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We report on the pH-dependent bioelectrocatalytic activity of the redox enzyme xanthine dehydrogenase (XDH) in the presence of sulfonated polyaniline PMSA1 (poly(2-methoxyaniline-5-sulfonic acid)-co-aniline). Ultraviolet-visible (UV-vis) spectroscopic measurements with both components in solution reveal electron transfer from the hypoxanthine (HX)-reduced enzyme to the polymer. The enzyme shows bioelectrocatalytic activity on indium tin oxide (ITO) electrodes, when the polymer is present. Depending on solution pH, different processes can be identified. It can be demonstrated that not only product-based communication with the electrode but also efficient polymer-supported bioelectrocatalysis occur. Interestingly, substrate dependent catalytic currents can be obtained in acidic and neutral solutions, although the highest activity of XDH with natural reaction partners is in the alkaline region. Furthermore, operation of the enzyme electrode without addition of the natural cofactor of XDH is feasible. Finally, macroporous ITO electrodes have been used as an immobilization platform for the fabrication of HX-sensitive electrodes. The study shows that the efficient polymer/enzyme interaction can be advantageously combined with the open structure of an electrode material of controlled pore size, resulting in good processability, stability, and defined signal transfer in the presence of a substrate.
In a series of experiments, we tested a recently proposed hypothesis stating that the degree of alignment between the form of a mental representation resulting from learning with a particular visualization format and the specific requirements of a learning task determines learning performance (task-appropriateness). Groups of participants were required to learn the stroke configuration, the stroke order, or the stroke directions of a set of Chinese pseudocharacters. For each learning task, participants were divided into groups receiving dynamic, static-sequential, or static visualizations. An old/new character recognition task was given at test. The results showed that learning both stroke configuration and stroke order was best with static pictures (Experiments 1 and 2), while there was no reliable difference between the groups for learning stroke direction (Experiment 3). An additional experiment, however, revealed that learning with sequential pictures was superior when testing was carried out with sequential pictures, irrespective of the learning task (Experiment 4). The combined evidence from all experiments speaks against task requirements playing a role in determining the effectiveness of a visualization format. Furthermore, the evidence supports the view that a high degree of congruence between information presented during learning and information presented at test results in better learning (study-test congruence). Implications for instructional design are discussed.
Many German lakes experienced significant water level declines in recent decades that are not fully understood due to the short observation period. At a typical northeastern German groundwater-fed lake with a complex basin morphology, an acoustic sub-bottom profile was analysed together with a transect of five sediment cores, which were correlated using multiple proxies (sediment facies, -XRF, macrofossils, subfossil Cladocera). Shifts in the boundary between sand and mud deposition were controlled by lake level changes, and hence, allowed the quantification of an absolute lake level amplitude of similar to 8m for the Holocene. This clearly exceeded observed modern fluctuations of 1.3m (AD 1973-2010). Past lake level changes were traced continuously using the calcium-record. During high lake levels, massive organic muds were deposited in the deepest lake basin, whereas lower lake levels isolated the sub-basins and allowed carbonate deposition. During the beginning of the Holocene (>9700cal. a BP), lake levels were high, probably due to final melting of permafrost and dead-ice remains. The establishment of water-use intensive Pinus forests caused generally low (3-4m below modern) but fluctuating lake levels (9700-6400cal. a BP). Afterwards, the lake showed an increasing trend and reached a short-term highstand at c.5000cal. a BP (4m above modern). At the transition towards a cooler and wetter late Holocene, forests dominated by Quercus and Fagus and initial human impact probably contributed more positively to groundwater recharge. Lake levels remained high between 3800 and 800cal. a BP, but the lake system was not sensitive enough to record short-term fluctuations during this period. Lake level changes were recorded again when humans profoundly affected the drainage system, land cover and lake trophy. Hence, local Holocene water level changes reflect feedbacks between catchment and vegetation characteristics and human impact superimposed by climate change at multiple temporal scales.
Permafrost degradation influences the morphology, biogeochemical cycling and hydrology of Arctic landscapes over a range of time scales. To reconstruct temporal patterns of early to late Holocene permafrost and thermokarst dynamics, site-specific palaeo-records are needed. Here we present a multi-proxy study of a 350-cm-long permafrost core from a drained lake basin on the northern Seward Peninsula, Alaska, revealing Lateglacial toHolocene thermokarst lake dynamics in a central location of Beringia. Use of radiocarbon dating, micropalaeontology (ostracods and testaceans), sedimentology (grain-size analyses, magnetic susceptibility, tephra analyses), geochemistry (total nitrogen and carbon, total organic carbon, C-13(org)) and stable water isotopes (O-18, D, dexcess) of ground ice allowed the reconstruction of several distinct thermokarst lake phases. These include a pre-lacustrine environment at the base of the core characterized by the Devil Mountain Maar tephra (22800 +/- 280cal. a BP, Unit A), which has vertically subsided in places due to subsequent development of a deep thermokarst lake that initiated around 11800cal. a BP (Unit B). At about 9000cal. a BP this lake transitioned from a stable depositional environment to a very dynamic lake system (Unit C) characterized by fluctuating lake levels, potentially intermediate wetland development, and expansion and erosion of shore deposits. Complete drainage of this lake occurred at 1060cal. a BP, including post-drainage sediment freezing from the top down to 154cm and gradual accumulation of terrestrial peat (Unit D), as well as uniform upward talik refreezing. This core-based reconstruction of multiple thermokarst lake generations since 11800cal. a BP improves our understanding of the temporal scales of thermokarst lake development from initiation to drainage, demonstrates complex landscape evolution in the ice-rich permafrost regions of Central Beringia during the Lateglacial and Holocene, and enhances our understanding of biogeochemical cycles in thermokarst-affected regions of the Arctic.
Anti-Stokes resonant x-ray Raman scattering for atom specific and excited state selective dynamics
(2016)
Ultrafast electronic and structural dynamics of matter govern rate and selectivity of chemical reactions, as well as phase transitions and efficient switching in functional materials. Since x-rays determine electronic and structural properties with elemental, chemical, orbital and magnetic selectivity, short pulse x-ray sources have become central enablers of ultrafast science. Despite of these strengths, ultrafast x-rays have been poor at picking up excited state moieties from the unexcited ones. With time-resolved anti-Stokes resonant x-ray Raman scattering (AS-RXRS) performed at the LCLS, and ab initio theory we establish background free excited state selectivity in addition to the elemental, chemical, orbital and magnetic selectivity of x-rays. This unparalleled selectivity extracts low concentration excited state species along the pathway of photo induced ligand exchange of Fe(CO)(5) in ethanol. Conceptually a full theoretical treatment of all accessible insights to excited state dynamics with AS-RXRS with transform-limited x-ray pulses is given-which will be covered experimentally by upcoming transform-limited x-ray sources.
We present an algorithm that performs sequentially one-dimensional inversion of subsurface magnetic permeability and electrical conductivity by using multi-configuration electromagnetic induction sensor data. The presented method is based on the conversion of the in-phase and out-of-phase data into effective magnetic permeability and electrical conductivity of the equivalent homogeneous half-space. In the case of small-offset systems, such as portable electromagnetic induction sensors, for which in-phase and out-of-phase data are moderately coupled, the effective half-space magnetic permeability and electrical conductivity can be inverted sequentially within an iterative scheme. We test and evaluate the proposed inversion strategy using synthetic and field examples. First, we apply it to synthetic data for some highly magnetic environments. Then, the method is tested on real field data acquired in a basaltic environment to image a formation of archaeological interest. These examples demonstrate that a joint interpretation of in-phase and out-of-phase data leads to a better characterisation of the subsurface in magnetic environments such as volcanic areas.
The effect of methods of statistical downscaling of daily precipitation on changes in extreme flow indices under a plausible future climate change scenario was investigated in 11 catchments selected from 9 countries in different parts of Europe. The catchments vary from 67 to 6171 km(2) in size and cover different climate zones. 15 regional climate model outputs and 8 different statistical downscaling methods, which are broadly categorized as change factor and bias correction based methods, were used for the comparative analyses. Different hydrological models were implemented in different catchments to simulate daily runoff. A set of flood indices were derived from daily flows and their changes have been evaluated by comparing their values derived from simulations corresponding to the current and future climate. Most of the implemented downscaling methods project an increase in the extreme flow indices in most of the catchments. The catchments where the extremes are expected to increase have a rainfall dominated flood regime. In these catchments, the downscaling methods also project an increase in the extreme precipitation in the seasons when the extreme flows occur. In catchments where the flooding is mainly caused by spring/summer snowmelt, the downscaling methods project a decrease in the extreme flows in three of the four catchments considered. A major portion of the variability in the projected changes in the extreme flow indices is attributable to the variability of the climate model ensemble, although the statistical downscaling methods contribute 35-60% of the total variance. (C) 2016 Elsevier B.V. All rights reserved.
The repeated occurrence of exceptional floods within a few years, such as the Rhine floods in 1993 and 1995 and the Elbe and Danube floods in 2002 and 2013, suggests that floods in Central Europe may be organized in flood-rich and flood-poor periods. This hypothesis is studied by testing the significance of temporal clustering in flood occurrence (peak-over-threshold) time series for 68 catchments across Germany for the period 1932-2005. To assess the robustness of the results, different methods are used: Firstly, the index of dispersion, which quantifies the departure from a homogeneous Poisson process, is investigated. Further, the time-variation of the flood occurrence rate is derived by non-parametric kernel implementation and the significance of clustering is evaluated via parametric and non-parametric tests. Although the methods give consistent overall results, the specific results differ considerably. Hence, we recommend applying different methods when investigating flood clustering. For flood estimation and risk management, it is of relevance to understand whether clustering changes with flood severity and time scale. To this end, clustering is assessed for different thresholds and time scales. It is found that the majority of catchments show temporal clustering at the 5% significance level for low thresholds and time scales of one to a few years. However, clustering decreases substantially with increasing threshold and time scale. We hypothesize that flood clustering in Germany is mainly caused by catchment memory effects along with intra- to inter-annual climate variability, and that decadal climate variability plays a minor role. (C) 2016 Elsevier B.V. All rights reserved.
It has previously been shown that fatigue and unstable surfaces affect jump performance. However, the combination thereof is unresolved. Thus, the purpose of this study was to examine the effects of fatigue and surface instability on jump performance and leg muscle activity. Twenty elite volleyball players (18 +/- 2 years) performed repetitive vertical double-leg box jumps until failure. Before and after a fatigue protocol, jump performance (i.e., jump height) and electromyographic activity of selected lower limb muscles were recorded during drop jumps (DJs) and countermovement jumps (CMJs) on a force plate on stable and unstable surfaces (i.e., balance pad on top of force plate). Jump performance (3-7%; P < 0.05; 1.14 <= d <= 2.82), and muscle activity (2-27%; P < 0.05; 0.59 <= d <= 3.13) were lower following fatigue during DJs and CMJs, and on unstable compared with stable surfaces during DJs only (jump performance: 8%; P < 0.01; d = 1.90; muscle activity: 9-25%; P < 0.05; 1.08 <= d <= 2.54). No statistically significant interactions of fatigue by surface condition were observed. Our findings revealed that fatigue impairs neuromuscular performance during DJs and CMJs in elite volleyball players, whereas surface instability affects neuromuscular DJ performance only. Absent fatigue x surface interactions indicate that fatigue-induced changes in jump performance are similar on stable and unstable surfaces in jump-trained athletes.
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.
p-Type Doping of Poly(3-hexylthiophene) with the Strong Lewis Acid Tris(pentafluorophenyl)borane
(2016)
State-of-the-art p-type doping of organic semiconductors is usually achieved by employing strong -electron acceptors, a prominent example being tetrafluorotetracyanoquinodimethane (F(4)TCNQ). Here, doping of the semiconducting model polymer poly(3-hexylthiophene), P3HT, using the strong Lewis acid tris(pentafluorophenyl)borane (BCF) as a dopant, is investigated by admittance, conductivity, and electron paramagnetic resonance measurements. The electrical characteristics of BCF- and F(4)TCNQ-doped P3HT layers are shown to be very similar in terms of the mobile hole density and the doping efficiency. Roughly 18% of the employed dopants create mobile holes in either F-4 TCNQ- or BCF-doped P3HT, while the majority of doping-induced holes remain strongly Coulomb-bound to the dopant anions. Despite similar hole densities, conductivity and hole mobility are higher in BCF-doped P3HT layers than in F(4)TCNQ-doped samples. This and the good solubility in many organic solvents render BCF very useful for p-type doping of organic semiconductors.
A dual-characteristic polymer field-effect transistor has markedly different characteristics in low and high voltage operations. In the low-voltage range (<5 V) it shows sharp subthreshold slopes (0.3–0.4 V dec−1), using which a low-voltage inverter with gain 8 is realized, while high-voltage (>5 V) induces symmetric current with regard to drain and gate voltages, leading to discrete differential (trans) conductances.
A synchronization experiment on two mutual interacting organ pipes is compared with a theoretical model which takes into account the coupling mechanisms by the underlying first principles of fluid mechanics and aeroacoustics. The focus is on the Arnold-tongue, a mathematical object in the parameter space of detuning and coupling strength which quantitatively captures the interaction of the synchronized sound sources. From the experiment, a nonlinearly shaped Arnold-tongue is obtained, describing the coupling of the synchronized pipe-pipe system. This is in contrast to the linear shaped Arnold-tongue found in a preliminary experiment of the coupled system pipe-loudspeaker. To understand the experimental result, a coarse-grained model of two nonlinear coupled self-sustained oscillators is developed. The model, integrated numerically, is in very good agreement with the synchronization experiment for separation distances of the pipes in the far field and in the intermediate field. The methods introduced open the door for a deeper understanding of the fundamental processes of sound generation and the coupling mechanisms on mutual interacting acoustic oscillators. (C) 2016 Acoustical Society of America.
Rotational Barriers of Substituted BIPHEP Ligands: A Comparative Experimental and Theoretical Study
(2016)
The interconversion barriers of 14 different 3,3- and 5,5-disubstituted tropos BIPHEP [2,2-bis(diphenylphosphino)-1,1-biphenyl] and BIPHEP(O) [2,2-bis(diphenylphosphoryl)-1,1-biphenyl] ligands were investigated by enantioselective dynamic high performance liquid chromatography (DHPLC) and DFT calculations using the B3LYP/6-31G* and M06-2X/6-31G* levels of theory. The experimentally determined enantiomerization barriers varied from 86.8 to 101.4 kJmol(-1) and were found to be in excellent agreement with the calculated data. The root-mean-square deviations are 7.3 kJmol(-1) for the B3LYP functional and 11.3 kJmol(-1) for the M06-2X method.
Let A be a nonlinear differential operator on an open set X subset of R-n and S a closed subset of X. Given a class F of functions in X, the set S is said to be removable for F relative to A if any weak solution of A(u) = 0 in XS of class F satisfies this equation weakly in all of X. For the most extensively studied classes F, we show conditions on S which guarantee that S is removable for F relative to A.
Hantaviruses are zoonotic viruses transmitted to humans by persistently infected rodents, giving rise to serious outbreaks of hemorrhagic fever with renal syndrome (HFRS) or of hantavirus pulmonary syndrome (HPS), depending on the virus, which are associated with high case fatality rates. There is only limited knowledge about the organization of the viral particles and in particular, about the hantavirus membrane fusion glycoprotein Gc, the function of which is essential for virus entry. We describe here the X-ray structures of Gc from Hantaan virus, the type species hantavirus and responsible for HFRS, both in its neutral pH, monomeric pre-fusion conformation, and in its acidic pH, trimeric post-fusion form. The structures confirm the prediction that Gc is a class II fusion protein, containing the characteristic beta-sheet rich domains termed I, II and III as initially identified in the fusion proteins of arboviruses such as alpha-and flaviviruses. The structures also show a number of features of Gc that are distinct from arbovirus class II proteins. In particular, hantavirus Gc inserts residues from three different loops into the target membrane to drive fusion, as confirmed functionally by structure-guided mutagenesis on the HPS-inducing Andes virus, instead of having a single "fusion loop". We further show that the membrane interacting region of Gc becomes structured only at acidic pH via a set of polar and electrostatic interactions. Furthermore, the structure reveals that hantavirus Gc has an additional N-terminal "tail" that is crucial in stabilizing the post-fusion trimer, accompanying the swapping of domain III in the quaternary arrangement of the trimer as compared to the standard class II fusion proteins. The mechanistic understandings derived from these data are likely to provide a unique handle for devising treatments against these human pathogens.
One hallmark of aging is the accumulation of protein aggregates, promoted by the unfolding of oxidized proteins. Unraveling the mechanism by which oxidized proteins are degraded may provide a basis to delay the early onset of features, such as protein aggregate formation, that contribute to the aging phenotype. In order to prevent aggregation of oxidized proteins, cells recur to the 20S proteasome, an efficient turnover proteolysis complex. It has previously been shown that upon oxidative stress the 26S proteasome, another form, dissociates into the 20S form. A critical player implicated in its dissociation is the Heat Shock Protein 70 (Hsp70), which promotes an increase in free 20S proteasome and, therefore, an increased capability to degrade oxidized proteins. The aim of this study was to test whether or not Hsp70 is involved in cooperating with the 20S proteasome for a selective degradation of oxidatively damaged proteins. Our results demonstrate that Hsp70 expression is induced in HT22 cells as a result of mild oxidative stress conditions. Furthermore, Hsp70 prevents the accumulation of oxidized proteins and directly promotes their degradation by the 20S proteasome. In contrast the expression of the Heat shock cognate protein 70 (Hsc70) was not changed in recovery after oxidative stress and Hsc70 has no influence on the removal of oxidatively damaged proteins. We were able to demonstrate in HT22 cells, in brain homogenates from 129/SV mice and in vitro, that there is an increased interaction of Hsp70 with oxidized proteins, but also with the 20S proteasome, indicating a role of Hsp70 in mediating the interaction of oxidized proteins with the 20S proteasome. Thus, our data clearly implicate an involvement of Hsp70 oxidatively damaged protein degradation by the 20S proteasome. c) 2016 The Authors. Published by Elsevier Inc. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Microelectrodes modified with electropolymerized plumbagin (PLG) were used for the generation of superoxide radical (O-2(center dot-)) and hydrogen peroxide (H2O2) during oxygen reduction reaction (ORR) in an aqueous medium, specifically in serum-free cell culture media. This is enabled by the specific design of a polymer film on the microelectrode. The generation and diffusion of O-2(center dot-) during electrocatalytic ORR at a positionable PLG polymer-modified microelectrode was followed by fluorescence microscopy with the selective dye 4-chloro-7-nitrobenzo-2-oxa-1,3-diazole (NBD-Cl) and by amperometric detection using a cytochrome c-modified electrode at + 0.13 V. H2O2 production, either by direct oxygen reduction or as product of O-2(center dot-) disproportionation, was monitored by the reaction with Amplex UltraRed. The PLG polymer-modified microelectrodes were used to expose mammalian B6-RPE07 retinal cells to defined local fluxes of reactive oxygen species (ROS), and cellular responses and morphological alterations were observed. The use of a controllable source of ROS opens many possibilities to study how living cells respond to the presence of a certain flux of specific ROS.
How does the selection of a classical language at school affect prospects on the labor market? Even though research on the impact of horizontal educational inequalities on labor market outcomes has become prominent recently, this question has not yet attracted scholarly attention. Based on several differing approaches (Human Capital Theory, Signaling Theory, Homophily Principle), hypotheses are derived about the impact of the language profile at school on labor market prospects at career entry. To test these assumptions, a field experiment was conducted in which applications were submitted in response to job advertisements. Results show that choosing Latin and Ancient Greek has a positive impact on the chances of being invited to a job interview.
Adaptation to physical activity and mental stress in the context of pain. Psychobiological aspects
(2016)
The genesis of chronic pain is predominantly explained by a multidimensional pain model approach that is based on the dysfunctional influence of biological, psychological and social variables as key risk factors inducing aberrant long-term changes. Biological facets comprise adaptation processes on the neuronal, musculoskeletal and (psycho) biological level that can be influenced by physical training or psychosocial factors, such as stress. These factors can play a causative role in developing dysfunctional adaptation mechanisms, which in turn prepare the biological ground to facilitate negative long-term changes in the peripheral and central nervous systems. Hence, these processes can be assumed to be fundamentally involved in the transition from acute to chronic and persistent pain. The aim of this review article is to discuss hypotheses for the genesis of chronic pain and possible treatment strategies. Selected research results about maladaptive processes in chronic pain due to psychological stress and physical activity are presented in order to inspire discussions about the ideal dose-response relationship of physical activity and the combination of different therapeutic concepts.
for educational aspirations
(2016)
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.
Neuromuscular response of the trunk to sudden gait disturbances: Forward vs. backward perturbation
(2016)
The study aimed to analyse neuromuscular activity of the trunk comparing four different perturbations during gait. Thirteen subjects (28 +/- 3 yrs) walked (1 m/s) on a split-belt treadmill, while 4 (belt) perturbations (F1, F2, B1, B2) were randomly applied. Perturbations differed, related to treadmill belt translation, in direction (forward (F)/backward (B)) and amplitude (20 m/s(2) (1)/40 m/s(2) (2)). Trunk muscle activity was assessed with a 12-lead-EMG. EMG-RMS [%] (0-200 ms after perturbation; normalized to RMS of normal gait) was analyzed for muscles and four trunk areas (ventral left/right; dorsal left/right). Ratio of ventral: dorsal muscles were calculated. Muscle onset [ms] was determined. Data analysis was conducted descriptively, followed by ANOVA (post hoc Tukey-Kramer (alpha = 0.05)). All perturbations lead to an increase in EMG-RMS (428 +/- 289%). F1 showed the lowest and F2 the highest increase for the flexors. B2 showed the highest increase for the extensors. Significant differences between perturbations could be observed for 6 muscles, as well as the 4 trunk areas. Ratio analysis revealed no significant differences (range 1.25 (B1) to 1.71 (F2) between stimuli. Muscle response time (ventral: 87.0 +/- 21.7 ms; dorsal: 88.4 +/- 17.0 ms) between stimuli was only significant (p = 0.005) for the dorsal muscles. Magnitude significantly influences neuromuscular trunk response patterns in healthy adults. Regardless of direction ventral muscles always revealed higher relative increase of activity while compensating the walking perturbations. (C) 2016 Elsevier Ltd. All rights reserved.
The xanthine oxidase (XO) family comprises molybdenum-dependent enzymes that usually form homodimers (or dimers of heterodimers/trimers) organized in three domains that harbor two [2Fe-2S] clusters, one FAD, and a Mo cofactor. In this work, we crystallized an unusual member of the family, the periplasmic aldehyde oxidoreductase PaoABC from Escherichia coli. This is the first example of an E. coli protein containing a molybdopterin-cytosine-dinucleotide cofactor and is the only heterotrimer of the XO family so far structurally characterized. The crystal structure revealed the presence of an unexpected [4Fe-4S] cluster, anchored to an additional 40 residues subdomain. According to phylogenetic analysis, proteins containing this cluster are widely spread in many bacteria phyla, putatively through repeated gene transfer events. The active site of PaoABC is highly exposed to the surface with no aromatic residues and an arginine (PaoC-R440) making a direct interaction with PaoC-E692, which acts as a base catalyst. In order to understand the importance of R440, kinetic assays were carried out, and the crystal structure of the PaoC-R440H variant was also determined.
Background. The bay cat Catopuma badia is endemic to Borneo, whereas its sister species the Asian golden cat Catopuma temminckii is distributed from the Himalayas and southern China through Indochina, Peninsular Malaysia and Sumatra. Based onmorphological data, up to five subspecies of the Asian golden cat have been recognized, but a taxonomic assessment, including molecular data and morphological characters, is still lacking. Results. We combined molecular data (whole mitochondrial genomes), morphological data (pelage) and species distribution projections (up to the Late Pleistocene) to infer how environmental changes may have influenced the distribution of these sister species over the past 120 000 years. The molecular analysis was based on sequenced mitogenomes of 3 bay cats and 40 Asian golden cats derived mainly from archival samples. Our molecular data suggested a time of split between the two species approximately 3.16 Ma and revealed very low nucleotide diversity within the Asian golden cat population, which supports recent expansion of the population. Discussion. The low nucleotide diversity suggested a population bottleneck in the Asian golden cat, possibly caused by the eruption of the Toba volcano in Northern Sumatra (approx. 74 kya), followed by a continuous population expansion in the Late Pleistocene/Early Holocene. Species distribution projections, the reconstruction of the demographic history, a genetic isolation-by-distance pattern and a gradual variation of pelage pattern support the hypothesis of a post-Toba population expansion of the Asian golden cat from south China/Indochina to PeninsularMalaysia and Sumatra. Our findings reject the current classification of five subspecies for the Asian golden cat, but instead support either a monotypic species or one comprising two subspecies: (i) the Sunda golden cat, distributed south of the Isthmus of Kra: C. t. temminckii and (ii) Indochinese, Indian, Himalayan and Chinese golden cats, occurring north of the Isthmus: C. t. moormensis.
Lake Meerfelder Maar (MFM) is the northernmost Western European sediment record with annual laminations across the Younger Dryas (YD), and the onset of the YD in the record of MFM has previously been defined as an increase in non-arboreal pollen abundance at ca. 12 680 varve a BP. Here we present a palynological record at unprecedented subdecadal resolution for MFM, covering the Allerod-YD transition. Our results show a fluctuation in pollen accumulation rates (PARs) before the onset of the YD, with lower rates between ca. 12 725 and 12 685 varve a BP. The fluctuation in PARs occurs simultaneous with a previously undescribed short fluctuation in sediment composition and varve thickness, as well as with changes in biogeochemical proxies. The combined evidence indicates signs of climatic instability ca. 45 years before the onset of the YD. The PAR records of Betula and Pinus furthermore show earlier and more abrupt changes at the onset of the YD than the percentage-records do. Finally, heliophilous herbaceous taxa show a delayed increase following the onset of the YD of ca. 145 years. This paper illustrates the potential to identify previously unrecognized climate variability and vegetation change when using subdecadal-resolution analyses. Copyright (C) 2016 John Wiley & Sons, Ltd.
The Pamirs represent the indented westward continuation of the northern margin of the Tibetan Plateau, dividing the Tarim and Tajik basins. Their evolution may be a key factor influencing aridification of the Asian interior, yet the tectonics of the Pamir Salient are poorly understood. We present a provenance study of the Aertashi section, a Paleogene to late Neogene clastic succession deposited in the Tarim basin to the north of the NW margin of Tibet (the West Kunlun) and to the east of the Pamirs. Our detrital zircon U-Pb ages coupled with zircon fission track, bulk rock Sm-Nd, and petrography data document changes in contributing source terranes during the Oligocene to Miocene, which can be correlated to regional tectonics. We propose a model for the evolution of the Pamir and West Kunlun (WKL), in which the WKL formed topography since at least similar to 200 Ma. By similar to 25 Ma, movement along the Pamir-bounding faults such as the Kashgar-Yecheng Transfer System had commenced, marking the onset of Pamir indentation into the Tarim-Tajik basin. This is coincident with basinward expansion of the northern WKL margin, which changed the palaeodrainage pattern within the Kunlun, progressively cutting off the more southerly WKL sources from the Tarim basin. An abrupt change in the provenance and facies of sediments at Aertashi has a maximum age of 14 Ma; this change records when the Pamir indenter had propagated sufficiently far north that the North Pamir was now located proximal to the Aertashi region.
Testate amoebae with self-secreted siliceous shell platelets ("idiosomes") play an important role in terrestrial silicon (Si) cycles. In this context, Si-dependent culture growth dynamics of idiosomic testate amoebae are of interest. Clonal cultures of idiosomic testate amoebae were analyzed under three different Si concentrations: low (50 mu mol L-1), moderate/site-specific (150 mu mol L-1) and high Si supply (500 mu mol L-1). Food (Saccharomyces cerevisiae) was provided in surplus. (i) Shell size of four different clones of idiosomic testate amoebae either decreased (Trinema galeata, Euglypha filifera cf.), increased (E. rotunda cf.), or did not change (E. rotunda) under the lowest Si concentration (50 mu mol Si L-1). (ii) Culture growth of idiosomic Euglypha rotunda was dependent on Si concentration. The more Si available in the culture medium, the earlier the entry into exponential growth phase. (iii) Culture growth of idiosomic Euglypha rotunda was dependent on origin of inoculum. Amoebae previously cultured under a moderate Si concentration revealed highest sustainability in consecutive cultures. Amoebae derived from cultures with high Si concentrations showed rapid culture growth which finished early in consecutive cultures. (iv) Si (diluted in the culture medium) was absorbed by amoebae and fixed in the amoeba shells resulting in decreased Si concentrations. (C) 2016 Elsevier GmbH. All rights reserved.
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.
The very high energy (VHE; E > 100 GeV) blazar Markarian 501 was observed between April 17 and May 5 (MJD 54 938-54 956), 2009, as part of an extensive multiwavelength campaign from radio to VHE. Strong VHE yray activity was detected on May 1st with Whipple and VERITAS, when the flux (E > 400 GeV) increased to 10 times the preflare baseline flux (3.9 x 10(-11) ph cm(-2) s(-1)), reaching five times the flux of the Crab Nebula. This coincided with a decrease in the optical polarization and a rotation of the polarization angle by 15. This VHE flare showed a fast flux variation with an increase of a factor similar to 4 in 25 min, and a falling time of similar to 50 min. We present the observations of the quiescent state previous to the flare and of the high state after the flare, focusing on the flux and spectral variability from Whipple, VERITAS, Fermi-LAT, RXTE, and Swift combined with optical and radio data.
The density of firn is an important property for monitoring and modeling the ice sheets as well as to model the pore close-off and thus to interpret ice core-based greenhouse gas records. One feature, which is still in debate, is the potential existence of an annual cycle of firn density in low-accumulation regions. Several studies describe or assume seasonally successive density layers, horizontally evenly distributed, as seen in radar data. On the other hand, high-resolution density measurements on firn cores in Antarctica and Greenland show no clear seasonal cycle in the top few meters. A major caveat of most existing snow-pit and firn-core-based studies is that they represent one vertical profile from a laterally heterogeneous density field. To overcome this, we created an extensive data set of horizontal and vertical density data at Kohnen Station, Dronning Maud Land, on the East Antarctic Plateau. We drilled and analyzed three 90m long firn cores as well as 143 one-meter-long vertical profiles from two elongated snow trenches to obtain a two-dimensional view of the density variations. The analysis of the 45m wide and 1m deep density fields reveals a seasonal cycle in density. However, the seasonality is overprinted by strong stratigraphic noise, making it invisible when analyzing single firn cores. Our density data set extends the view from the local ice core perspective to a hundred meter scale and thus supports linking spatially integrating methods such as radar and seismic studies to ice and firn cores.
Communicative Reason Juergen Habermas, interviewed by Christoph Demmerling and Hans-Peter Krueger
(2016)
Jurgen Habermas explicates the concept of communicative reason. He explains the key assumptions of the philosophy of language and social theory associated with this concept. Also discussed is the category of life-world and the role of the body-mind difference for the consciousness of exclusivity in our access to subjective experience. as well as the role of emotions and perceptions in the context of a theory of communicative action. The question of the redemption of the various validity claims as they are associated with the performance of speech acts is related to processes of social learning and to the role of negative experiences. Finally the interview deals with the relationship between religion and reason and the importance of religion in modern, post-secular societies. Questions about the philosophical culture of our present times are discussed at the end of the conversation.
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.
X-ray free electron lasers (XFELs) enable unprecedented new ways to study the electronic structure and dynamics of transition metal systems. L-edge absorption spectroscopy is a powerful technique for such studies and the feasibility of this method at XFELs for solutions and solids has been demonstrated. However, the required x-ray bandwidth is an order of magnitude narrower than that of self-amplified spontaneous emission (SASE), and additional monochromatization is needed. Here we compare L-edge x-ray absorption spectroscopy (XAS) of a prototypical transition metal system based on monochromatizing the SASE radiation of the linac coherent light source (LCLS) with a new technique based on self-seeding of LCLS. We demonstrate how L-edge XAS can be performed using the self-seeding scheme without the need of an additional beam line monochromator. We show how the spectral shape and pulse energy depend on the undulator setup and how this affects the x-ray spectroscopy measurements. (C) 2016 Optical Society of America
Bats are top insect predators on farmland, yet they suffer from intensive farmland management. Here, we evaluated the seasonal activity patterns of European bats above large, arable fields and compared these patterns between ecologically distinct bat species. Using repeated passive acoustic monitoring on a total of 93 arable fields in 2 years in Brandenburg, Germany, we surveyed the activity of different bat species between early spring and autumn. We then used generalized additive mixed models to describe and compare the seasonal bat activity patterns between bat categories, which were build based on the affiliation to a functional group and migratory class, while controlling for local weather conditions. In general, the affiliation to a bat category in interaction with the season in addition to cloud cover and ambient air temperature explained a major part of bat activity. The season was also an important factor for the foraging activity of open-space specialists such as Nyctalus noctula but showed only a weak effect on species such as Pipistreilus nathusii which are adapted to edge-space habitats. Across the seasons, habitat use intensity was high during the period of swarming and migration and low during the energy demanding period of lactation. Seasonal patterns in foraging activity showed that open-space specialists foraged more intensively above agricultural fields during the migration period, while edge-space specialists foraged also during the energy demanding period of lactation. We conclude that the significant seasonal fluctuations in bat activity and significant differences between bat categories in open agricultural landscapes should be taken into consideration when designing monitoring schemes and management plans for bat species in regions dominated by agriculture. Also, management plans should be directed to improve the conditions on arable land especially for bat species which would be classified as narrow-space foragers such as Myotis species. (C) 2016 Elsevier B.V. All rights reserved.
An atomic scale molecular dynamics simulation (100 ns) was carried out to reveal the conformational features of a cationic polyelectrolyte, i.e., hyperbranched polyethyleneimine (PEI), inside of water-in-oil microemulsion droplets stabilized by the anionic sodium dodecyl sulfate surfactant (SDS) layer. Simulations show that the polymer reorients very quickly and is localized at the headgroup region, i.e., the polymer nitrogens are close to SDS sulfur atoms. In spite of the availability of surface roughness caused by the polymer, we track a stable inverse micelle during the production run. In overall, the obtained parameters are well compared with experimental findings. (C) 2016 Elsevier B.V. All rights reserved.
The high potential of bottom-up fabrication strategies for realizing sophisticated optical sensors combining the high sensitivity of a surface plasmon resonance with the exceptional properties of stimuli-responsive hydrogel is demonstrated. The sensor is composed of a periodic hole array in a gold film whose holes are filled with gold-capped poly(N-isoproyl-acrylamide) (polyNIPAM) microspheres. The production of this sensor relies on a pure chemical approach enabling simple, time-efficient, and cost-efficient preparation of sensor platforms covering areas of cm(2). The transmission spectrum of this plasmonic sensor shows a strong interaction between propagating surface plasmon polaritons at the metal film surface and localized surface plasmon resonance of the gold cap on top of the polyNIPAM microspheres. Computer simulations support this experimental observation. These interactions lead to distinct changes in the transmission spectrum, which allow for the simultaneous, sensitive optical detection of refractive index changes in the surrounding medium and the swelling state of the embedded polyNIPAM microsphere under the gold cap. The volume of the polyNIPAM microsphere located underneath the gold cap can be changed by certain stimuli such as temperature, pH, ionic strength, and distinct molecules bound to the hydrogel matrix facilitating the detection of analytes which do not change the refractive index of the surrounding medium significantly.
Species diversity is changing globally and locally, but the complexity of ecological communities hampers a general understanding of the consequences of animal species loss on ecosystem functioning. High animal diversity increases complementarity of herbivores but also increases feeding rates within the consumer guild. Depending on the balance of these counteracting mechanisms, species-rich animal communities may put plants under top-down control or may release them from grazing pressure. Using a dynamic food-web model with body-mass constraints, we simulate ecosystem functions of 20,000 communities of varying animal diversity. We show that diverse animal communities accumulate more biomass and are more exploitative on plants, despite their higher rates of intra-guild predation. However, they do not reduce plant biomass because the communities are composed of larger, and thus energetically more efficient, plant and animal species. This plasticity of community body-size structure reconciles the debate on the consequences of animal species loss for primary productivity.
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.
Ongoing climate change is known to cause an increase in the frequency and amplitude of local temperature and precipitation extremes in many regions of the Earth. While gradual changes in the climatological conditions have already been shown to strongly influence plant flowering dates, the question arises if and how extremes specifically impact the timing of this important phenological phase. Studying this question calls for the application of statistical methods that are tailored to the specific properties of event time series. Here, we employ event coincidence analysis, a novel statistical tool that allows assessing whether or not two types of events exhibit similar sequences of occurrences in order to systematically quantify simultaneities between meteorological extremes and the timing of the flowering of four shrub species across Germany. Our study confirms previous findings of experimental studies by highlighting the impact of early spring temperatures on the flowering of the investigated plants. However, previous studies solely based on correlation analysis do not allow deriving explicit estimates of the strength of such interdependencies without further assumptions, a gap that is closed by our analysis. In addition to direct impacts of extremely warm and cold spring temperatures, our analysis reveals statistically significant indications of an influence of temperature extremes in the autumn preceding the flowering.
The LEA (late embryogenesis abundant) proteins COR15A and COR15B from Arabidopsis thaliana are intrinsically disordered under fully hydrated conditions, but obtain alpha-helical structure during dehydration, which is reversible upon rehydration. To understand this unusual structural transition, both proteins were investigated by circular dichroism (CD) and molecular dynamics (MD) approaches. MD simulations showed unfolding of the proteins in water, in agreement with CD data obtained with both HIS-tagged and untagged recombinant proteins. Mainly intramolecular hydrogen bonds (H-bonds) formed by the protein backbone were replaced by H-bonds with water molecules. As COR15 proteins function in vivo as protectants in leaves partially dehydrated by freezing, unfolding was further assessed under crowded conditions. Glycerol reduced (40%) or prevented (100%) unfolding during MD simulations, in agreement with CD spectroscopy results. H-bonding analysis indicated that preferential exclusion of glycerol from the protein backbone increased stability of the folded state.
A search for dark matter linelike signals iss performed in the vicinity of the Galactic Center by the H.E.S.S. experiment on observational data taken in 2014. An unbinned likelihood analysis iss developed to improve the sensitivity to linelike signals. The upgraded analysis along with newer data extend the energy coverage of the previous measurement down to 100 GeV. The 18 h of data collected with the H.E.S.S. array allow one to rule out at 95% C.L. the presence of a 130 GeV line (at l = -1.5 degrees, b = 0 degrees and for a dark matter profile centered at this location) previously reported in Fermi-LAT data. This new analysis overlaps significantly in energy with previous Fermi-LAT and H.E.S.S. results. No significant excess associated with dark matter annihilations was found in the energy range of 100 GeV to 2 TeV and upper limits on the gamma-ray flux and the velocity weighted annihilation cross section are derived adopting an Einasto dark matter halo profile. Expected limits for present and future large statistics H.E.S.S. observations are also given.
In this Comment, we review the results of pattern formation in a reaction-diffusion-advection system following the kinetics of the Gray-Scott model. A recent paper by Das [Phys. Rev. E 92, 052914 (2015)] shows that spatiotemporal chaos of the intermittency type can disappear as the advective flow is increased. This study, however, refers to a single point in the space of kinetic parameters of the original Gray-Scott model. Here we show that the wealth of patterns increases substantially as some of these parameters are changed. In addition to spatiotemporal intermittency, defect-mediated turbulence can also be found. In all cases, however, the chaotic behavior is seen to disappear as the advective flow is increased, following a scenario similar to what was reported in our earlier work [I. Berenstein and C. Beta, Phys. Rev. E 86, 056205 (2012)] as well as by Das. We also point out that a similar phenomenon can be found in other reaction-diffusion-advection models, such as the Oregonator model for the Belousov-Zhabotinsky reaction under flow conditions.
National doping prevention guidelines: Intent, efficacy and lessons learned - A 4-year evaluation
(2016)
Background: Doping presents a potential health risk for young athletes. Prevention programs are intended to prevent doping by educating athletes about banned substances. However, such programs have their limitations in practice. This led Germany to introduce the National Doping Prevention Plan (NDPP), in hopes of ameliorating the situation among young elite athletes. Two studies examined 1) the degree to which the NDPP led to improved prevention efforts in elite sport schools, and 2) the extent to which newly developed prevention activities of the national anti-doping agency (NADA) based on the NDPP have improved knowledge among young athletes within elite sports schools. Methods: The first objective was investigated in a longitudinal study (Study I: t0 = baseline, t1 = follow-up 4 years after NDPP introduction) with N = 22 teachers engaged in doping prevention in elite sports schools. The second objective was evaluated in a cross-sectional comparison study (Study II) in N = 213 elite sports school students (54. 5 % male, 45.5 % female, age M = 16.7 +/- 1.3 years (all students had received the improved NDDP measure in school; one student group had received additionally NADA anti-doping activities and a control group did not). Descriptive statistics were calculated, followed by McNemar tests, Wilcoxon tests and Analysis of Covariance (ANCOVA). Results: Results indicate that 4 years after the introduction of the NDPP there have been limited structural changes with regard to the frequency, type, and scope of doping prevention in elite sport schools. On the other hand, in study II, elite sport school students who received further NADA anti-doping activities performed better on an anti-doping knowledge test than students who did not take part (F(1, 207) = 33.99, p < 0.001), although this difference was small. Conclusion: The integration of doping-prevention in elite sport schools as part of the NDPP was only partially successful. The results of the evaluation indicate that the introduction of the NDPP has contributed more to a change in the content of doping prevention activities than to a structural transformation in anti-doping education in elite sport schools. Moreover, while students who did receive additional education in the form of the NDPP "booster sessions" had significantly more knowledge about doping than students who did not receive such education, this difference was only small and may not translate to actual behavior.
Background: Environmental stress puts organisms at risk and requires specific stress-tailored responses to maximize survival. Long-term exposure to stress necessitates a global reprogramming of the cellular activities at different levels of gene expression. Results: Here, we use ribosome profiling and RNA sequencing to globally profile the adaptive response of Arabidopsis thaliana to prolonged heat stress. To adapt to long heat exposure, the expression of many genes is modulated in a coordinated manner at a transcriptional and translational level. However, a significant group of genes opposes this trend and shows mainly translational regulation. Different secondary structure elements are likely candidates to play a role in regulating translation of those genes. Conclusions: Our data also uncover on how the subunit stoichiometry of multimeric protein complexes in plastids is maintained upon heat exposure.
The interplay of an enzyme with a multiblock copolymer PDLCL containing two segments of different hydrophilicity and degradability is explored in thin films at the air-water interface. The enzymatic degradation was studied in homogenous Langmuir monolayers, which are formed when containing more than 40 wt% oligo(epsilon-caprolactone) (OCL). Enzymatic degradation rates were significantly reduced with increasing content of hydrophobic oligo(omega-pentadecalactone) (OPDL). The apparent deceleration of the enzymatic process is caused by smaller portion of water-soluble degradation fragments formed from degradable OCL fragments. Beside the film degradation, a second competing process occurs after adding lipase from Pseudomonas cepacia into the subphase, namely the enrichment of the lipase molecules in the polymeric monolayer. The incorporation of the lipase into the Langmuir film is experimentally revealed by concurrent surface area enlargement and by Brewster angle microscopy (BAM). Aside from the ability to provide information about the degradation behavior of polymers, the Langmuir monolayer degradation (LMD) approach enables to investigate polymer-enzyme interactions for non-degradable polymers. (C) 2016 Elsevier Ltd. All rights reserved.
Unwanted shrinkage behaviors or failure in structural functions such as mechanical strength or deformability of polymeric products related to their thermomechanical history are a major challenge in production of plastics. Here, we address the question whether we can turn this challenge into an opportunity by creating defined thermomechanical histories in polymers, represented by a specific morphology and nanostructure, to equip polymeric shaped bodies with desired functions, e.g. a temperature-memory, by hot, warm or cold deformation into multiblock copolymers having two partially overlapping melting transitions. A copolyesterurethane named PDLCL, consisting of poly(epsilon-caprolactone) (PCL) and poly(omega-pentadecalactone) (PPDL) crystalline domains, exhibiting a pronounced phase-segregated morphology and partially overlapping melting transitions was selected for this study. Different types of PCL and PPDL crystals as well as distinct degrees of orientation in both amorphous and crystalline domains were obtained after deformation at 20 or 40 degrees C and to a lower extent at 60 degrees C. The generated non-isotropic structures were stable at ambient temperature and represent the different stresses stored. Stress-free heating experiments showed that the relaxation in both amorphous and crystalline phases occurred predominantly with melting of PCL crystals. When the switching temperature, which was similar to the applied deformation temperature (temperature-memory), was exceeded in stress-free heating experiments, the implemented thermomechanical history could be reversed. In contrast, during constant-strain heating to 60 degrees C the generated structural features remained almost unchanged. These findings provide insights about the structure function relation in multiblock copolymers with two crystalline phases exhibiting a temperature-memory effect by implementation of specific thermomechanical histories, which might be a general principle for tailoring other functions like mechanical strength or deformability in polymers. (C) 2016 Elsevier Ltd. All rights reserved.
We present a summary on the current status of two inversion algorithms that are used in EARLINET (European Aerosol Research Lidar Network) for the inversion of data collected with EARLINET multiwavelength Raman lidars. These instruments measure backscatter coefficients at 355, 532, and 1064 nm, and extinction coefficients at 355 and 532 nm. Development of these two algorithms started in 2000 when EARLINET was founded. The algorithms are based on a manually controlled inversion of optical data which allows for detailed sensitivity studies. The algorithms allow us to derive particle effective radius as well as volume and surface area concentration with comparably high confidence. The retrieval of the real and imaginary parts of the complex refractive index still is a challenge in view of the accuracy required for these parameters in climate change studies in which light absorption needs to be known with high accuracy. It is an extreme challenge to retrieve the real part with an accuracy better than 0.05 and the imaginary part with accuracy better than 0.005-0.1 or +/- 50 %. Single-scattering albedo can be computed from the retrieved microphysical parameters and allows us to categorize aerosols into high-and low-absorbing aerosols. On the basis of a few exemplary simulations with synthetic optical data we discuss the current status of these manually operated algorithms, the potentially achievable accuracy of data products, and the goals for future work. One algorithm was used with the purpose of testing how well microphysical parameters can be derived if the real part of the complex refractive index is known to at least 0.05 or 0.1. The other algorithm was used to find out how well microphysical parameters can be derived if this constraint for the real part is not applied. The optical data used in our study cover a range of Angstrom exponents and extinction-to-backscatter (lidar) ratios that are found from lidar measurements of various aerosol types. We also tested aerosol scenarios that are considered highly unlikely, e.g. the lidar ratios fall outside the commonly accepted range of values measured with Raman lidar, even though the underlying microphysical particle properties are not uncommon. The goal of this part of the study is to test the robustness of the algorithms towards their ability to identify aerosol types that have not been measured so far, but cannot be ruled out based on our current knowledge of aerosol physics. We computed the optical data from monomodal logarithmic particle size distributions, i.e. we explicitly excluded the more complicated case of bimodal particle size distributions which is a topic of ongoing research work. Another constraint is that we only considered particles of spherical shape in our simulations. We considered particle radii as large as 7-10 mu m in our simulations where the Potsdam algorithm is limited to the lower value. We considered optical-data errors of 15% in the simulation studies. We target 50% uncertainty as a reasonable threshold for our data products, though we attempt to obtain data products with less uncertainty in future work.
Electrostatic attraction between charged nano particles and oppositely charged nanopatterned polymeric films enables tailored structuring of functional nanoscopic surfaces. The bottom-up fabrication of organic/inorganic composites for example bears promising potential toward cheap fabrication of catalysts, optical sensors, and the manufacture of miniaturized electric circuitry. However, only little is known about the time-dependent adsorption behavior and the electronic or ionic charge transfer in the film bulk and at interfaces during nanoparticle assembly via electrostatic interactions. In situ electrochemical impedance spectroscopy (EIS) in combination with a microfluidic system for fast and reproducible liquid delivery was thus applied to monitor the selective deposition of negatively charged gold nanoparticles on top of positively charged poly(2-vinylpyridinium) (qP2VP) domains of phase separated lamellar poly(styrene)-block-poly(2-vinylpyridinium) (PS-b-qP2VP) diblock copolymer thin films. The acquired impedance data delivered information with respect to interfacial charge alteration, ionic diffusion, and the charge dependent nanoparticle adsorption kinetics, considering this yet unexplored system. We demonstrate that the selective adsorption of negatively charged gold nanoparticles (AuNPs) on positively charged qP2VP domains of lamellar PS-b-qP2VP thin films can indeed be tracked by EIS. Moreover, we show that the nanoparticle adsorption kinetics and the nanoparticle packing density are functions of the charge density in the qP2VP domains.
The past two decades witnessed tremendous progress in the field of creation of different types of responsive materials. Cholesteric polymer networks present a very promising class of smart materials due to the combination of the unique optical properties of cholesteric mesophase and high mechanical properties of polymer networks. In the present work we demonstrate the possibility of fast and reversible photocontrol of the optical properties of cholesteric polymer networks. Several cholesteric photopolymerizable mixtures are prepared, and porous cholesteric network films with different helix pitches are produced by polymerization of these mixtures. An effective and simple method of the introduction of photochromic azobenzene-containing nematic mixture capable of isothermal photoinducing the nematic isotropic phase transition into the porous polymer matrix is developed, It is found that cross-linking density and degree of polymer network filling with a photochromic nematic mixture strongly influence the photo-optical behavior of the obtained composite films. In particular, the densely cross-linked films are characterized by a decrease in selective light reflection bandwidth, whereas weakly cross-linked systems display two processes: the shift of selective light reflection peak and decrease of its width. It is noteworthy that the obtained cholesteric materials are shown to be very promising for the variety applications in optoelectronics and photonics.
We consider the dynamical atom-surface Casimir-Polder force in the nonequilibrium configuration of an atom near a perfectly conducting wall, initially prepared in an excited state with the field in its vacuum state. We evaluate the time-dependent Casimir-Polder force on the atom and find that it shows an oscillatory behavior from attractive to repulsive both in time and in space. We also investigate the asymptotic behavior in time of the dynamical force and of related local field quantities, showing that the static value of the force, as obtained by a time-independent approach, is recovered for times much longer than the time scale of the atomic self-dressing but shorter than the atomic decay time. We then discuss the evolution of global quantities such as atomic and field energies and their asymptotic behavior. We also compare our results for the dynamical force on the excited atom with analogous results recently obtained for an initially bare ground-state atom. We show that new relevant features are obtained in the case of an initially excited atom, for example, much larger values of the dynamical force with respect to the static one, allowing for an easier way to single out and observe the dynamical Casimir-Polder effect.
Sunspot positions from various historical sets of solar drawings are analyzed with respect to the tilt angles of bipolar sunspot groups. Data by Scheiner, Hevelius, Staudacher, Zucconi, Schwabe, and Sporer deliver a series of average tilt angles spanning a period of 270 years, additional to previously found values for 20th-century data obtained by other authors. We find that the average tilt angles before the Maunder minimum were not significantly different from the modem values. However, the average tilt angles of a period 50 years after the Maunder minimum, namely for cycles 0 and 1, were much lower and near zero. The normal tilt angles before the Maunder minimum suggest that it was not abnormally low tilt angles which drove the solar cycle into a grand minimum. (C) 2016 COSPAR. Published by Elsevier Ltd. All rights reserved.
CD4(+) Foxp3(+) regulatory T cells (Tregs) depend on CD28 signaling for their survival and function, a receptor that has been previously shown to activate the acid sphingomyelinase (Asm)/ceramide system. In this article, we show that the basal and CD28-induced Asm activity is higher in Tregs than in conventional CD4(+) T cells (Tconvs) of wild-type (wt) mice. In Asm-deficient (Smpd1(-/-); Asm(-/-)) mice, as compared with wt mice, the frequency of Tregs among CD4(+) T cells, turnover of the effector molecule CTLA-4, and their suppressive activity in vitro were increased. The biological significance of these findings was confirmed in our Treg-sensitive mouse model of measles virus (MV) CNS infection, in which we observed more infected neurons and less MV-specific CD8(+) T cells in brains of Asm(-/-) mice compared with wt mice. In addition to genetic deficiency, treatment of wt mice with the Asm inhibitor amitriptyline recapitulated the phenotype of Asm-deficient mice because it also increased the frequency of Tregs among CD4(+) T cells. Reduced absolute cell numbers of Tconvs after inhibitor treatment in vivo and extensive in vitro experiments revealed that Tregs are more resistant toward Asm inhibitor-induced cell death than Tconvs. Mechanistically, IL-2 was capable of providing crucial survival signals to the Tregs upon inhibitor treatment in vitro, shifting the Treg/Tconv ratio to the Treg side. Thus, our data indicate that Asm-inhibiting drugs should be further evaluated for the therapy of inflammatory and autoimmune disorders.
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.
Recent technological developments have increased the number of variables being monitored in lakes and reservoirs using automatic high frequency monitoring (AHFM). However, design of AHFM systems and posterior data handling and interpretation are currently being developed on a site-by-site and issue-by-issue basis with minimal standardization of protocols or knowledge sharing. As a result, many deployments become short-lived or underutilized, and many new scientific developments that are potentially useful for water management and environmental legislation remain underexplored. This Critical Review bridges scientific uses of AHFM with their applications by providing an overview of the current AHFM capabilities, together with examples of successful applications. We review the use of AHFM for maximizing the provision of ecosystem services supplied, by lakes and reservoirs (consumptive and non consumptive uses, food production, and recreation), and for reporting lake status in the EU Water Framework Directive. We also highlight critical issues to enhance the application of AHFM, and suggest the establishment of appropriate networks to facilitate knowledge sharing and technological transfer between potential users. Finally, we give advice on how modern sensor technology can successfully be applied on a larger scale to the management of lakes and reservoirs and maximize the ecosystem services they provide.
Practical use of many bioelectronic and bioanalytical devices is limited by the need of expensive materials and time consuming fabrication. Here we demonstrate the use of nickel electrodes as a simple and cheap solid support material for bioelectronic applications. The naturally nanostructured electrodes showed a surprisingly high electromagnetic surface enhancement upon light illumination such that immobilization and electron transfer reactions of the model redox proteins cytochrome b(5) (Cyt b(5)) and cytochrome c (Cyt c) could be followed via surface enhanced resonance Raman spectroscopy. It could be shown that the nickel surface, when used as received, promotes a very efficient binding of the proteins upon preservation of their native structure. The immobilized redox proteins could efficiently exchange electrons with the electrode and could even act as an electron relay between the electrode and solubilized myoglobin. Our results open up new possibility for nickel electrodes as an exceptional good support for bioelectronic devices and biosensors on the one hand and for surface enhanced spectroscopic investigations on the other hand. (C) 2016 Elsevier B.V. All rights reserved.
Yolk@Shell Nanoarchitectures with Bimetallic Nanocores - Synthesis and Electrocatalytic Applications
(2016)
A combination of three innovative materials within one hybrid structure to explore the synergistic interaction of their individual properties is presented. The unique electronic, mechanical, and thermal properties of graphene are combined with the plasmonic properties of gold nanoparticle (AuNP) dimers, which are assembled using DNA origami nanostructures. This novel hybrid structure is characterized by means of correlated atomic force microscopy and surface-enhanced Raman scattering (SERS). It is demonstrated that strong interactions between graphene and AuNPs result in superior SERS performance of the hybrid structure compared to their individual components. This is particularly evident in efficient fluorescence quenching, reduced background, and a decrease of the photobleaching rate up to one order of magnitude. The versatility of DNA origami structures to serve as interface for complex and precise arrangements of nanoparticles and other functional entities provides the basis to further exploit the potential of the here presented DNA origami-AuNP dimer-graphene hybrid structures.
It has long been appreciated that material chemistry and topology profoundly affect cell adhesion and migration. Here, aqueous poly(N- isopropyl acrylamide) nanogels are designed, synthesized and printed in form of colloidal arrays on glass substrates using wrinkled polydimethylsiloxane templates. Using low-temperature plasma treatment, nanogels are chemically grafted onto glass supports thus leading to highly stable nanogel layers in cell culture media. Liquid cell atomic force microscopy investigations show that surface-grafted nanogels retain their swelling behavior in aqueous media and that extracellular matrix protein coating do not alter their stability and topography. It is demonstrated that surface-grafted nanogels could serve as novel substrates for the analysis of cell adhesion and migration. Nanogels influence size, speed, and dynamics of focal adhesions and cell motility forcing cells to move along highly directional trajectories. Moreover, modulation of nanogel state or spacing serves as an effective tool for regulation of cell motility. It is suggested that nanogel arrays deposited on solid surfaces could be used to provide a precise and tunable system to understand and control cell migration. Additionally, such nanogel arrays will contribute to the development of implantable systems aimed at supporting and enhancing cell migration during, for instance, wound healing and tissue regeneration.
Background: Arising from the relevance of sensorimotor training in the therapy of nonspecific low back pain patients and from the value of individualized therapy, the present trial aims to test the feasibility and efficacy of individualized sensorimotor training interventions in patients suffering from nonspecific low back pain. Methods and study design: A multicentre, single-blind two-armed randomized controlled trial to evaluate the effects of a 12-week (3 weeks supervised centre-based and 9 weeks home-based) individualized sensorimotor exercise program is performed. The control group stays inactive during this period. Outcomes are pain, and pain-associated function as well as motor function in adults with nonspecific low back pain. Each participant is scheduled to five measurement dates: baseline (M1), following centre-based training (M2), following home-based training (M3) and at two follow-up time points 6 months (M4) and 12 months (M5) after M1. All investigations and the assessment of the primary and secondary outcomes are performed in a standardized order: questionnaires - clinical examination biomechanics (motor function). Subsequent statistical procedures are executed after the examination of underlying assumptions for parametric or rather non-parametric testing. Discussion: The results and practical relevance of the study will be of clinical and practical relevance not only for researchers and policy makers but also for the general population suffering from nonspecific low back pain.
Rainfall in the central Andes associated with the South American Monsoon and the South American Low-Level Jet results from orographic effects on atmospheric circulation exerted by the Andean Plateau and the Eastern Cordillera. However, despite its importance for South American climate, no reliable records exist that allow decoding the evolution of thresholds and interactions between Andean topography and atmospheric circulation, especially regarding the onset of humid conditions in the inherently dry southern central Andes. Here, we employ multi-proxy isotope data of lipid biomarkers, pedogenic carbonates and volcanic glass from the Eastern Cordillera of NW Argentina and present the first long-term evapotranspiration record. We find that regional eco-hydrology and vegetation changes are associated with initiation of moisture transport via the South American Low-Level Jet at 7.6 Ma, and subsequent lateral growth of the orogen at 6.5 Ma. Our results highlight that topographically induced changes in atmospheric circulation patterns, not global climate change, were responsible for late Miocene environmental change in this part of the southern hemisphere. This suggests that mountain building over time fundamentally controlled habitat evolution along the central Andes.
To understand past flood changes in the Rhine catchment and in particular the role of anthropogenic climate change in extreme flows, an attribution study relying on a proper GCM (general circulation model) downscaling is needed. A downscaling based on conditioning a stochastic weather generator on weather patterns is a promising approach. This approach assumes a strong link between weather patterns and local climate, and sufficient GCM skill in reproducing weather pattern climatology. These presuppositions are unprecedentedly evaluated here using 111 years of daily climate data from 490 stations in the Rhine basin and comprehensively testing the number of classification parameters and GCM weather pattern characteristics. A classification based on a combination of mean sea level pressure, temperature, and humidity from the ERA20C reanalysis of atmospheric fields over central Europe with 40 weather types was found to be the most appropriate for stratifying six local climate variables. The corresponding skill is quite diverse though, ranging from good for radiation to poor for precipitation. Especially for the latter it was apparent that pressure fields alone cannot sufficiently stratify local variability. To test the skill of the latest generation of GCMs from the CMIP5 ensemble in reproducing the frequency, seasonality, and persistence of the derived weather patterns, output from 15 GCMs is evaluated. Most GCMs are able to capture these characteristics well, but some models showed consistent deviations in all three evaluation criteria and should be excluded from further attribution analysis.
The mechanism of nanotriangle formation in multivesicular vesicles (MMV) is investigated by using time-dependent SAXS measurements in combination with UV-vis spectroscopy, light, and transmission electron microscopy. In the first time period 6.5 nm sized spherical gold nanoparticles are formed inside of the vesicles, which build up soft nanoparticle aggregates. a) In situ SAXS experiments show a linear increase of the volume and molar mass of nanotriangles in the second time period. The volume growth rate of the triangles is 16.1 nm(3)/min, and the growth rate in the vertical direction is only 0.02 nm/min. Therefore, flat nanotriangles with a thickness of 7 nm and a diameter of 23 nm are formed. This process can be described by a diffusion limited Ostwald ripening growth mechanism. TEM micrographs visualize soft coral-like structures with thin nanoplatelets at the periphery of the aggregates, which disaggregate in the third time period into nanotriangles and spherical particles. The 16 times faster growth of nanotriangles in the lateral than that in the vertical direction is related to the adsorption of symmetry breaking components, i.e., AOT and the polyampholyte PalPhBisCarb, on the {111} facets of the gold nanoplatelets in combination with confinement effects of the vesicular template phase.
The population structure of the highly mobile marine mammal, the harbor porpoise (Phocoena phocoena), in the Atlantic shelf waters follows a pattern of significant isolation-by-distance. The population structure of harbor porpoises from the Baltic Sea, which is connected with the North Sea through a series of basins separated by shallow underwater ridges, however, is more complex. Here, we investigated the population differentiation of harbor porpoises in European Seas with a special focus on the Baltic Sea and adjacent waters, using a population genomics approach. We used 2872 single nucleotide polymor-phisms (SNPs), derived from double digest restriction-site associated DNA sequencing (ddRAD-seq), as well as 13 microsatellite loci and mitochondrial haplotypes for the same set of individuals. Spatial principal components analysis (sPCA), and Bayesian clustering on a subset of SNPs suggest three main groupings at the level of all studied regions: the Black Sea, the North Atlantic, and the Baltic Sea. Furthermore, we observed a distinct separation of the North Sea harbor porpoises from the Baltic Sea populations, and identified splits between porpoise populations within the Baltic Sea. We observed a notable distinction between the Belt Sea and the Inner Baltic Sea sub-regions. Improved delineation of harbor porpoise population assignments for the Baltic based on genomic evidence is important for conservation management of this endangered cetacean in threatened habitats, particularly in the Baltic Sea proper. In addition, we show that SNPs outperform microsatellite markers and demonstrate the utility of RAD-tags from a relatively small, opportunistically sampled cetacean sample set for population diversity and divergence analysis.
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.
We present new experimental data of the low-temperature metastable region of liquid water derived from high-density synthetic fluid inclusions (996-916 kg m(-3)) in quartz. Microthermometric measurements include: (i) prograde (upon heating) and retrograde (upon cooling) liquid-vapour homogenisation. We used single ultrashort laser pulses to stimulate vapour bubble nucleation in initially monophase liquid inclusions. Water densities were calculated based on prograde homogenisation temperatures using the IAPWS-95 formulation. We found retrograde liquid-vapour homogenisation temperatures in excellent agreement with IAPWS-95. (ii) Retrograde ice nucleation. Raman spectroscopy was used to determine the nucleation of ice in the absence of the vapour bubble. Our ice nucleation data in the doubly metastable region are inconsistent with the low-temperature trend of the spinodal predicted by IAPWS-95, as liquid water with a density of 921 kg m(-3) remains in a homogeneous state during cooling down to a temperature of -30.5 degrees C, where it is transformed into ice whose density corresponds to zero pressure. (iii) Ice melting. Ice melting temperatures of up to 6.8 degrees C were measured in the absence of the vapour bubble, i.e. in the negative pressure region. (iv) Spontaneous retrograde and, for the first time, prograde vapour bubble nucleation. Prograde bubble nucleation occurred upon heating at temperatures above ice melting. The occurrence of prograde and retrograde vapour bubble nucleation in the same inclusions indicates a maximum of the bubble nucleation curve in the R-T plane at around 40 degrees C. The new experimental data represent valuable benchmarks to evaluate and further improve theoretical models describing the p-V-T properties of metastable water in the low-temperature region.
A Model Analysis of Mechanisms for Radial Microtubular Patterns at Root Hair Initiation Sites
(2016)
Plant cells have two main modes of growth generating anisotropic structures. Diffuse growth where whole cell walls extend in specific directions, guided by anisotropically positioned cellulose fibers, and tip growth, with inhomogeneous addition of new cell wall material at the tip of the structure. Cells are known to regulate these processes via molecular signals and the cytoskeleton. Mechanical stress has been proposed to provide an input to the positioning of the cellulose fibers via cortical microtubules in diffuse growth. In particular, a stress feedback model predicts a circumferential pattern of fibers surrounding apical tissues and growing primordia, guided by the anisotropic curvature in such tissues. In contrast, during the initiation of tip growing root hairs, a star-like radial pattern has recently been observed. Here, we use detailed finite element models to analyze how a change in mechanical properties at the root hair initiation site can lead to star-like stress patterns in order to understand whether a stress-based feedback model can also explain the microtubule patterns seen during root hair initiation. We show that two independent mechanisms, individually or combined, can be sufficient to generate radial patterns. In the first, new material is added locally at the position of the root hair. In the second, increased tension in the initiation area provides a mechanism. Finally, we describe how a molecular model of Rho-of-plant (ROP) GTPases activation driven by auxin can position a patch of activated ROP protein basally along a 2D root epidermal cell plasma membrane, paving the way for models where mechanical and molecular mechanisms cooperate in the initial placement and outgrowth of root hairs.
Previous clinical research has shown a positive effect of instrumentality on verb retrieval in individuals with aphasia. Performance on instrumental verbs incorporating an obligatory tool into their conceptual representation (e.g., to cut) is more accurate compared to non instrumental verbs (e.g., to tear), possibly due to more specific conceptual representations of instrumental verbs. Seeking the neural correlates of the differences between instrumental and non-instrumental verbs, we conducted an fMRI study with 16 German speakers who performed a verb-object matching task with instrumental and non instrumental verbs. We found that an extensive neural network. including but not limited to frontal and temporal language-related areas was more involved in the semantic processing of non-instrumental compared to instrumental verbs. We argue that this reflects a greater load associated with the processing of less semantically structured/restricted representations of non-instrumental verbs. The unavailability of additional neural resources needed for the processing of non-instrumental verbs in individuals with aphasia may lead to better behavioral performance on instrumental than non instrumental verbs. (C) 2016 Elsevier Ltd. All rights reserved.
Elevation-dependent changes in n-alkane delta D and soil GDGTs across the South Central Andes
(2016)
Surface uplift of large plateaus may significantly influence regional climate and more specifically precipitation patterns and temperature, sometimes complicating paleoaltimetry interpretations. Thus, understanding the topographic evolution of tectonically active mountain belts benefits from continued development of reliable proxies to reduce uncertainties in paleoaltimetry reconstructions. Lipid biomarker-based proxies provide a novel approach to stable isotope paleoaltimetry and complement authigenic or pedogenic mineral proxy materials, in particular outside semi-arid climate zones where soil carbonates are not abundant but (soil) organic matter has a high preservation potential. Here we present delta D values of soil-derived n-alkanes and mean annual air temperature (MAT) estimates based on branched glycerol dialkyl glycerol tetraether (brGDGT) distributions to assess their potential for paleoelevation reconstructions in the southern central Andes. We analyzed soil samples across two environmental and hydrological gradients that include a hillslope (26-28 degrees S) and a valley (22-24 degrees S) transect on the windward flanks of Central Andean Eastern Cordillera in NW Argentina. Our results show that present-day n-alkane delta D values and brGDGT-based MAT estimates are both linearly related with elevation and in good agreement with present-day climate conditions. Soil n-alkanes show a delta D lapse rate (A(delta D)) of -1.64 parts per thousand/100 m (R-2 = 0.91, p < 0.01) at the hillslope transect, within the range of delta D lapse rates from precipitation and surface waters in other tropical regions in the Andes like the Eastern Cordillera in Colombia and Bolivia and the Equatorial and Peruvian Andes. BrGDGT-derived soil temperatures are similar to monitored winter temperatures in the region and show a lapse rate of Delta T = -0.51 degrees C/100 m (R-2 = 0.91, p < 0.01), comparable with lapse rates from in situ soil temperature measurements, satellite derived land-surface temperatures at this transect, and weather stations from the Eastern Cordillera at similar latitude. As a result of an increasing leeward sampling position along the valley transect lapse rates are biased towards lower values and display higher scatter (Delta(delta D) = -0.9 parts per thousand/100 m, R-2 = 0.76, p < 0.01 and Delta T = -0.19 degrees C/100 m, R-2 = 0.48, p < 0.05). Despite this higher complexity, they are in line with lapse rates from stream-water samples and in situ soil temperature measurements along the same transect. Our results demonstrate that both soil n-alkane delta D values and MAT reconstructions based on brGDGTs distributions from the hillslope transect (Delta(delta D) = -1.64 parts per thousand/100 m, R-2 = 0.91, p < 0.01 and Delta T = -0.51 degrees C/100 m, R-2 = 0.91, p < 0.01) track the direct effects of orography on precipitation and temperature and hence the combined effects of local and regional hydrology as well as elevation. (C) 2016 Elsevier B.V. All rights reserved.
Here, we study the 3-D subduction initiation process induced by the interaction between a hot thermochemical mantle plume and oceanic lithosphere using thermo-mechanical viscoplastic finite difference marker-in-cell models. Our numerical modeling results show that self-sustaining subduction is induced by plume-lithosphere interaction when the plume is sufficiently buoyant, the oceanic lithosphere is sufficiently old and the plate is weak enough to allow the buoyant plume to. pass through it. Subduction initiation occurs following penetration of the lithosphere by the hot plume and the downward displacement of broken, nearly circular segments of lithosphere (proto-slabs) as a result of partially molten plume rocks overriding the proto-slabs. Our experiments show four different deformation regimes in response to plume-lithosphere interaction: a) self-sustaining subduction initiation, in which subduction becomes self-sustaining; b) frozen subduction initiation, in which subduction stops at shallow depths; c) slab break-off, in which the subducting circular slab breaks off soon after formation; and d) plume underplating, in which the plume does not pass through the lithosphere and instead spreads beneath it (i.e., failed subduction initiation). These regimes depend on several parameters, such as the size, composition, and temperature of the plume, the brittle/plastic strength and age of the oceanic lithosphere, and the presence/absence of lithospheric heterogeneities. The results show that subduction initiates and becomes self-sustaining when the lithosphere is older than 10 Myr and the non dimensional ratio of the plume buoyancy force and lithospheric strength above the plume is higher than approximately 2. The outcomes of our numerical experiments are applicable for subduction initiation in the modern and Precambrian Earth and for the origin of plume-related corona structures on Venus. (C) 2016 Elsevier B.V. All rights reserved.
We study the z approximate to 3.5 intergalactic medium (IGM) by comparing new, high-quality absorption spectra of eight QSOs with < z(QSO)> = 3.75, to virtual observations of the Evolution and Assembly of Galaxies and their Environments (EAGLE) cosmological hydrodynamical simulations. We employ the pixel optical depth method and uncover strong correlations between various combinations of H I, C III, C IV, Si III, Si IV, and O VI. We find good agreement between many of the simulated and observed correlations, including tau(O) (VI) (tau(H) (I)). However, the observed median optical depths for the tau(C) (IV) (tau(H) (I)) and tau(Si) (IV) (tau(H) (I)) relations are higher than those measured from the mock spectra. The discrepancy increases from up to approximate to 0.1 dex at tau(H) (I) = 1 to approximate to 1 dex at tau(H) (I) = 10(2), where we are likely probing dense regions at small galactocentric distances. As possible solutions, we invoke (a) models of ionizing radiation softened above 4 Ryd to account for delayed completion of He II reionization; (b) simulations run at higher resolution; (c) the inclusion of additional line broadening due to unresolved turbulence; and (d) increased elemental abundances; however, none of these factors can fully explain the observed differences. Enhanced photoionization of H I by local sources, which was not modelled, could offer a solution. However, the much better agreement with the observed O VI(H I) relation, which we find probes a hot and likely collisionally ionized gas phase, indicates that the simulations are not in tension with the hot phase of the IGM, and suggests that the simulated outflows may entrain insufficient cool gas.
We discuss the chiral anomaly for a Weyl field in a curved background and show that a novel index theorem for the Lorentzian Dirac operator can be applied to describe the gravitational chiral anomaly. A formula for the total charge generated by the gravitational and gauge field background is derived directly in Lorentzian signature and in a mathematically rigorous manner. It contains a term identical to the integrand in the Atiyah-Singer index theorem and another term involving the.-invariant of the Cauchy hypersurfaces.
The spatial and temporal control over presentation of protein-based biomolecules such as growth factors and hormones is crucial for in vitro applications to mimic the complex in vivo environment. We investigated the interaction of a model protein lysozyme (Lys) with poly(L-lysine)/hyaluronic acid (PLL/HA) multilayer films. We focused on Lys diffusion as well as adsorption and retention within the film as a function of the film deposition conditions and post-treatment. Additionally, an effect of Lys concentration on its mobility was probed. A combination of confocal fluorescence microscopy, fluorescence recovery after photobleaching, and microfluidics was employed for this investigation. Our main finding is that adsorption of PLL and HA after protein loading induces acceleration and reduction of Lys mobility, respectively. These results suggest that a charge balance in the film to a high extent governs the protein-film interaction. We believe that control over protein mobility is a key to reach the full potential of the PLL/HA films as reservoirs for biomolecules depending on the application demand. (C) 2016 The Authors. Published by Elsevier B.V.
Leaf wax n-alkane H-2 values carry important information about environmental and ecophysiological processes in plants. However, the physiological and biochemical drivers that shape leaf wax n-alkane H-2 values are not completely understood. It is particularly unclear why n-alkanes in grasses are typically H-2-depleted compared with plants from other taxonomic groups such as dicotyledonous plants and why C3 grasses are H-2-depleted compared with C4 grasses. To resolve these uncertainties, we quantified the effects of leaf water evaporative H-2-enrichment and biosynthetic hydrogen isotope fractionation on n-alkane H-2 values for a range of C3 and C4 grasses grown in climate-controlled chambers. We found that only a fraction of leaf water evaporative H-2-enrichment is imprinted on the leaf wax n-alkane H-2 values in grasses. This is interesting, as previous studies have shown in dicotyledonous plants a nearly complete transfer of this H-2-enrichment to the n-alkane H-2 values. We thus infer that the typically observed H-2-depletion of n-alkanes in grasses (as opposed to dicots) is because only a fraction of the leaf water evaporative H-2-enrichment is imprinted on the H-2 values. Our experiments also show that differences in n-alkane H-2 values between C3 and C4 grasses are largely the result of systematic differences in biosynthetic fractionation between these two plant groups, which was on average -198 and-159 parts per thousand for C3 and C4 grasses, respectively. We present novel and exciting data on how leaf wax n-alkane 2H values from grasses are affected by plant physiological (leaf water evaporative 2H-enrichment) or biochemical processes (biosynthetic hydrogen isotope fractionation). These results are very interesting because they shed new light on how naturally observed differences between 2H values from C3 and C4 grasses and dicots can be explained by systematic differences in the biosynthesis of n-alkanes between these plant group (i.e. largely driven by NADPH origins).
Massive stars are extremely luminous and drive strong winds, blowing a large part of their matter into the galactic environment before they finally explode as a supernova. Quantitative knowledge of massive star feedback is required to understand our Universe as we see it. Traditionally, massive stars have been studied under the assumption that their winds are homogeneous and stationary, largely relying on the Sobolev approximation. However, Observations with the newest instruments, together with progress in model calculations, ultimately dictate a cardinal change of this paradigm: stellar winds are highly inhomogeneous. Hence, we are now advancing to a new stage in our understanding of stellar winds. Using the foundations laid by V.V. Sobolev and his school, we now update and further develop the stellar spectral analysis techniques. New sophisticated 3-D models of radiation transfer in inhomogeneous expanding media elucidate the physics of stellar winds and improve classical empiric mass-loss rate diagnostics. Applications of these new techniques to multiwavelength observations of massive stars yield consistent and robust stellar wind parameters. (C) 2016 Elsevier Ltd. All rights reserved.
The research on protein-polymer conjugates by grafting from the surface of proteins has gained significant interest in the last decade. While there are many studies with globular proteins, membrane proteins have remained untouched to the best of our knowledge. In this study, we established the conjugate formation with a class of transmembrane proteins and grow polymer chains from the ferric hydroxamate uptake protein component A (FhuA; a beta-barrel transmembrane protein of Escherichia coli). As the lysine residues of naturally occurring FhuA are distributed over the whole protein, FhuA was reengineered to have up to 11 lysines, distributed symmetrically in a rim on the membrane exposed side (outside) of the protein channel and exclusively above the hydrophobic region. Reengineering of FhuA ensures a polymer growth only on the outside of the beta-barrel and prevents blockage of the channel as a result of the polymerization. A water-soluble initiator for controlled radical polymerization (CRP) was consecutively linked to the lysine residues of FhuA and N-isopropylacrylamide (NIPAAm) polymerized under copper mediated CRP conditions. The conjugate formation was analyzed by using MALDI-ToF mass spectrometry, SDS-PAGE, circular dichroism spectroscopy, analytical ultracentrifugation, dynamic light scattering, transmission electron microscopy and size exclusion chromatography. Such conjugates combine the specific functions of the transmembrane proteins, like maintaining membrane potential gradients or translocation of substrates with the unique properties of synthetic polymers such as temperature and pH stimuli handles. FhuA-PNIPAAm conjugates will serve as functional nanosized building blocks for applications in targeted drug delivery, self-assembly systems, functional membranes and transmembrane protein gated nanoreactors. (C) 2016 Elsevier Ltd. All rights reserved.
In Turkey, there is a shortage of studies on the prevalence of sexual aggression among young adults. The present study examined sexual aggression victimization and perpetration since the age of 15 in a convenience sample of N=1,376 college students (886 women) from four public universities in Ankara, Turkey. Prevalence rates for different coercive strategies, victim-perpetrator constellations, and sexual acts were measured with a Turkish version of the Sexual Aggression and Victimization Scale (SAV-S). Overall, 77.6% of women and 65.5% of men reported at least one instance of sexual aggression victimization, and 28.9% of men and 14.2% of women reported at least one instance of sexual aggression perpetration. Prevalence rates of sexual aggression victimization and perpetration were highest for current or former partners, followed by acquaintances/friends and strangers. Alcohol was involved in a substantial proportion of the reported incidents. The findings are the first to provide systematic evidence on sexual aggression perpetration and victimization among college students in Turkey, including both women and men.
Electromyographic adjustments during continuous and intermittent incremental fatiguing cycling
(2016)
We studied the sensitivity of electromyographic (EMG) variables to load and muscle fatigue during continuous and intermittent incremental cycling. Fifteen men attended three laboratory sessions. Visit 1: lactate threshold, peak power output, and VO2max. Visits 2 and 3: Continuous (more fatiguing) and intermittent (less fatiguing) incremental cycling protocols [20%, 40%, 60%, 80% and 100% of peak power output (PPO)]. During both protocols, multichannel EMG signals were recorded from vastus lateralis: muscle fiber conduction velocity (MFCV), instantaneous mean frequency (iMNF), and absolute and normalized root mean square (RMS) were analyzed. MFCV differed between protocols (P<0.001), and only increased consistently with power output during intermittent cycling. RMS parameters were similar between protocols, and increased linearly with power output. However, only normalized RMS was higher during the more fatiguing 100% PPO stage of the continuous protocol [continuous-intermittent mean difference (95% CI): 45.1 (8.5% to 81.7%)]. On the contrary, iMNF was insensitive to load changes and muscle fatigue (P=0.14). Despite similar power outputs, continuous and intermittent cycling influenced MFCV and normalized RMS differently. Only normalized RMS was sensitive to both increases in power output (in both protocols) and muscle fatigue, and thus is the most suitable EMG parameter to monitor changes in muscle activation during cycling.
A loss of dehydration tolerance in wheat seedlings on the fifth day following imbibition is associated with a disturbance in cellular redox homeostasis, as documented by a shift of the reduced/oxidized glutathione ratio to a more oxidized state and a significant increase in the ratio of protein thiols to the total thiol group content. Therefore, the identification and characterization of redox-sensitive proteins are important steps toward understanding the molecular mechanisms of the loss of dehydration tolerance. In the present study, proteins that were differentially expressed between fully turgid (control), dehydrated tolerant (four-day-old) and dehydrated sensitive (six-day-old) wheat seedlings were analysed. Protein spots having at least a significant (p < 0.05) two-fold change in protein abundance were selected by Delta2D as differentially expressed, identified by MALDI-TOF and LC-MS/MS, and classified according to their function. The observed changes in the proteomic patterns of the differentially S-nitrosylated and S-glutathionylated proteins were highly specific in dehydration-tolerant and-sensitive wheat seedlings. The metabolic function of these proteins indicates that dehydration tolerance is mainly related to nucleic acids, protein metabolism, and energy metabolism. It has been proven that leaf-specific thionins BTH6 and DB4, chloroplastic 50S ribosomal protein L16, phospholipase A1-II delta, and chloroplastic thioredoxin M2 are both S-nitrosylated and S-glutathionylated upon water deficiency. Our results revealed the existence of interplay between S-nitrosylation and S-glutathionylation, two redox-regulated protein posttranslational modifications that could enhance plant defence mechanisms and/or facilitate the acclimation of plants to unfavourable environmental conditions. (C) 2016 Elsevier Masson SAS. All rights reserved.
Knowledge of the quality factor of near-surface materials is of fundamental interest in various applications. Attenuation can be very strong close to the surface and thus needs to be properly assessed. In recent years, several researchers have studied the retrieval of attenuation coefficients from the cross correlation of ambient seismic noise. Yet, the determination of exact amplitude information from noise-correlation functions is, in contrast to the extraction of traveltimes, not trivial. Most of the studies estimated attenuation coefficients on the regional scale and within the microseism band. In this paper, we investigate the possibility to derive attenuation coefficients from seismic noise at much shallower depths and higher frequencies (> 1 Hz). The Euroseistest area in northern Greece offers ideal conditions to study quality factor retrieval from ambient noise for different rock types. Correlations are computed between the stations of a small scale array experiment (station spacings < 2 km) that was carried out in the Euroseistest area in 2011. We employ the correlation of the coda of the correlation (C-3) method instead of simple cross correlations to mitigate the effect of uneven noise source distributions on the correlation amplitude. Transient removal and temporal flattening are applied instead of 1-bit normalization in order to retain relative amplitudes. The C-3 method leads to improved correlation results (higher signal-to-noise ratio and improved time symmetry) compared to simple cross correlations. The C-3 functions are rotated from the ZNE to the ZRT system and we focus on Love wave arrivals on the transverse component and on Love wave quality factors Q(L). The analysis is performed for selected stations being either situated on soft soil or on weathered rock. Phase slowness is extracted using a slant-stack method. Attenuation parameters are inferred by inspecting the relative amplitude decay of Love waves with increasing interstation distance. We observe that the attenuation coefficient gamma and Q(L) can be reliably extracted for stations situated on soft soil whereas the derivation of attenuation parameters is more problematic for stations that are located on weathered rock. The results are in acceptable conformance with theoretical Love wave attenuation curves that were computed using 1-D shear wave velocity and quality factor profiles from the Euroseistest area.
We study the properties of ageing Scher-Montroll transport in terms of a biased subdiffusive continuous time random walk in which the waiting times between consecutive jumps of the charge carriers are distributed according to the power law probability with . As we show, the dynamical properties of the Scher-Montroll transport depend on the ageing time span between the initial preparation of the system and the start of the observation. The Scher-Montroll transport theory was originally shown to describe the photocurrent in amorphous solids in the presence of an external electric field, but it has since been used in many other fields of physical sciences, in particular also in the geophysical context for the description of the transport of tracer particles in subsurface aquifers. In the absence of ageing () the photocurrent of the classical Scher-Montroll model or the breakthrough curves in the groundwater context exhibit a crossover between two power law regimes in time with the scaling exponents and . In the presence of ageing a new power law regime and an initial plateau regime of the current emerge. We derive the different power law regimes and crossover times of the ageing Scher-Montroll transport and show excellent agreement with simulations of the process. Experimental data of ageing Scher-Montroll transport in polymeric semiconductors are shown to agree well with the predictions of our theory.
Restoring degraded lands in rural environments that are heavily managed to meet subsistence needs is a challenge due to high rates of disturbance and resource extraction. This study investigates the efficacy of erosion control structures (ECSs) as restoration tools in the context of a watershed rehabilitation and wet meadow (bofedal) restoration program in the Bolivian Andes. In an effort to enhance water security and increase grazing stability, Aymara indigenous communities built over 15,000 check dams, 9,100 terraces, 5,300 infiltration ditches, and 35 pasture improvement trials. Communities built ECSs at different rates, and we compared vegetation change in the highest restoration management intensity, lowest restoration management intensity, and nonproject control communities. We used line transects to measure changes in vegetation cover and standing water in gullies with check dams and without check dams, and related these ground measurements to a time series (1986-2009) of normalized difference vegetation index derived from Landsat TM5 images. Evidence suggests that check dams increase bofedal vegetation and standing water at a local scale, and lead to increased greenness at a basin scale when combined with other ECSs. Watershed rehabilitation enhances ecosystem services significant to local communities (grazing stability, water security), which creates important synergies when conducting land restoration in rural development settings.