) imidazol-2-ylidene] and [PdCl(ppy){(CN)(2)IMes}] (6) [(CN)(2)IMes = 4,5-dicyano-1,3-bis(mesityl) imidazol-2-ylidene] were prepared by facile two step syntheses, starting with the reaction of palladium(II) chloride with 2-phenylpyridine followed by subsequent addition of the NHC ligand to the precatalyst precursor [PdCl(ppy)](2). Suitable crystals for the X-ray analysis of the complexes 4 and 6 were obtained. It was shown that 6 has a shorter NHC-palladium bond than the IMes complex 4. The difference of the palladium carbene bond lengths based on the higher pi-acceptor strength of (CN)(2)IMes in comparison to IMes. Thus, (CN)(2)IMes should stabilize the catalytically active central palladium atom better than IMes. As a measure for the pi-acceptor strength of (CN)(2)IMes compared to IMes, the selone (CN)(2)IMes center dot Se (7) was prepared and characterized by Se-77-NMR spectroscopy. The pi-acceptor strength of 7 was illuminated by the shift of its Se-77-NMR signal. The Se-77-NMR signal of 7 was shifted to much higher frequencies than the Se-77-NMR signal of IMes center dot Se. Catalytic experiments using the Mizoroki-Heck reaction of aryl chlorides with n-butyl acrylate showed that 6 is the superior performer in comparison to 4. Using complex 6, an extensive substrate screening of 26 different aryl bromides with n-butyl acrylate was performed. Complex 6 is a suitable precatalyst for para-substituted aryl bromides. The catalytically active species was identified by mercury poisoning experiments to be palladium nanoparticles.
A desirable goal is to synthesize easily accessible and highly K+/Na+-selective fluoroionophores to monitor physiological K+ levels in vitro and in vivo. Therefore, highly K+/Na+-selective ionophores have to be developed. Herein, we obtained in a sequence of only four synthetic steps a set of K+-responsive fluorescent probes 4, 5 and 6. In a systematic study, we investigated the influence of the alkoxy substitution in ortho position of the aniline moiety in -conjugated aniline-1,2,3-triazole-coumarin-fluoroionophores 4, 5 and 6 [R=MeO (4), EtO (5) and iPrO (6)] towards the K+-complex stability and K+/Na+ selectivity. The highest K+-complex stability showed fluoroionophore 4 with a dissociation constant K-d of 19mm, but the K-d value increases to 31mm in combined K+/Na+ solutions, indicating a poor K+/Na+ selectivity. By contrast, 6 showed even in the presence of competitive Na+ ions equal K-d values (K-d(K+)=45mm and K-d(K+/Na+)=45mm) and equal K+-induced fluorescence enhancement factors (FEFs=2.3). Thus, the fluorescent probe 6 showed an outstanding K+/Na+ selectivity and is a suitable fluorescent tool to measure physiological K+ levels in the range of 10-80mm in vitro. Further, the isopropoxy-substituted N-phenylaza[18]crown-6 ionophore in 6 is a highly K+-selective building block with a feasible synthetic route.
The first heterodinuclear ruthenium(II) complexes of the 1,6,7,12-tetraazaperylene (tape) bridging ligand with iron(II), cobalt(II), and nickel(II) were synthesized and characterized. The metal coordination sphere in this complexes is filled by the tetradentate N,N-dimethyl-2,11-diaza[3.3](2,6)-pyridinophane (L-N4Me2) ligand, yielding complexes of the general formula [(L-N4Me2)Ru(mu-tape)M(L-N4Me2)](ClO4)(2)(PF6)(2) with M = Fe {[2](ClO4)(2)(PF6)(2)}, Co {[3](ClO4)(2)(PF6)(2)}, and Ni {[4](ClO4)(2)(PF6)(2)}. Furthermore, the heterodinuclear tape ruthenium(II) complexes with palladium(II)- and platinum(II)-dichloride [(bpy)(2)Ru(-tape)PdCl2](PF6)(2) {[5](PF6)(2)} and [(dmbpy)(2)Ru(-tape)PtCl2](PF6)(2) {[6](PF6)(2)}, respectively were also prepared. The molecular structures of the complex cations [2](4+) and [4](4+) were discussed on the basis of the X-ray structures of [2](ClO4)(4)MeCN and [4](ClO4)(4)MeCN. The electrochemical behavior and the UV/Vis absorption spectra of the heterodinuclear tape ruthenium(II) complexes were explored and compared with the data of the analogous mono- and homodinuclear ruthenium(II) complexes of the tape bridging ligand.
Himalayan water resources attract a rapidly growing number of hydroelectric power projects (HPP) to satisfy Asia's soaring energy demands. Yet HPP operating or planned in steep, glacier-fed mountain rivers face hazards of glacial lake outburst floods (GLOFs) that can damage hydropower infrastructure, alter water and sediment yields, and compromise livelihoods downstream. Detailed appraisals of such GLOF hazards are limited to case studies, however, and a more comprehensive, systematic analysis remains elusive. To this end we estimate the regional exposure of 257 Himalayan HPP to GLOFs, using a flood-wave propagation model fed by Monte Carlo-derived outburst volumes of >2300 glacial lakes. We interpret the spread of thus modeled peak discharges as a predictive uncertainty that arises mainly from outburst volumes and dam-breach rates that are difficult to assess before dams fail. With 66% of sampled HPP are on potential GLOF tracks, up to one third of these HPP could experience GLOF discharges well above local design floods, as hydropower development continues to seek higher sites closer to glacial lakes. We compute that this systematic push of HPP into headwaters effectively doubles the uncertainty about GLOF peak discharge in these locations. Peak discharges farther downstream, in contrast, are easier to predict because GLOF waves attenuate rapidly. Considering this systematic pattern of regional GLOF exposure might aid the site selection of future Himalayan HPP. Our method can augment, and help to regularly update, current hazard assessments, given that global warming is likely changing the number and size of Himalayan meltwater lakes.
Geomorphic footprints of past large Himalayan earthquakes are elusive, although they are urgently needed for gauging and predicting recovery times of seismically perturbed mountain landscapes. We present evidence of catastrophic valley infill following at least three medieval earthquakes in the Nepal Himalaya. Radiocarbon dates from peat beds, plant macrofossils, and humic silts in fine-grained tributary sediments near Pokhara, Nepal’s second-largest city, match the timing of nearby M > 8 earthquakes in ~1100, 1255, and 1344 C.E. The upstream dip of tributary valley fills and x-ray fluorescence spectrometry of their provenance rule out local sources. Instead, geomorphic and sedimentary evidence is consistent with catastrophic fluvial aggradation and debris flows that had plugged several tributaries with tens of meters of calcareous sediment from a Higher Himalayan source >60 kilometers away.
Teachers’ professional knowledge is assumed to be a key variable for effective teaching. As teacher education has the goal to enhance professional knowledge of current and future teachers, this knowledge should be described and assessed. Nevertheless, only a limited number of studies quantitatively measures physics teachers’ professional knowledge. The study reported in this paper was part of a bigger project with the broader goal of understanding teacher professional knowledge. We designed a test instrument to assess the professional knowledge of physics teachers (N = 186) in the dimensions of content knowledge (CK), pedagogical content knowledge (PCK), and pedagogical knowledge (PK). A model describing the relationships between these three dimensions of professional knowledge was created to inform the design of the tests used to measure CK, PCK, and PK. In this paper, we describe the model with particular emphasis on the PCK part, and the subsequent PCK test development and its implementation in detail. We report different approaches to evaluate the PCK test, including the description of content validity, the examination of the internal structure of professional knowledge, and the analysis of construct validity by testing teachers across different school subjects, teachers from different school types, pre-service teachers, and physicists. Our findings demonstrate that our PCK test results could distinguish physics teachers from the other groups tested. The PCK test results could not be explained by teachers’ CK or PK, cognitive abilities, computational skills, or science knowledge.
Floods frequently cause substantial economic and human losses, particularly in developing countries. For the development of sound flood risk management schemes that reduce flood consequences, detailed insights into the different components of the flood risk management cycle, such as preparedness, response, flood impact analyses and recovery, are needed. However, such detailed insights are often lacking: commonly, only (aggregated) data on direct flood damage are available. Other damage categories such as losses owing to the disruption of production processes are usually not considered, resulting in incomplete risk assessments and possibly inappropriate recommendations for risk management. In this paper, data from 858 face-to-face interviews among flood-prone households and small businesses in Can Tho city in the Vietnamese Mekong Delta are presented to gain better insights into the damage caused by the 2011 flood event and its management by households and businesses.
The current view regarding the timing of regionally developed penetrative tectonic fabrics in sedimentary rocks is that their development postdates lithification of those rocks. In this case, fabric development is achieved by a number of deformation mechanisms, including grain rigid body rotation, crystal-plastic deformation, and pressure solution. The latter is believed to be the primary mechanism responsible for the domainal structure of cleavage in low-grade metamorphic rocks. In this study we combine field observations with strain studies to characterize considerable (>50%) Acadian crustal shortening in a Devonian clastic sedimentary sequence from southwest Ireland. Despite these high levels of shortening there is a marked absence of the domainal cleavage structure and intraclast deformation that are expected with this level of deformation. Fabrics in these rocks are predominantly a product of rigid body rotation and repacking of extraformational clasts during deformation of a clastic sedimentary sequence before lithification was complete.
A Conjunction of Mysteries
(2016)
The concept of bonding and antibonding orbitals is fundamental in chemistry. The population of those orbitals and the energetic difference between the two reflect the strength of the bonding interaction. Weakening the bond is expected to reduce this energetic splitting, but the transient character of bond-activation has so far prohibited direct experimental access. Here we apply time-resolved soft X-ray spectroscopy at a free electron laser to directly observe the decreased bonding antibonding splitting following bond-activation using an ultrashort optical laser pulse.
1. Migration conveys an immense challenge, especially for juvenile birds coping with enduring and risky journeys shortly after fledging. Accordingly, juveniles exhibit considerably lower survival rates compared to adults, particularly during migration. Juvenile white storks (Ciconia ciconia), which are known to rely on adults during their first fall migration presumably for navigational purposes, also display much lower annual survival than adults.
2. Using detailed GPS and body acceleration data, we examined the patterns and potential causes of age-related differences in fall migration properties of white storks by comparing first-year juveniles and adults. We compared juvenile and adult parameters of movement, behaviour and energy expenditure (estimated from overall dynamic body acceleration) and placed this in the context of the juveniles’ lower survival rate.
3. Juveniles used flapping flight vs. soaring flight 23% more than adults and were estimated to expend 14% more energy during flight. Juveniles did not compensate for their higher flight costs by increased refuelling or resting during migration. When juveniles and adults migrated together in the same flock, the juvenile flew mostly behind the adult and was left behind when they separated. Juveniles showed greater improvement in flight efficiency throughout migration compared to adults which appears crucial because juveniles exhibiting higher flight costs suffered increased mortality.
4. Our findings demonstrate the conflict between the juveniles’ inferior flight skills and their urge to keep up with mixed adult–juvenile flocks. We suggest that increased flight costs are an important proximate cause of juvenile mortality in white storks and likely in other soaring migrants and that natural selection is operating on juvenile variation in flight efficiency.
We investigate the influence of the Coriolis force on mass motion related to the Rheasilvia impact on asteroid Vesta. Observations by the NASA Dawn mission revealed a pattern of curved radial ridges, which are related to Coriolis-deflected mass-wasting during the initial modification stage of the crater. Utilizing the projected curvature of the mass-wasting trajectories, we developed a method that enabled investigation of the initial mass wasting of the Rheasilvia impact by observational means. We demonstrate that the Coriolis force can strongly affect the crater formation processes on rapidly rotating objects, and we derive the material's velocities (28.9 ± 22.5 m/s), viscosities (1.5–9.0 × 106 Pa s) and coefficients of friction (0.02–0.81) during the impact modification stage. The duration of the impact modification stage could be estimated to (1.1 ± 0.5) h. By analyzing the velocity distribution with respect to the topography, we deduce that the Rheasilvia impactor hit a heterogeneous target and that the initial crater walls were significantly steeper during the modification stage.
Ice-rich permafrost coasts in the Arctic are highly sensitive to climate warming and erode at a pace that exceeds the global average. Permafrost coasts deliver vast amounts of organic carbon into the nearshore zone of the Arctic Ocean. Numbers on flux exist for particulate organic carbon (POC) and total or soil organic carbon (TOC, SOC). However, they do not exist for dissolved organic carbon (DOC), which is known to be highly bioavailable. This study aims to estimate DOC stocks in coastal permafrost as well as the annual flux into the ocean. DOC concentrations in ground ice were analyzed along the ice-rich Yukon coast (YC) in the western Canadian Arctic. The annual DOC flux was estimated using available numbers for coast length, cliff height, annual erosion rate, and volumetric ice content in different stratigraphic horizons. Our results showed that DOC concentrations in ground ice range between 0.3 and 347.0mgL(-1) with an estimated stock of 13.63.0gm(-3) along the YC. An annual DOC flux of 54.90.9Mgyr(-1) was computed. These DOC fluxes are low compared to POC and SOC fluxes from coastal erosion or POC and DOC fluxes from Arctic rivers. We conclude that DOC fluxes from permafrost coasts play a secondary role in the Arctic carbon budget. However, this DOC is assumed to be highly bioavailable. We hypothesize that DOC from coastal erosion is important for ecosystems in the Arctic nearshore zones, particularly in summer when river discharge is low, and in areas where rivers are absent.
Ice-wedge polygon (IWP) peatlands in the Arctic and Subarctic are extremely vulnerable to climatic and environmental change. We present the results of a multidisciplinary paleoenvironmental study on IWPs in the northern Yukon, Canada. High-resolution laboratory analyses were carried out on a permafrost core and the overlying seasonally thawed (active) layer, from an IWP located in a drained lake basin on Herschel Island. In relation to 14 Accelerator Mass Spectrometry (AMS) radiocarbon dates spanning the last 5000 years, we report sedimentary data including grain size distribution and biogeochemical parameters (organic carbon, nitrogen, C/N ratio, delta C-13), stable water isotopes (delta O-18, delta D), as well as fossil pollen, plant macrofossil and diatom assemblages. Three sediment units (SUS) correspond to the main stages of deposition (1) in a thermokarst lake (SW : 4950 to 3950 cal yrs BP), (2) during transition from lacustrine to palustrine conditions after lake drainage (SU2: 3950 to 3120 cal yrs BP), and (3) in palustrine conditions of the IWP field that developed after drainage (SU3: 3120 cal yrs BP to 2012 CE). The lacustrine phase (pre 3950 cal yrs BP) is characterized by planktonic-benthic and pioneer diatom species indicating circumneutral waters, and very few plant macrofossils. The pollen record has captured a regional signal of relatively stable vegetation composition and climate for the lacustrine stage of the record until 3950 cal yrs BP. Palustrine conditions with benthic and acidophilic diatom species characterize the peaty shallow-water environments of the low-centered IWP. The transition from lacustrine to palustrine conditions was accompanied by acidification and rapid revegetation of the lake bottom within about 100 years. Since the palustrine phase we consider the pollen record as a local vegetation proxy dominated by the plant communities growing in the IWP. Ice-wedge cracking in water-saturated sediments started immediately after lake drainage at about 3950 cal yrs BP and led to the formation of an IWP mire. Permafrost aggradation through downward closed-system freezing of the lake talik is indicated by the stable water isotope record. The originally submerged IWP center underwent gradual drying during the past 2000 years. This study highlights the sensitivity of permafrost landscapes to climate and environmental change throughout the Holocene. (C) 2016 Elsevier Ltd. All rights reserved.
Arctic coastal infrastructure and cultural and archeological sites are increasingly vulnerable to erosion and flooding due to amplified warming of the Arctic, sea level rise, lengthening of open water periods, and a predicted increase in frequency of major storms. Mitigating these hazards necessitates decision-making tools at an appropriate scale. The objectives of this paper are to provide such a tool by assessing potential erosion and flood hazards at Herschel Island, a UNESCO World Heritage candidate site. This study focused on Simpson Point and the adjacent coastal sections because of their archeological, historical, and cultural significance. Shoreline movement was analyzed using the Digital Shoreline Analysis System (DSAS) after digitizing shorelines from 1952, 1970, 2000, and 2011. For purposes of this analysis, the coast was divided in seven coastal reaches (CRs) reflecting different morphologies and/or exposures. Using linear regression rates obtained from these data, projections of shoreline position were made for 20 and 50 years into the future. Flood hazard was assessed using a least cost path analysis based on a high-resolution light detection and ranging (LiDAR) dataset and current Intergovernmental Panel on Climate Change sea level estimates. Widespread erosion characterizes the study area. The rate of shoreline movement in different periods of the study ranges from -5.5 to 2.7 mI double dagger a(-1) (mean -0.6 mI double dagger a(-1)). Mean coastal retreat decreased from -0.6 mI double dagger a(-1) to -0.5 mI double dagger a(-1), for 1952-1970 and 1970-2000, respectively, and increased to -1.3 mI double dagger a(-1) in the period 2000-2011. Ice-rich coastal sections most exposed to wave attack exhibited the highest rates of coastal retreat. The geohazard map combines shoreline projections and flood hazard analyses to show that most of the spit area has extreme or very high flood hazard potential, and some buildings are vulnerable to coastal erosion. This study demonstrates that transgressive forcing may provide ample sediment for the expansion of depositional landforms, while growing more susceptible to overwash and flooding.
Talbot-Lau interferometry provides X-ray imaging techniques with significant enhancement of the radiographic contrast of weakly absorbing objects. The grating based technique allows separation of absorption, refraction and small angle scattering effects. The different efficiency of rectangular and triangular shaped phase gratings at varying detector distances is investigated. The interference patterns (Talbot carpets) are modeled for parallel monochromatic radiation and measured by synchrotron radiation. In comparison to rectangular shapes of phase gratings much higher visibility is obtained for triangular shapes which yield enhanced contrast of a glass capillary test specimen.
Visuospatial attention and gaze control depend on the interaction of foveal and peripheral processing. The foveal and peripheral regions of the visual field are differentially sensitive to parts of the spatial frequency spectrum. In two experiments, we investigated how the selective attenuation of spatial frequencies in the central or the peripheral visual field affects eye-movement behavior during real-world scene viewing. Gaze-contingent low-pass or high-pass filters with varying filter levels (i.e., cutoff frequencies; Experiment 1) or filter sizes (Experiment 2) were applied. Compared to unfiltered control conditions, mean fixation durations increased most with central high-pass and peripheral low-pass filtering. Increasing filter size prolonged fixation durations with peripheral filtering, but not with central filtering. Increasing filter level prolonged fixation durations with low-pass filtering, but not with high-pass filtering. These effects indicate that fixation durations are not always longer under conditions of increased processing difficulty. Saccade amplitudes largely adapted to processing difficulty: amplitudes increased with central filtering and decreased with peripheral filtering; the effects strengthened with increasing filter size and filter level. In addition, we observed a trade-off between saccade timing and saccadic selection, since saccade amplitudes were modulated when fixation durations were unaffected by the experimental manipulations. We conclude that interactions of perception and gaze control are highly sensitive to experimental manipulations of input images as long as the residual information can still be accessed for gaze control. (C) 2016 Elsevier Ltd. All rights reserved.
Natural vision is characterized by alternating sequences of rapid gaze shifts (saccades) and fixations. During fixations, microsaccades and slower drift movements occur spontaneously, so that the eye is never motionless. Theoretical models of fixational eye movements predict that microsaccades are dynamically coupled to slower drift movements generated immediately before microsaccades, which might be used as a criterion to distinguish microsaccades from small voluntary saccades. Here we investigate a sequential scanning task, where participants generate goal-directed saccades and microsaccades with overlapping amplitude distributions. We show that properties of microsaccades are correlated with precursory drift motion, while amplitudes of goal-directed saccades do not dependent on previous drift epochs. We develop and test a mathematical model that integrates goal-directed and fixational eye movements, including microsaccades. Using model simulations, we reproduce the experimental finding of correlations within fixational eye movement components (i.e., between physiological drift and microsaccades) but not between goal-directed saccades and fixational drift motion. These results lend support to a functional difference between microsaccades and goal-directed saccades, while, at the same time, both types of behavior may be part of an oculomotor continuum that is quantitatively described by our mathematical model. (C) 2015 Elsevier Ltd. All rights reserved.
Coupling of attention and saccades when viewing scenes with central and peripheral degradation
(2016)
Degrading real-world scenes in the central or the peripheral visual field yields a characteristic pattern: Mean saccade amplitudes increase with central and decrease with peripheral degradation. Does this pattern reflect corresponding modulations of selective attention? If so, the observed saccade amplitude pattern should reflect more focused attention in the central region with peripheral degradation and an attentional bias toward the periphery with central degradation. To investigate this hypothesis, we measured the detectability of peripheral (Experiment 1) or central targets (Experiment 2) during scene viewing when low or high spatial frequencies were gaze-contingently filtered in the central or the peripheral visual field. Relative to an unfiltered control condition, peripheral filtering induced a decrease of the detection probability for peripheral but not for central targets (tunnel vision). Central filtering decreased the detectability of central but not of peripheral targets. Additional post hoc analyses are compatible with the interpretation that saccade amplitudes and direction are computed in partial independence. Our experimental results indicate that task-induced modulations of saccade amplitudes reflect attentional modulations.
The gravitational field of a laser pulse of finite lifetime, is investigated in the framework of linearized gravity. Although the effects are very small, they may be of fundamental physical interest. It is shown that the gravitational field of a linearly polarized light pulse is modulated as the norm of the corresponding electric field strength, while no modulations arise for circular polarization. In general, the gravitational field is independent of the polarization direction. It is shown that all physical effects are confined to spherical shells expanding with the speed of light, and that these shells are imprints of the spacetime events representing emission and absorption of the pulse. Nearby test particles at rest are attracted towards the pulse trajectory by the gravitational field due to the emission of the pulse, and they are repelled from the pulse trajectory by the gravitational field due to its absorption. Examples are given for the size of the attractive effect. It is recovered that massless test particles do not experience any physical effect if they are co-propagating with the pulse, and that the acceleration of massless test particles counter-propagating with respect to the pulse is four times stronger than for massive particles
at rest. The similarities between the gravitational effect of a laser pulse and Newtonian gravity in two dimensions are pointed out. The spacetime curvature close to the pulse is compared to that induced by gravitational waves from astronomical sources.
Teacher judgments in terms of grades, proficiency assessments, and recommending placement in ability groups can have important consequences for a child’s future educational path. Whether or not students’ sociodemographic background characteristics are systematically related to teacher judgments has been a controversial topic of discussion. Using data from the TIMSS-Transition Study (N = 3285 fourth graders) administered across 13 German federal states in the 2006–2007 school year and survey data from parents and teachers, we investigated whether or not the average classroom socioeconomic status is reflected in teacher judgments and also examined possible underlying processes. We also probed the role of teachers’ own socioeconomic backgrounds (at the age of 16) in their later susceptibility to differentially judge students from different socioeconomic backgrounds and in differentially composed classrooms. Multilevel regression analyses revealed that, after controlling for differences in achievement (as indicated by standardized tests), teachers’ judgments were associated with the classrooms’ socioeconomic composition, and this finding could not be attributed to the average levels of motivation or behavior in the classroom. Teachers were similarly likely to exhibit such differential judgments regardless of their own socioeconomic background. These findings are discussed in the context of their implications for educational policy.
The gravitational field of a laser pulse of finite lifetime, is investigated in the framework of linearized gravity. Although the effects are very small, they may be of fundamental physical interest. It is shown that the gravitational field of a linearly polarized light pulse is modulated as the norm of the corresponding electric field strength, while no modulations arise for circular polarization. In general, the gravitational field is independent of the polarization direction. It is shown that all physical effects are confined to spherical shells expanding with the speed of light, and that these shells are imprints of the spacetime events representing emission and absorption of the pulse. Nearby test particles at rest are attracted towards the pulse trajectory by the gravitational field due to the emission of the pulse, and they are repelled from the pulse trajectory by the gravitational field due to its absorption. Examples are given for the size of the attractive effect. It is recovered that massless test particles do not experience any physical effect if they are co-propagating with the pulse, and that the acceleration of massless test particles counter-propagating with respect to the pulse is four times stronger than for massive particles at rest. The similarities between the gravitational effect of a laser pulse and Newtonian gravity in two dimensions are pointed out. The spacetime curvature close to the pulse is compared to that induced by gravitational waves from astronomical sources.
The differential cross-section for gravitational photon-photon scattering calculated in perturbative quantum gravity is shown to depend on the degree of polarization entanglement of the two photons. The interaction between photons in the symmetric Bell state is stronger than between not entangled photons. In contrast, the interaction between photons in the anti-symmetric Bell state is weaker than between not entangled photons. The results are interpreted in terms of quantum interference, and it is shown how they fit into the idea of distance-dependent forces. Copyright (C) EPLA, 2016
Himalayan water resources attract a rapidly growing number of hydroelectric power projects (HPP) to satisfy Asia's soaring energy demands. Yet HPP operating or planned in steep, glacier-fed mountain rivers face hazards of glacial lake outburst floods (GLOFs) that can damage hydropower infrastructure, alter water and sediment yields, and compromise livelihoods downstream. Detailed appraisals of such GLOF hazards are limited to case studies, however, and a more comprehensive, systematic analysis remains elusive. To this end we estimate the regional exposure of 257 Himalayan HPP to GLOFs, using a flood-wave propagation model fed by Monte Carlo-derived outburst volumes of >2300 glacial lakes. We interpret the spread of thus modeled peak discharges as a predictive uncertainty that arises mainly from outburst volumes and dam-breach rates that are difficult to assess before dams fail. With 66% of sampled HPP are on potential GLOF tracks, up to one third of these HPP could experience GLOF discharges well above local design floods, as hydropower development continues to seek higher sites closer to glacial lakes. We compute that this systematic push of HPP into headwaters effectively doubles the uncertainty about GLOF peak discharge in these locations. Peak discharges farther downstream, in contrast, are easier to predict because GLOF waves attenuate rapidly. Considering this systematic pattern of regional GLOF exposure might aid the site selection of future Himalayan HPP. Our method can augment, and help to regularly update, current hazard assessments, given that global warming is likely changing the number and size of Himalayan meltwater lakes.
An English double-embedded relative clause from which the middle verb is omitted can often be processed more easily than its grammatical counterpart, a phenomenon known as the grammaticality illusion. This effect has been found to be reversed in German, suggesting that the illusion is language specific rather than a consequence of universal working memory constraints. We present results from three self-paced reading experiments which show that Dutch native speakers also do not show the grammaticality illusion in Dutch, whereas both German and Dutch native speakers do show the illusion when reading English sentences. These findings provide evidence against working memory constraints as an explanation for the observed effect in English. We propose an alternative account based on the statistical patterns of the languages involved. In support of this alternative, a single recurrent neural network model that is trained on both Dutch and English sentences is shown to predict the cross-linguistic difference in the grammaticality effect.
We present the fundamental ideas underlying statistical hypothesis testing using the frequentist framework. We start with a simple example that builds up the one-sample t-test from the beginning, explaining important concepts such as the sampling distribution of the sample mean, and the iid assumption. Then, we examine the meaning of the p-value in detail and discuss several important misconceptions about what a p-value does and does not tell us. This leads to a discussion of Type I, II error and power, and Type S and M error. An important conclusion from this discussion is that one should aim to carry out appropriately powered studies. Next, we discuss two common issues that we have encountered in psycholinguistics and linguistics: running experiments until significance is reached and the ‘garden-of-forking-paths’ problem discussed by Gelman and others. The best way to use frequentist methods is to run appropriately powered studies, check model assumptions, clearly separate exploratory data analysis from planned comparisons decided upon before the study was run, and always attempt to replicate results.
With the arrival of the R packages nlme and lme4, linear mixed models (LMMs) have come to be widely used in experimentally-driven areas like psychology, linguistics, and cognitive science. This tutorial provides a practical introduction to fitting LMMs in a Bayesian framework using the probabilistic programming language Stan. We choose Stan (rather than WinBUGS or JAGS) because it provides an elegant and scalable framework for fitting models in most of the standard applications of LMMs. We ease the reader into fitting increasingly complex LMMs, using a two-condition repeated measures self-paced reading study.
We present a simple setup that exploits the interference of entangled photon pairs. 'Signal' photons are sent through a Mach–Zehnder-like interferometer, while 'idlers' are detected in a variable polarization state. Two-photon interference (in coincidence detection) is observed with very high contrast and for significant time delays between signal and idler detection events. This is explained by quantum erasure of the polarization tag and a delayed choice protocol involving a non-local virtual polarizer. The phase of the two-photon fringes is scanned by varying the path length in the signal beam or by rotating a birefringent crystal in the idler beam. We exploit this to characterize one beam splitter of the signal photon interferometer (reflection and transmission amplitudes including losses), using only information about coincidences and control parameters in the idler path. This is possible because our bi-photon state saturates the Greenberger–Yelin–Englert inequality between contrast and predictability.
A Langevin model accounting for all six molecular degrees of freedom is applied to femtosecond-laser induced, hot-electron driven dynamics of Ru(0001)(2 x 2): CO. In our molecular dynamics with electronic friction approach, a recently developed potential energy surface based on gradient-corrected density functional theory accounting for van der Waals interactions is adopted. Electronic friction due to the coupling of molecular degrees of freedom to electron-hole pairs in the metal are included via a local density friction approximation, and surface phonons by a generalized Langevin oscillator model. The action of ultrashort laser pulses enters through a substrate-mediated, hot-electron mechanism via a time-dependent electronic temperature (derived from a two-temperature model), causing random forces acting on the molecule. The model is applied to laser induced lateral diffusion of CO on the surface, "hot adsorbate" formation, and laser induced desorption. Reaction probabilities are strongly enhanced compared to purely thermal processes, both for diffusion and desorption. Reaction yields depend in a characteristic (nonlinear) fashion on the applied laser fluence, as well as branching ratios for various reaction channels. Computed two-pulse correlation traces for desorption and other indicators suggest that aside from electron-hole pairs, phonons play a non-negligible role for laser induced dynamics in this system, acting on a surprisingly short time scale. Our simulations on precomputed potentials allow for good statistics and the treatment of long-time dynamics (300 ps), giving insight into this system which hitherto has not been reached. We find generally good agreement with experimental data where available and make predictions in addition. A recently proposed laser induced population of physisorbed precursor states could not be observed with the present low-coverage model.
Action spectroscopy has emerged as an analytical tool to probe excited states in the gas phase. Although comparison of gas-phase absorption properties with quantum-chemical calculations is, in principle, straightforward, popular methods often fail to describe many molecules of interest-such as xanthene analogues. We, therefore, face their nano-and picosecond laser-induced photofragmentation with excited-state computations by using the CC2 method and time-dependent density functional theory (TDDFT). Whereas the extracted absorption maxima agree with CC2 predictions, the TDDFT excitation energies are blueshifted. Lowering the amount of Hartree-Fock exchange in the DFT functional can reduce this shift but at the cost of changing the nature of the excited state. Additional bandwidth observed in the photofragmentation spectra is rationalized in terms of multiphoton processes. Observed fragmentation from higher-lying excited states conforms to intense excited-to-excited state transitions calculated with CC2. The CC2 method is thus suitable for the comparison with photofragmentation in xanthene analogues.
In this work, we study the adsorption of CO from low to high coverage at a defect-free NaCl(100) surface by means of duster and periodic models, using highly accurate wave function-based QM:QM embedding as well as density functional theory. At low coverages, the most accurate methods predict a zero-point-corrected adsorption energy of around 13 kJ/mol, and the CO molecules are found to be oriented perpendicular to the surface. At higher coverages, lower-energy phases with nonparallel/upright, tilted orientations emerge. Besides the well-known p(2 x 1)/antiparallel phase (T/A), we find other tilted phases (tilted/irregular, T/I; tilted/spiral, T/S) as local minima. Vibrational frequencies for CO adsorbed on NaCl(100) and Davydov splittings of the C-O stretch vibration are also determined. The IR spectra are characteristic fingerprints for the relative orientation of CO molecules and may therefore be used as sensitive probes to distinguish parallel/upright from various tilted adsorption phases.
While azobenzenes readily photoswitch in solution, their photoisomerization in densely packed self-assembled monolayers (SAMs) can be suppressed. Reasons for this can be steric hindrance and/or electronic quenching, e.g., by exciton coupling. We address these possibilities by means of nonadiabatic molecular dynamics with trajectory surface hopping calculations, investigating the trans -> cis isomerization of azobenzene after excitation into the pi pi* absorption band. We consider a free monomer, an isolated dimer and a dimer embedded in a SAM-like environment of additional azobenzene molecules, imitating in this way the gradual transition from an unconstrained over an electronically coupled to an electronically coupled and sterically hindered, molecular switch. Our simulations reveal that in comparison to the single molecule the quantum yield of the trans -> cis photoisomerization is similar for the isolated dimer, but greatly reduced in the sterically constrained situation. Other implications of dimerization and steric constraints are also discussed.
In recent simulations of femtosecond laser induced desorption of molecular oxygen from the Ag(110) surface, it has been shown that depending on the properties (depth and electronic environment) of the well in which 02 is adsorbed, the desorption can be either induced dominantly by hot electrons or via excitations of phonons. In this work we explore whether the ratios between the desorption yields from different adsorption wells can be tuned by changing initial surface temperature and laser pulse properties. We show that the initial surface temperature is an important parameter, and that by using low initial surface temperatures the electronically mediated process can be favored. In contrast, laser properties seem to have only a modest influence on the results. (C) 2016 Elsevier B.V. All rights reserved.
Recent progress in manipulating atomic and condensed matter systems has instigated a surge of interest in nonequilibrium physics, including many-body dynamics of trapped ultracold atoms and ions, near-field radiative heat transfer, and quantum friction. Under most circumstances the complexity of such nonequilibrium systems requires a number of approximations to make theoretical descriptions tractable. In particular, it is often assumed that spatially separated components of a system thermalize with their immediate surroundings, although the global state of the system is out of equilibrium. This powerful assumption reduces the complexity of nonequilibrium systems to the local application of well-founded equilibrium concepts. While this technique appears to be consistent for the description of some phenomena, we show that it fails for quantum friction by underestimating by approximately 80% the magnitude of the drag force. Our results show that the correlations among the components of driven, but steady-state, quantum systems invalidate the assumption of local thermal equilibrium, calling for a critical reexamination of this approach for describing the physics of nonequilibrium systems.
We discuss the failure of the Markov approximation in the description of atom-surface fluctuation-induced interactions, both in equilibrium (Casimir-Polder forces) and out of equilibrium (quantum friction). Using general theoretical arguments, we show that the Markov approximation can lead to erroneous predictions of such phenomena with regard to both strength and functional dependencies on system parameters. In particular, we show that the long-time power-law tails of two-time dipole correlations and their corresponding low-frequency behavior, neglected in the Markovian limit, affect the prediction of the force. Our findings highlight the importance of non-Markovian effects in dispersion interactions.
In some countries including Germany unemployed workers can increase their income by working a few hours per week. The intention is to keep unemployed job seekers attached to the labour market and to increase their job-finding probabilities. To analyze the unemployment dynamics of job seekers with and without marginal employment, we consider an inflow sample into unemployment and estimate multivariate duration models. While we do not find any significant impact on the job finding probability in a model with homogeneous effects, models allowing for time-varying coefficients indicate a decreased job finding probability of marginal employment at the beginning of the unemployment spell and an increased job finding probability for the long-term unemployed. Our results suggest that job seekers with marginal employment find more stable post-unemployment jobs, and we find some evidence that the relationship between marginal employment and wages and employment stability varies with respect to skill levels, sector and labor market tightness. (C) 2016 Elsevier B.V. All rights reserved.
We investigate the role of interatomic interactions when a Bose gas, in a double-well potential with a finite tunneling probability (a 'Bose–Josephson junction'), is exposed to external noise. We examine the rate of decoherence of a system initially in its ground state with equal probability amplitudes in both sites. The noise may induce two kinds of effects: firstly, random shifts in the relative phase or number difference between the two wells and secondly, loss of atoms from the trap. The effects of induced phase fluctuations are mitigated by atom–atom interactions and tunneling, such that the dephasing rate may be suppressed by half its single-atom value. Random fluctuations may also be induced in the population difference between the wells, in which case atom–atom interactions considerably enhance the decoherence rate. A similar scenario is predicted for the case of atom loss, even if the loss rates from the two sites are equal. We find that if the initial state is number-squeezed due to interactions, then the loss process induces population fluctuations that reduce the coherence across the junction. We examine the parameters relevant for these effects in a typical atom chip device, using a simple model of the trapping potential, experimental data, and the theory of magnetic field fluctuations near metallic conductors. These results provide a framework for mapping the dynamical range of barriers engineered for specific applications and set the stage for more complex atom circuits ('atomtronics').
The electric-field noise above a layered structure composed of a planar metal electrode covered by a thin dielectric is evaluated and it is found that the dielectric film considerably increases the noise level, in proportion to its thickness. Importantly, even a thin (mono) layer of a low-loss dielectric can enhance the noise level by several orders of magnitude compared to the noise above a bare metal. Close to this layered surface, the power spectral density of the electric field varies with the inverse fourth power of the distance to the surface, rather than with the inverse square, as it would above a bare metal surface. Furthermore, compared to a clean metal, where the noise spectrum does not vary with frequency (in the radio-wave and microwave bands), the dielectric layer can generate electricfield noise which scales in inverse proportion to the frequency. For various realistic scenarios, the noise levels predicted from this model are comparable to those observed in trapped-ion experiments. Thus, these findings are of particular importance for the understanding and mitigation of unwanted heating and decoherence in miniaturized ion traps.
The Paleocene was a time of transition for the Arctic, with magmatic activity of the High Arctic Large Igneous Province (HALIP) giving way to magmatism of the North Atlantic Large Igneous Province in connection to plate tectonic changes in the Arctic and North Atlantic. In this study we investigate the Paleocene magmatic record and sediment pathways of the Basilika Formation exposed in the Central Tertiary Basin of Svalbard. By means of geochemistry, SmNd isotopic signatures, and zircon UPb geochronology we investigate the characteristics of several bentonite layers contained in the Basilika Formation, as well as the provenance of the intercalated clastic sediments. Our data show that the volcanic ash layers of the Basilika Formation, which were diagenetically altered to bentonites, originate from alkaline continental-rift magmatism such as the last, explosive stages of the HALIP in North Greenland and the Canadian Arctic. The volcanic ash layers were deposited on Svalbard in a flat shelf environment with dominant sediment supply from the east. Dating of detrital zircons suggests that the detritus was derived from Siberian sources, primarily from the Verkhoyansk Fold-and-Thrust Belt, which would require transport over similar to 3000 km across the Arctic.
Carbon fiber based felt materials are widely used as gas diffusion layer (GDL) in fuel cells. Their transport properties can be adjusted by adding hydrophobic agents such as polytetrafluoroethylene (PTFE). We present a synchrotron X-ray tomographic study on the felt material Freudenberg H2315 with different PIPE finishing. In this study, we analyze changes in microstructure and shape of GDLs at increasing degree of compression which are related to their specific PTFE load. A dedicated compression device mimicking the channel-land pattern of the flowfield is used to reproduce the inhomogeneous compression found in a fuel cell. Transport relevant geometrical parameters such as porosity, pore size distribution and geometric tortuosity are calculated and consequences for media transport discussed. PTFE finishing results in a marked change of shape of compressed GDLs: surface is smoothed and the invasion of GDL fibers into the flow field channel strongly mitigated. Furthermore, the PTFE impacts the microstructure of the compressed GDL. The number of available wide transport paths is significantly increased as compared to the untreated material. These changes improve the transport capacity liquid water through the GDL and promote the discharge of liquid water droplets from the cell. (C) 2016 Elsevier B.V. All rights reserved.
Spatial analysis of the impacts of the Chaiten volcano eruption (Chile) in three fluvial systems
(2016)
The eruption of the Chaiten volcano in May 2008 generated morphological and ecological disturbances in adjacent river basins, and the magnitude of these disturbances depended on the type of dominant volcanic process affecting each of them. The aim of this study is to analyse the morphological changes in different periods in river segments of the Blanco, El Amarillo and Rayas river basins located near the Chaiten volcano. These basins suffered disturbances of different intensity and spatial distribution caused by tephra fall, dome collapses and pyroclastic density currents that damaged hillslope forests, widened channels and destroyed island and floodplain vegetation. Changes continued to occur in the fluvial systems in the years following the eruption, as a consequence of the geomorphic processes indirectly induced by the eruption. Channel changes were analyzed by comparing remote images of pre and post eruption conditions. Two periods were considered: the first from 2008 to 2009-2010 associated with the explosive and effusive phases of the eruption and the second that correspond to the post-eruption stage from 2009-2010 to 2013. Following the first phases channel segments widened 91% (38 m/yr), 6% (7 m/yr) and 7% (22 m/yr) for Blanco, Rayas and El Amarillo Rivers, respectively, compared to pre-eruption condition. In the second period, channel segments additionally widened 42% (8 m/yr), 2% (2 m/yr) and 5% (4 m/yr) for Blanco, Rayas and El Amarillo Rivers, respectively. In the Blanco River 62 and 82% of the islands disappeared in the first and second period, respectively, which is 6-8 times higher than in the El Amarillo approximately twice the Rayas. Sinuosity increased after the eruption only in the Blanco River but the three study channels showed a high braiding intensity mainly during the first post-eruption period. The major disturbances occurred during the eruptive and effusive phases of Chaiten volcano, and the intensity of these disturbances reflects the magnitude of the dominant volcanic processes affecting each basin. Inputs of sediment from dome collapses and pyroclastic density currents and not ash fall seem to explain morphologic channel change magnitudes in the study segments. The resulting knowledge can facilitate land use planning and design of river restoration projects in areas affected by volcanic eruptions disturbances. (C) 2016 Elsevier Ltd. All rights reserved.
We introduce a technique for the modeling and separation of geomagnetic field components that is based on an analysis of their correlation structures alone. The inversion is based on a Bayesian formulation, which allows the computation of uncertainties. The technique allows the incorporation of complex measurement geometries like observatory data in a simple way. We show how our technique is linked to other well-known inversion techniques. A case study based on observational data is given.
We demonstrate that a single-layer graphene replicates the shape of DNA origami nanostructures very well. It can be employed as a protective layer for the enhancement of structural stability of DNA origami nanostructures. Using the AFM based manipulation, we show that the normal force required to damage graphene encapsulated DNA origami nanostructures is over an order of magnitude greater than for the unprotected ones. In addition, we show that graphene encapsulation offers protection to the DNA origami nanostructures against prolonged exposure to deionized water, and multiple immersions. Through these results we demonstrate that graphene encapsulated DNA origami nanostructures are strong enough to sustain various solution phase processing, lithography and transfer steps, thus extending the limits of DNA-mediated bottom-up fabrication.
In this study, a new reliable, economic, and environmentally-friendly one-step synthesis is established to obtain carbon nanodots (CNDs) with well-defined and reproducible photoluminescence (PL) properties via the microwave-assisted hydrothermal treatment of starch and Tris-acetate-EDTA (TAE) buffer as carbon sources. Three kinds of CNDs are prepared using different sets of above mentioned starting materials. The as-synthesized CNDs: C-CND (starch only), N-CND 1 (starch in TAE) and N-CND 2 (TAE only) exhibit highly homogenous PL and are ready to use without need for further purification. The CNDs are stable over a long period of time (>1 year) either in solution or as freeze-dried powder. Depending on starting material, CNDs with PL quantum yield (PLQY) ranging from less than 1% up to 28% are obtained. The influence of the precursor concentration, reaction time and type of additives on the optical properties (UV-Vis absorption, PL emission spectrum and PLQY) is carefully investigated, providing insight into the chemical processes that occur during CND formation. Remarkably, upon freeze-drying the initially brown CND-solution turns into a non-fluorescent white/slightly brown powder which recovers PL in aqueous solution and can potentially be applied as fluorescent marker in bio-imaging, as a reduction agent or as a photocatalyst.
The folding of single-stranded telomeric DNA into guanine (G) quadruplexes is a conformational change that plays a major role in sensing and drug targeting. The telomeric DNA can be placed on DNA origami nanostructures to make the folding process extremely selective for K+ ions even in the presence of high Na+ concentrations. Here, we demonstrate that the K+-selective G-quadruplex formation is reversible when using a cryptand to remove K+ from the G-quadruplex. We present a full characterization of the reversible switching between single-stranded telomeric DNA and G-quadruplex structures using Förster resonance energy transfer (FRET) between the dyes fluorescein (FAM) and cyanine3 (Cy3). When attached to the DNA origami platform, the G-quadruplex switch can be incorporated into more complex photonic networks, which is demonstrated for a three-color and a four-color FRET cascade from FAM over Cy3 and Cy5 to IRDye700 with G-quadruplex-Cy3 acting as a switchable transmitter.
DNA origami nanostructures are a versatile tool to arrange metal nanostructures and other chemical entities with nanometer precision. In this way gold nanoparticle dimers with defined distance can be constructed, which can be exploited as novel substrates for surface enhanced Raman scattering (SERS). We have optimized the size, composition and arrangement of Au/Ag nanoparticles to create intense SERS hot spots, with Raman enhancement up to 1010, which is sufficient to detect single molecules by Raman scattering. This is demonstrated using single dye molecules (TAMRA and Cy3) placed into the center of the nanoparticle dimers. In conjunction with the DNA origami nanostructures novel SERS substrates are created, which can in the future be applied to the SERS analysis of more complex biomolecular targets, whose position and conformation within the SERS hot spot can be precisely controlled.
Polysarcosine (Mn = 3650–20 000 g mol−1, Đ ∼ 1.1) was synthesized from the air and moisture stable N-phenoxycarbonyl-N-methylglycine. Polymerization was achieved by in situ transformation of the urethane precursor into the corresponding N-methylglycine-N-carboxyanhydride, when in the presence of a non-nucleophilic tertiary amine base and a primary amine initiator.
Background: Antiphospholipid antibodies (aPL) can be detected in asymptomatic carriers and infectious patients. The aim was to investigate whether a novel line immunoassay (LIA) differentiates between antiphospholipid syndrome (APS) and asymptomatic aPL+ carriers or patients with infectious diseases (infectious diseases controls (IDC)). Methods: Sixty-one patients with APS (56 primary, 22/56 with obstetric events only, and 5 secondary), 146 controls including 24 aPL+ asymptomatic carriers and 73 IDC were tested on a novel hydrophobic solid phase coated with cardiolipin (CL), phosphatic acid, phosphatidylcholine, phosphatidylethanolamine, phosphatidylglycerol, phosphatidylinositol, phosphatidylserine, beta2-glycoprotein I (beta 2GPI), prothrombin, and annexin V. Samples were also tested by anti-CL and anti-beta 2GPI ELISAs and for lupus anticoagulant activity. Human monoclonal antibodies (humoAbs) against human beta 2GPI or PL alone were tested on the same LIA substrates in the absence or presence of human serum, purified human beta 2GPI or after CL-micelle absorption. Results: Comparison of LIA with the aPL-classification assays revealed good agreement for IgG/IgM a beta 2GPI and aCL. Anti-CL and anti-beta 2GPI IgG/IgM reactivity assessed by LIA was significantly higher in patients with APS versus healthy controls and IDCs, as detected by ELISA. IgG binding to CL and beta 2GPI in the LIA was significantly lower in aPL+ carriers and Venereal Disease Research Laboratory test (VDRL) + samples than in patients with APS. HumoAb against domain 1 recognized beta 2GPI bound to the LIA-matrix and in anionic phospholipid (PL) complexes. Absorption with CL micelles abolished the reactivity of a PL-specific humoAb but did not affect the binding of anti-beta 2GPI humoAbs. Conclusions: The LIA and ELISA have good agreement in detecting aPL in APS, but the LIA differentiates patients with APS from infectious patients and asymptomatic carriers, likely through the exposure of domain 1.
Epitope mapping is crucial for the characterization of protein-specific antibodies. Commonly, small overlapping peptides are chemically synthesized and immobilized to determine the specific peptide sequence. In this study, we report the use of a fast and inexpensive planar microbead chip for epitope mapping. We developed a generic strategy for expressing recombinant peptide libraries instead of using expensive synthetic peptide libraries. A biotin moiety was introduced in vivo at a defined peptide position using biotin ligase. Peptides in crude Escherichia coli lysate were coupled onto streptavidin-coated microbeads by incubation, thereby avoiding tedious purification procedures. For read-out we used a multiplex planar microbead chip with size- and fluorescence-encoded microbead populations. For epitope mapping, up to 18 populations of peptide-loaded microbeads (at least 20 microbeads per peptide) displaying the primary sequence of a protein were analyzed simultaneously. If an epitope was recognized by an antibody, a secondary fluorescence-labeled antibody generated a signal that was quantified, and the mean value of all microbeads in the population was calculated. We mapped the epitopes for rabbit anti-PA28 gamma (proteasome activator 28 gamma) polyclonal serum, for a murine monoclonal antibody against PA28 gamma, and for a murine monoclonal antibody against the hamster polyoma virus major capsid protein VP1 as models. In each case, the identification of one distinct peptide sequence out of up to 18 sequences was possible. Using this approach, an epitope can be mapped multiparametrically within three weeks. (C) 2016 Elsevier B.V. All rights reserved.
This paper studies the effectiveness of building height limits as a policy to limit greenhouse gas (GHG) emissions. It shows that building height limits lead to urban sprawl and higher emissions from commuting. On the other hand, aggregate housing consumption may decrease, which reduces emissions from residential energy use. A numerical model is used to evaluate whether total GHG emissions may be lower under building height restrictions. Welfare is not concave in the strictness of building height limits, so either no limit or a very strict one (depending on the strength of the externality) might maximize welfare. The paper discusses several extensions, such as congestion, endogenous transport mode choice, migration, and urban heat island effect. (C) 2016 Elsevier B.V. All rights reserved
This article studies the effect of child care provision on family structure. We present a model of a marriage market with positive assortative matching, where in equilibrium, the poorest women stay single. Couples have to decide on the number of children and spousal specialization in home production of public goods and child care. We then study how child care provision affects the equilibrium. Due to specialization in home production, the incentive to use child care is smaller for married mothers than for single mothers. We show that this increases the number of single mothers and the divorce rate. Using survey data from Germany, we present suggestive empirical evidence consistent with this finding. (JEL codes: J12 and J13).
With increasing numbers of flights worldwide and a continuing rise in airport traffic, air-traffic management is faced with a number of challenges. These include monitoring, reporting, planning, and problem analysis of past and current air traffic, e.g., to identify hotspots, minimize delays, or to optimize sector assignments to air-traffic controllers. To cope with these challenges, cyber worlds can be used for interactive visual analysis and analytical reasoning based on aircraft trajectory data. However, with growing data size and complexity, visualization requires high computational efficiency to process that data within real-time constraints. This paper presents a technique for real-time animated visualization of massive trajectory data. It enables (1) interactive spatio-temporal filtering, (2) generic mapping of trajectory attributes to geometric representations and appearance, and (3) real-time rendering within 3D virtual environments such as virtual 3D airport or 3D city models. Different visualization metaphors can be efficiently built upon this technique such as temporal focus+context, density maps, or overview+detail methods. As a general-purpose visualization technique, it can be applied to general 3D and 3+1D trajectory data, e.g., traffic movement data, geo-referenced networks, or spatio-temporal data, and it supports related visual analytics and data mining tasks within cyber worlds.
Solving problems combining task and motion planning requires searching across a symbolic search space and a geometric search space. Because of the semantic gap between symbolic and geometric representations, symbolic sequences of actions are not guaranteed to be geometrically feasible. This compels us to search in the combined search space, in which frequent backtracks between symbolic and geometric levels make the search inefficient.We address this problem by guiding symbolic search with rich information extracted from the geometric level through culprit detection mechanisms.
The whey protein beta-lactoglobulin has been proposed as a transporter for covalent bound bioactive compounds in order to enhance their stability and reduce their sensory perception. The garlic derived compounds allicin and diallyl disulfide were bound covalently to the native and heat denatured protein. The binding site and the influence of the modification on the digestibility were determined by mass spectrometric analysis of the modified beta-lactoglobulin. Further, the conformation of the modified protein was assessed by circular dichroism and dynamic light scattering. The free thiol group of Cys(121) turned out to be the major binding site. After proteolysis with trypsin at pH 7 but not with pepsin at pH 2, a limited transfer to other cysteinyl residues was observed. The covalently bound ligands did not mask any proteolytic cleavage sites of pepsin, trypsin or chymotrypsin. The modified beta-lactoglobulin showed a native like conformation, besides a moderate loosening of protein folding. The covalent binding of organosulfur compounds to beta-lactoglobulin provides a bioactive ingredient without impairing the digestibility and functional properties of the protein. (C) 2015 Elsevier Ltd. All rights reserved.
Polyelectrolyte multilayers (PEMs) with stratification of the internal structure were assembled from statistical amphiphilic copolyelectrolytes of opposite charges. These polyelectrolytes organize in aqueous solutions into micellar structures with fluoroalkyl and aromatic nanodomains, respectively, that were also preserved after deposition as thin films via layer-by-layer (LbL) electrostatic self-assembly. The unimolecular micelles, formed due to statistical compositions of amphiphilic polyelectrolytes used, were shown to suppress chain interdiffusion between adjacent layers in resulting micellar PEMs, as evidenced by spectroscopic ellipsometry, atomic force microscopy (AFM), and neutron reflectometry (NR) measurements. Additionally, hydrophobic cores of the micelles were used as hosts for photoactive molecules, namely, ferrocene and perfluorinated magnesium phthalocyanine. Stratified micellar multilayers were then deposited as hollow capsules using CaCO3 microparticles as templates. Photoinduced electron transfer (PET) between ferrocene and phthalocyanine solubilized in the polymer micelles was demonstrated to occur efficiently inside the stratified, polyelectrolyte walls of the capsules, due to the polarity gradient created by the incompatible aromatic and fluoroalkyl domains. The obtained results present a new approach to construct well-organized, self-assembled nanostructured materials for solar energy conversion.
Biomembranes are exceptionally crowded with proteins with typical protein-to-lipid ratios being around 1:50 - 1:100. Protein crowding has a decisive role in lateral membrane dynamics as shown by recent experimental and computational studies that have reported anomalous lateral diffusion of phospholipids and membrane proteins in crowded lipid membranes. Based on extensive simulations and stochastic modeling of the simulated trajectories, we here investigate in detail how increasing crowding by membrane proteins reshapes the stochastic characteristics of the anomalous lateral diffusion in lipid membranes. We observe that correlated Gaussian processes of the fractional Langevin equation type, identified as the stochastic mechanism behind lipid motion in noncrowded bilayer, no longer adequately describe the lipid and protein motion in crowded but otherwise identical membranes. It turns out that protein crowding gives rise to a multifractal, non-Gaussian, and spatiotemporally heterogeneous anomalous lateral diffusion on time scales from nanoseconds to, at least, tens of microseconds. Our investigation strongly suggests that the macromolecular complexity and spatiotemporal membrane heterogeneity in cellular membranes play critical roles in determining the stochastic nature of the lateral diffusion and, consequently, the associated dynamic phenomena within membranes. Clarifying the exact stochastic mechanism for various kinds of biological membranes is an important step towards a quantitative understanding of numerous intramembrane dynamic phenomena.
Subsurface water flows play a key role in the distribution of water and solutes and thereby in the water availability for plants. However, the characterization of different flow processes (i.e.matrix and preferential flow), the frequency and factors that cause them, is relatively rare. This characterization enables a better understanding of spatio-temporal variability of water resources and allows for the design of models to be improved. Using a method based on the time derivative of soil moisture variation known as maximum wetting slope, types of soil wetting processes were classified and quantified. For this, capacitance sensors, which registered the volumetric water content at high temporal resolution (30min) for more than two hydrological years, were installed at different depths and placed in soil moisture stations with different vegetation covers, lithology and topographic position. Results indicated that there is a general behaviour or pattern of soil moisture dynamics in the catchment with a dominant occurrence of slower soil wetting processes (>50%), caused by matrix flows, and a low occurrence of those faster processes (<30%), originated by preferential flows. Nevertheless, when the total volume of water is considered, preferential flow becomes the dominant process, so that the ecological role of both flow types becomes prominent in water-limited environments. Statistical multivariate analyses based on data-mining techniques proved that although both flow types depend on variables associated with precipitation and antecedent soil moisture conditions, faster soil wetting processes are mainly related to variables such as rainfall intensity and topography, while slower soil wetting processes are related to flow velocity, soils or vegetation. Copyright (c) 2015 John Wiley & Sons, Ltd.
The spherical vaterite CaCO3 microcrystals are nowadays widely used as sacrificial templates for fabrication of various microcarriers made of biopolymers (e.g., proteins, nucleic acids, enzymes) due to porous structure and mild template elimination conditions. Here, we demonstrated for the first time that polymer microcarriers with tuned internal nanoarchitecture can be designed by employing the CaCO3 crystals of controlled porosity. The layer-by-layer deposition has been utilized to assemble shell-like (hollow) and matrix-like (filled) polymer capsules due to restricted and free polymer diffusion through the crystal pores, respectively. The crystal pore size in the range of few tens of nanometers can be adjusted without any additives by variation of the crystal preparation temperature in the range 745 degrees C. The temperature-mediated growth mechanism is explained by the Ostwald ripening of nanocrystallites forming the crystal secondary structure. Various techniques including SEM, AFM, CLSM, Raman microscopy, nitrogen adsorptiondesorption, and XRD have been employed for crystal and microcapsule analysis. A three-dimensional model is introduced to describe the crystal internal structure and predict the pore cutoff and available surface for the pore diffusing molecules. Inherent biocompatibility of CaCO3 and a possibility to scale the porosity in the size range of typical biomacromolecules make the CaCO3 crystals extremely attractive tools for template assisted designing tailor-made biopolymer-based architectures in 2D to 3D targeted at drug delivery and other bioapplications.
This study explores (mis)interpretation of biclausal wh-questions by French-speaking adults and children, aiming to investigate cross-linguistic differences in sentence revision mechanisms. Following previous work in Japanese the ambiguity of wh-questions was manipulated: In ambiguous questions, the fronted wh-phrase could be associated with the first, main-clause verb or the second, embedded-clause verb, while in garden-path questions, an inserted filled-gap prepositional phrase (PP) blocked main-clause attachment. Importantly, French differs from Japanese in that the filled gap arises after the first verb-that is, after the wh-phrase has been interpreted within the main clause. Two story-based comprehension experiments were conducted to probe the effect of word order on revision performance. Adults and children frequently provided main-clause interpretations of ambiguous questions. In filled-gap questions, children displayed relatively acute sensitivity to the filled-gap in wh-argument questions (Experiment 2), but not in wh-adjunct questions (Experiment 1); adults showed surprisingly low sensitivity to it, frequently misinterpreting adjunct and argument questions. Acceptability ratings (Experiment 3) showed that adults systematically prefer in situ questions over wh-fronting questions. We conclude that timing of the error signal influences revision, and that whereas French-speaking children prioritize syntactic cues, adults prioritize distributional information about the optionality of wh-fronting in French.
Teachers’ beliefs are crucial to the success of inclusion programmes and reform efforts for children with special educational needs (SEN). Based on this evidence, one hundred and thirty-nine primary pre-service teachers from one training institution in the Netherlands completed an adapted version of a measure of beliefs towards inclusive education. In contrast to previous studies on pre-service teachers, results of this study showed participants held neutral or negative beliefs towards this matter. In addition, limited time for pupils received the highest rating as a barrier to inclusion, whereas direct teaching experience was the most preferred method of inclusion. The implications of this study for practice and indications for future research are discussed.
Water research is introduced from the combined perspectives of natural and social science and cases of citizen and stakeholder coproduction of knowledge. Using the overarching notion of transdisciplinarity, we examine how interdisciplinary and participatory water research has taken place and could be developed further. It becomes apparent that water knowledge is produced widely within society, across certified disciplinary experts and noncertified expert stakeholders and citizens. However, understanding and management interventions may remain partial, or even conflicting, as much research across and between traditional disciplines has failed to integrate disciplinary paradigms due to philosophical, methodological, and communication barriers. We argue for more agonistic relationships that challenge both certified and noncertified knowledge productively. These should include examination of how water research itself embeds and is embedded in social context and performs political work. While case studies of the cultural and political economy of water knowledge exist, we need more empirical evidence on how exactly culture, politics, and economics have shaped this knowledge and how and at what junctures this could have turned out differently. We may thus channel the coproductionist critique productively to bring perspectives, alternative knowledges, and implications into water politics where they were not previously considered; in an attempt to counter potential lock-in to particular water policies and technologies that may be inequitable, unsustainable, or unacceptable. While engaging explicitly with politics, transdisciplinary water research should remain attentive to closing down moments in the research process, such as framings, path-dependencies, vested interests, researchers’ positionalities, power, and scale.
The matrix metalloproteinases (MMP) MMP-2 and MMP-9 are physiological regulators of vascular remodelling. Their dysregulation could contribute to vascular calcification. We examined the role of the MMP-2 and MMP-9 in uraemic vascular calcification in vivo and in vitro. The impact of pharmacological MMP inhibition on the development of media calcifications was explored in an aggressive animal model of uraemic calcification. In addition, the selective effects of addition and inhibition, respectively, of MMP-2 and MMP-9 on calcium-/phosphate-induced calcifications were studied in a murine cell line of vascular smooth muscle cells (VSMCs). High-dose calcitriol treatment of uraemic rats given a high phosphate diet induced massive calcifications, apoptosis and increased gene expressions of MMP-2, MMP-9 and of osteogenic transcription factors and proteins in aortic VSMC. The MMP inhibitor doxycycline prevented the VSMC transdifferentiation to osteoblastic cells, suppressed transcription of mediators of matrix remodelling and almost completely blocked aortic calcifications while further increasing apoptosis. Similarly, specific inhibitors of either MMP-2 or -9, or of both gelatinases (Ro28-2653) and a selective knockdown of MMP-2/-9 mRNA expression blocked calcification of murine VSMC induced by calcification medium (CM). In contrast to MMP inhibition, recombinant MMP-2 or MMP-9 enhanced CM-induced calcifications and the secretion of gelatinases. These data indicate that both gelatinases provide essential signals for phenotypic VSMC conversion, matrix remodelling and the initiation of vascular calcification. Their inhibition seems a promising strategy in the prevention of vascular calcifications.
Positive coping styles and perigenual ACC volume: two related mechanisms for conferring resilience?
(2016)
Stress exposure has been linked to increased rates of depression and anxiety in adults, particularly in females, and has been associated with maladaptive changes in the anterior cingulate cortex (ACC), which is an important brain structure involved in internalizing disorders. Coping styles are important mediators of the stress reaction by establishing homeostasis, and may thus confer resilience to stress-related psychopathology. Anatomical scans were acquired in 181 healthy participants at age 25 years. Positive coping styles were determined using a self-report questionnaire (German Stress Coping Questionnaire, SVF78) at age 22 years. Adult anxiety and depression symptoms were assessed at ages 22, 23 and 25 years with the Young Adult Self-Report. Information on previous internalizing diagnoses was obtained by diagnostic interview (2-19 years). Positive coping styles were associated with increased ACC volume. ACC volume and positive coping styles predicted anxiety and depression in a sex-dependent manner with increased positive coping and ACC volume being related to lower levels of psychopathology in females, but not in males. These results remained significant when controlled for previous internalizing diagnoses. These findings indicate that positive coping styles and ACC volume are two linked mechanisms, which may serve as protective factors against internalizing disorders.
Being motivated by open questions in gauge field theories, we consider non-standard de Rham cohomology groups for timelike compact and spacelike compact support systems. These cohomology groups are shown to be isomorphic respectively to the usual de Rham cohomology of a spacelike Cauchy surface and its counterpart with compact support. Furthermore, an analog of the usual Poincare duality for de Rham cohomology is shown to hold for the case with non-standard supports as well. We apply these results to find optimal spaces of linear observables for analogs of arbitrary degree k of both the vector potential and the Faraday tensor. The term optimal has to be intended in the following sense: The spaces of linear observables we consider distinguish between different configurations; in addition to that, there are no redundant observables. This last point in particular heavily relies on the analog of Poincare duality for the new cohomology groups. Published by AIP Publishing.
Small rodents serve as reservoir hosts for tick-borne pathogens, such as the spirochetes causing Lyme disease. Whether natural coinfections with other macroparasites alter the success of tick feeding, antitick immunity, and the host's reservoir competence for tick-borne pathogens remains to be determined. In a parasitological survey of wild mice in Berlin, Germany, approximately 40% of Ixodes ricinus-infested animals simultaneously harbored a nematode of the genus Heligmosomoides. We therefore aimed to analyze the immunological impact of the nematode/tick coinfection as well as its effect on the tick-borne pathogen Borrelia afzelii. Hosts experimentally coinfected with Heligmosomoides polygyrus and larval/nymphal I. ricinus ticks developed substantially stronger systemic type 2 T helper cell (Th2) responses, on the basis of the levels of GATA-3 and interleukin-13 expression, than mice infected with a single pathogen. During repeated larval infestations, however, anti-tick Th2 reactivity and an observed partial immunity to tick feeding were unaffected by concurrent nematode infections. Importantly, the strong systemic Th2 immune response in coinfected mice did not affect susceptibility to tick-borne B. afzelii. An observed trend for decreased local and systemic Th1 reactivity against B. afzelii in coinfected mice did not result in a higher spirochete burden, nor did it facilitate bacterial dissemination or induce signs of immunopathology. Hence, this study indicates that strong systemic Th2 responses in nematode/tick-coinfected house mice do not affect the success of tick feeding and the control of the causative agent of Lyme disease.
Background: Epidemiological research indicates that the use of prescription drugs to enhance cognitive functioning is prevalent in Western countries, however, research on this phenomenon in Arab countries is lacking. Our study aimed to investigate the frequency of neuroenhancement (NE) using prescription drugs in a sample of employees in Jordan. Methods: A sample of 1186 employees (37.11 +/- 8.37 years old, 495 female), of whom 723 (35.65 +/- 7.53 years old, 396 female) served as teachers, completed a paper-pencil questionnaire. The single sample count technique (SSC) was used in order to secure confidential, self-reporting of prescription drug NE. Results: The 12-month prevalence of NE, estimated with the SSC was 15.43%. At 26.16%, the prevalence estimate was markedly higher in the subsample of teachers compared to non-teachers, 0.29%. Surprisingly, 336 participants did not use the SSC and directly affirmed or denied prescription drug NE. These direct responses yielded a prevalence of 11.57% for the full sample, 9.73% for the teachers and 15.60% for the non-teachers. Conclusion: This is the first study of the frequency of NE in an Arab sample. Results indicate that the use of prescription drug NE is not limited to Western countries and that teachers in Jordan might constitute a high-risk population. Further, participants seem to differ in their use of indirect estimation methods for reporting prescription drug NE. For future research, it might be useful to triangulate standard self reports and indirect estimation methods to assess NE. Possible cultural differences and specific high-risk populations for NE should be investigated further. (C) 2015 Elsevier B.V. All rights reserved.
Phenothiazine-modified redox hydrogels were synthesized and used for the wiring of the aldehyde oxidoreductase PaoABC to electrode surfaces. The effects of the pH value and electrode surface modification on the biocatalytic activity of the layers were studied in the presence of vanillin as the substrate. The enzyme electrodes were successfully employed as bioanodes in vanillin/O-2 biofuel cells in combination with a high potential bilirubin oxidase biocathode. Open circuit voltages of around 700 mV could be obtained in a two compartment biofuel cell setup. Moreover, the use of a rather hydrophobic polymer with a high degree of crosslinking sites ensures the formation of stable polymer/enzyme films which were successfully used as bioanode in membrane-less biofuel cells. (C) 2015 Elsevier B.V. All rights reserved.
To turn or not to turn?
(2016)
Bacteria typically swim in straight runs, interruped by sudden turning events. In particular, some species are limited to a reversal in the swimming direction as the only turning maneuver at their disposal. In a recent article, Grossmann et al (2016 New J. Phys. 18 043009) introduce a theoretical framework to analyze the diffusive properties of active particles following this type of run-and-reverse pattern. Based on a stochastic clock model to mimic the regulatory pathway that triggers reversal events, they show that a run-and-reverse swimmer can optimize its diffusive spreading by tuning the reversal rate according to the level of rotational noise. With their approach, they open up promising new perspectives of how to incorporate the dynamics of intracellular signaling into coarse-grained active particle descriptions.
Surveys for more than 9,500 households were conducted in the growing seasons 2002/2003 or 2003/2004 in eleven African countries: Burkina Faso, Cameroon, Ghana, Niger and Senegal in western Africa; Egypt in northern Africa; Ethiopia and Kenya in eastern Africa; South Africa, Zambia and Zimbabwe in southern Africa. Households were chosen randomly in districts that are representative for key agro-climatic zones and farming systems. The data set specifies farming systems characteristics that can help inform about the importance of each system for a country’s agricultural production and its ability to cope with short- and long-term climate changes or extreme weather events. Further it informs about the location of smallholders and vulnerable systems and permits benchmarking agricultural systems characteristics.
Grazing by domestic ungulates can have substantial impacts on forests in arid and semi-arid regions, possibly including severe loss of carbon from the soil. Predicting net livestock impacts on soil organic carbon stocks remains challenging, however, due to the dependence on animal loads and on soil and environmental parameters. The objective of this study was to better understand grazing effects on soil organic carbon in seasonal tropical dry forests of north-eastern Brazil (Caatinga) by quantifying carbon stocks of the upper soil profile (0–5 cm depth) and greater soil depths (>5 cm depth down to bedrock) along a gradient of grazing intensity while accounting for other influencing factors such as soil texture, vegetation, landscape topography, and water availability. We analysed soil organic carbon, soil clay content, altitude above sea level, soil depth to bedrock, distance to the nearest permanent water body, species diversity of perennial plants and aboveground biomass on 45 study plots located in the vicinity of the Itaparica Reservoir, Pernambuco, Brazil. Livestock (mainly goats and cattle) are unevenly distributed in the studied ecosystem, thus grazing intensity was accounted for based on the weight of livestock droppings per square metre and classified as no or light, intermediate, or heavy grazing. The mean soil organic carbon in the area was 16.86 ± 1.28 Mg ha−1 C with approximately one-quarter found in the upper 5 cm of the soil profile (4.14 ± 0.43 Mg ha−1 C) and the remainder (12.57 ± 0.97 Mg ha−1 C) in greater soil depths (>5 cm). Heavy grazing led to significantly lower soil organic carbon stocks in the upper 5 cm, whereas no effect on soil organic carbon of the soil overall or in greater soil depths was detectable. The soil’s clay content and the altitude proved to be the most relevant factors influencing overall soil organic carbon stocks and those in greater soil depths (>5 cm). Our findings suggest that grazing causes substantial release of carbon from Brazilian dry forest soils, which should be addressed through improved grazing management via a legally compulsory rotation system. This would ultimately contribute to the conservation of a unique forest system and associated ecosystem services.
Language and communication disorders are often associated with deficits in working memory (WM) and interference control. WM studies involving children with specific language impairment (SLI) have traditionally been framed using either resource theories or decay accounts, particularly Baddeley's model. Although significant interference problems in children with SLI are apparent in error analysis data from WM and language tasks, interference theories and paradigms have not been widely used in the SLI literature. A primary goal of the present paper is to provide an overview of interference deficits in children with SLI. Review of the extant literature on interference control shows deficits in this population; however, the source and the nature of the deficit remain unclear. Thus, a second key aim in our review is to demonstrate the need for theoretically driven experimental paradigms in order to better understand individual variations associated with interference weaknesses in children with SLI.
Surface movements during the largest subduction zone earthquakes commonly drown coastlines. Yet, on geological timescales, coastlines above subduction zones uplift. Here I use a morphometric analysis combined with a numerical model of landscape evolution to estimate uplift rates along the central Andean rasa-a low-relief coastal surface bounded by a steep cliff formed by wave erosion. I find that the rasa has experienced steady uplift of 0.13 +/- 0.04 mm per year along a stretch of more than 2,000 km in length, during the Quaternary. These long-term uplift rates do not correlate with Global Positioning System (GPS) measurements of interseismic movements over the decadal scale, which implies that permanent uplift is not predominantly accumulated during the interseismic period. Instead, the rate of rasa uplift correlates with slip during earthquakes straddling the crust-mantle transition, the Moho. Such deeper earthquakes with magnitude 7 to 8 that occurred between 1995 and 2012 resulted in decimetres of coastal uplift. Slip during these earthquakes is located below the locked portion of the plate interface, and therefore may translate into permanent deformation of the overlying plate, where it causes uplift of the coastline. Thus, lower parts of the plate boundary are stably segmented over hundreds to millions of years. I suggest the coastline marks the surface expression of the transition between the shallow, locked seismogenic domain and the deeper, conditionally stable domain where modest earthquakes build up topography.
para-Substituted aryl prenyl ethers undergo a deprenylation reaction upon microwave irradiation. This offers the opportunity to use a prenyl ether as a thermolabile protecting group in the synthesis of natural products with a chromone structure, which proceeds via a tandem deprenylation/6-endo-cyclization sequence.
Formate dehydrogenases (FDHs) are capable of performing the reversible oxidation of formate and are enzymes of great interest for fuel cell applications and for the production of reduced carbon compounds as energy sources from CO2. Metal containing FDHs in general contain a highly conserved active site, comprising a molybdenum (or tungsten) center coordinated by two molybdopterin guanine dinucleotide molecules, a sulfido and a (seleno-)cysteine ligand, in addition to a histidine and arginine residue in the second coordination sphere. So far, the role of these amino acids in catalysis has not been studied in detail, because of the lack of suitable expression systems and the lability or oxygen sensitivity of the enzymes. Here, the roles of these active site residues is revealed using the Mo-containing FDH from Rhodobacter capsulatus. Our results show that the cysteine ligand at the Mo ion is displaced by the formate substrate during the reaction, the arginine has a direct role in substrate binding and stabilization, and the histidine elevates the pK(a) of the active site cysteine. We further found that in addition to reversible formate oxidation, the enzyme is further capable of reducing nitrate to nitrite. We propose a mechanistic scheme that combines both functionalities and provides important insights into the distinct mechanisms of C-H bond cleavage and oxygen atom transfer catalyzed by formate dehydrogenase.
Recruitment of European eels (Anguilla anguilla) has declined to the extent that they have been added to the IUCN Red List of Threatened Species. Therefore, it is critical to ensure that eels complete their outward river migration in order to contribute to the available spawning stock. We conducted a 4-year (2007-2011) telemetry study to understand the migratory behaviour and potential impact of environmental factors on the eel during this critical life stage. Out of 399 female eels tagged with acoustic transmitters, only 28% demonstrated clear downstream migratory behaviour. Fifty-five percent were detected exhibiting no downstream migration behaviour and 17% were not detected at any monitoring station. Movement patterns of downstream-migrating (silver) eels were characterized by nocturnal activity and seasonal migration, with distinct peaks in autumn and spring. Migration was often discontinuous and exhibited phases of active locomotion and expanded stopovers. The most important determinants of movement activity were water temperature, cumulative precipitation and moonlight, although the significance varied by season and location in the river basin. Our results evidence a discontinuous, stepwise migration over an extended period. Furthermore, our findings indicate that migration success depends on holding duration prior to tagging and environmental predictors with varying importance depending on the season, as well as the locations of capture, tagging and release. Copyright (c) 2015 John Wiley & Sons, Ltd.
Purpose Persons with work-anxieties are especially endangered for work capacity impairment and sick leave. Work capacity impairment is not directly due to symptoms but due to illness-related capacity disorders. Work capacity impairments can be described on different dimensions (e.g., social interaction, decision making and judgment, endurance, mobility). Understanding the type of work capacity impairment is important for reintegration interventions. This is the first study to investigate work capacity impairment in risk patients with different work-anxieties. Results Patients with different work-anxieties were impaired in different capacity dimensions: Work-related social anxiety went along with clinically relevant impairment in capacity of assertiveness (M = 2.40), anxiety of insufficiency went along with impaired capacity of endurance (M = 2.20), and work-related generalized worrying was accompanied by impairment in the capacity for decision making (M = 1.82). Specific capacity impairment dimensions were related to sick leave duration, while a global work ability prognosis was not. Conclusions The capacity approach is useful to describe work impairment more precisely and beyond symptoms. On this basis, reintegration-focusing interventions such as capacity training (e.g., social interaction training) or work adjustment (e.g., reducing exposure with interactional work tasks) can be initiated.
Cognitive Function in Adolescent Patients with Anorexia Nervosa and Unipolar Affective Disorders
(2016)
Studies have shown impairments in cognitive function among adult patients with anorexia nervosa (AN) and affective disorders (AD). The association between cognitive dysfunctions, AN and AD as well as the specificity for these psychiatric diagnoses remains unclear. Therefore, we examined cognitive flexibility and processing speed in 47 female adolescent patients with AN, 21 female adolescent patients with unipolar affective disorders and 48 female healthy adolescents. All participants completed a neuropsychological test battery. There were no significant group differences regarding cognitive function, except for psychomotor processing speed with poorer performance in patients with AN. A further analysis revealed that all groups performed with the normal range, although patients with AN were over represented in the poorest performing quartile. We found no severe cognitive impairments in either patient group. Nevertheless, belonging to the AN group contributed significantly to poor performances in neuropsychological tasks. Therefore, we conclude that the risk for cognitive impairments is slightly higher for patients with AN. Copyright (c) 2015 John Wiley & Sons, Ltd and Eating Disorders Association.
We examined the spontaneous association between numbers and space by documenting attention deployment and the time course of associated spatial-numerical mapping with and without overt oculomotor responses. In Experiment 1, participants maintained central fixation while listening to number names. In Experiment 2, they made horizontal target-direct saccades following auditory number presentation. In both experiments, we continuously measured spontaneous ocular drift in horizontal space during and after number presentation. Experiment 2 also measured visual-probe-directed saccades following number presentation. Reliable ocular drift congruent with a horizontal mental number line emerged during and after number presentation in both experiments. Our results provide new evidence for the implicit and automatic nature of the oculomotor resonance effect associated with the horizontal spatial-numerical mapping mechanism.
Spatial-numerical associations (small numbers-left/lower space and large numbers-right/upper space) are regularly found in simple number categorization tasks. These associations were taken as evidence for a spatially oriented mental number line. However, the role of spatial-numerical associations during more complex number processing, such as counting or mental arithmetic is less clear. Here, we investigated whether counting is associated with a movement along the mental number line. Participants counted aloud upward or downward in steps of 3 for 45 s while looking at a blank screen. Gaze position during upward counting shifted rightward and upward, while the pattern for downward counting was less clear. Our results, therefore, confirm the hypothesis of a movement along the mental number line for addition. We conclude that space is not only used to represent number magnitudes but also to actively operate on numbers in more complex tasks such as counting, and that the eyes reflect this spatial mental operation.
A gelatin-poly(lactic-co-glycolic acid), PLGA, composite scaffold, featuring a highly oriented pore channel structure, was developed as a template for articular cartilage regeneration. As a design principle the composite scaffold was optimized to contain only medical grade educts and accordingly no chemical cross linking agents or other toxicological relevant substances or methods were used. Scaffolds were synthesized using a freeze structuring method combined with an electrochemical process followed by freeze-drying. Finally, cross linking was performed using dehydrothermal treatment, which was simultaneously used for sterilization purposes. These composite scaffolds were analyzed in regard to structural and biomechanical properties, and to their degradation behavior. Furthermore, cell culture performance was tested using chondrocytes originated from joint articular cartilage tissue from 6 to 10 months old domestic pigs. Finally, the scaffolds were tested for tissue biocompatibility and their ability for tissue integration in a rat model. The scaffolds showed both excellent functional performance and high biocompatibility in vitro and in vivo. We expect that these gelatin-PLGA scaffolds can effectively support chondrogenesis in vivo demonstrating great potential for the use in cartilage defect treatment. (C) 2016 Elsevier B.V. All rights reserved.
In this article, we examined to what extent parental offending influences the timing of entry into parenthood of children. Based on a literature review, we hypothesized that children of delinquent parents would be more likely to enter into parenthood at a relatively young age, and that part of that association could be explained by differences between children of delinquent and non-delinquent parents in the timing of entry into marriage and in their own delinquent behaviour. Using data from a five-generation study of high risk families in the Netherlands, we found that parental delinquency increases the chance of early childbearing among daughters, but not among sons. Among sons, parental delinquency increased son's delinquency, suggesting that parental delinquency has different consequences for the life courses of their sons and daughters.
Offending and mortality
(2016)
Background: Previous research has shown that offenders are at increased risk to die prematurely, but the etiology of this association is still unknown. Moreover, most previous studies use relatively short follow-up periods and do not take into account variation within the offender population with respect to frequency, timing and types of offenses. Method: Using conviction data for a number of families at high-risk of offending born on average in 1932, we study mortality in both offenders and non-offenders, from a similar socio-economic background, until 2007. We condition on life expectancy of the parents, age, gender, year of birth and marital status. We investigate associations between mortality and offending for different types of offenses: violent offenses, property offenses, weapons offenses, drugs offenses and driving under influence. Results: In general, offending sample members were not significantly more likely to have died than non offending sample members. Compared to the general population, however, both the offending and non offending sample members were at increased risk to die. Sample members who were convicted for driving under the influence of alcohol or weapons offenses were at increased risk to die prematurely compared to non-offending sample members. Conclusions: The relationship between offending in general and mortality is largely spurious. Limitations: The use of official conviction data might have influenced the results. (C) 2015 Elsevier Ltd. All rights reserved.
Uncovering the acoustic vowel space of a previously undescribed language: The vowels of Nambo
(2016)
This study presents the first acoustic description of the vowel space of a Papuan language—Nambo, spoken in southern Papua New Guinea—based on duration and first and second formant measurements from 19 adult male and female speakers across three age groups (young, middle-aged, senior). Phonemically, Nambo has six full vowels /i, e, æ, ɑ, o, u/ and a reduced vowel tentatively labeled /ə/. Unlike the full vowels, the quality of /ə/ showed great variation: seniors' and young females' realizations tended to be more open and retracted than those by young males, while middle-aged speakers' productions fell between these two variants.
Background: Cannabis is the most commonly used illegal substance among adolescents and young adults. Problematic cannabis use is often associated with comorbid psychopathological problems. The purpose of the current study was to elucidate the underlying developmental processes connecting externalizing and internalizing psychopathology in childhood and adolescence with problematic cannabis use in young adulthood. Methods: Data were drawn from the Mannheim Study of Children at Risk, an ongoing epidemiological cohort study from birth to adulthood. For n = 307 participants, symptom scores of conduct/oppositional defiant disorder, attention problems, hyperactivity/impulsivity, and internalizing disorders were available for the periods of childhood (4.5-11 years) and adolescence (15 years). At age 25 years, problematic cannabis use was assessed via clinical interview and a self-rating questionnaire. Results: At age 25 years, problematic cannabis use was identified in n = 28 participants (9.1%). Childhood conduct/oppositional behavior problems were predictive of problematic cannabis use during young adulthood when comorbid symptoms were controlled for. No such effect was found for childhood attention, hyperactivity/impulsivity or internalizing problems. With respect to psychopathological symptoms during adolescence, only attention problems were significantly related to later problematic cannabis use when controlling for comorbidity. Conclusions: The current study highlights the role of conduct/oppositional behavior problems during childhood and attention problems during adolescence in later problematic cannabis use. It sheds more light on the developmental sequence of childhood and adolescence psychopathology and young adult cannabis use, which is a prerequisite for effective prevention approaches. (C) 2016 Elsevier Ireland Ltd. All rights reserved.
The aim of the present study was to investigate nutritional and metabolic parameters during the dry and early postpartum periods of ovulatory and anovulatory cows, as well as their postpartum reproductive performance. Blood samples from 20 multiparous Holstein cows were collected once a week from the far-off dry period to 3 weeks postpartum. Early postpartum (0-3 weeks) ovulation was confirmed using plasma progesterone concentration profiles, and cows were considered ovulatory if they had resumed luteal activity by this point (n = 9), whereas cows that had not were considered anovulatory (n = 11). Data from the ovulatory and anovulatory cows were analyzed separately for the far-off dry period (7-4 weeks prepartum), the close-up dry period (3-1 weeks prepartum), and the early postpartum period (0-3 weeks). Serum gamma-glutamyl transpeptidase activity (far-off, P = 0.065; close-up, P = 0.051; and early postpartum, P = 0.030) and aspartate aminotransferase (close-up, P = 0.050 and early postpartum, P = 0.087) activities were higher in anovulatory than in ovulatory cows. The days open period was longer (P = 0.019) in anovulatory than in ovulatory cows, and the number of artificial inseminations per conception (P = 0.025) was greater. In conclusion, we found that continuously high gamma-glutamyl transpeptidase activities in serum, which may be induced by liver disorders, prevent subsequent ovulation and affect subsequent fertility, even if cows obtain sufficient ovulation-related energy and beta-carotene.
Magnetic reconnection is a fundamental process of topology change and energy release, taking place in plasmas on the Sun, in space, in astrophysical objects and in the laboratory. However, observational evidence has been relatively rare and typically only partial. Here we present evidence of fast reconnection in a solar filament eruption using high-resolution H-alpha images from the New Vacuum Solar Telescope, supplemented by extreme ultraviolet observations. The reconnection is seen to occur between a set of ambient chromospheric fibrils and the filament itself. This allows for the relaxation of magnetic tension in the filament by an untwisting motion, demonstrating a flux rope structure. The topology change and untwisting are also found through nonlinear force-free field modelling of the active region in combination with magnetohydrodynamic simulation. These results demonstrate a new role for reconnection in solar eruptions: the release of magnetic twist.