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Rezensiertes Werk:
George, Rosemary Marangoly, Indian English and the Fiction of National Literature - Cambridge: Cambridge University Press, 2013. - Hb. viii, 285 pp. - (Zeitschrift für Anglistik und Amerikanistik ; 62(4)) ISBN 978-1-107-04000-7.
A Little Piece of the Shire
(2014)
Rezensiertes Werk
George, Rosemary Marangoly, Indian English and the Fiction of National Literature - Cambridge: Cambridge University Press, 2013. - Hb. viii, 285 pp. - (Zeitschrift für Anglistik und Amerikanistik ; 62(4))
ISBN 978-1-107-04000-7.
Masked priming research with late (non-native) bilinguals has reported facilitation effects following morphologically derived prime words (scanner - scan). However, unlike for native speakers, there are suggestions that purely orthographic prime-target overlap (scandal - scan) also produces priming in non-native visual word recognition. Our study directly compares orthographically related and derived prime-target pairs. While native readers showed morphological but not formal overlap priming, the two prime types yielded the same magnitudes of facilitation for non-natives. We argue that early word recognition processes in a non-native language are more influenced by surface-form properties than in one's native language.
Two experiments examined the effects of dispositional optimism and attributions on feelings of success in a performance setting. In Experiment 1, participants successfully solved three cognitive tasks and attributed the success either internally (i.e., to themselves) or externally (i.e., to a teammate). We found no effect of optimism, but a significant effect of the attribution: Internal attribution predicted an increase in feelings of success. In Experiment 2, we replicated the design and adopted an extreme groups approach in order to include the extremes of the optimism dimension. Only optimism affected feelings of success in this sample: Pessimistic participants showed higher increases in feelings of success than optimistic participants. We conclude that optimism, if disentangled from attribution, may have an effect on affect, with pessimism showing potential affective benefits. However, this association may be concealed if samples with a restricted range of the optimism dimension are studied.
Purpose of reviewIncretin-based therapy with glucagon-like peptide-1 receptor (GLP-1R) agonists and dipeptidyl peptidase-4 (DPP-4) inhibitors is considered a promising therapeutic option for type 2 diabetes mellitus. Cumulative evidence, mainly from preclinical animal studies, reveals that incretin-based therapies also may elicit beneficial effects on kidney function. This review gives an overview of the physiology, pathophysiology, and pharmacology of the renal incretin system.Recent findingsActivation of GLP-1R in the kidney leads to diuretic and natriuretic effects, possibly through direct actions on renal tubular cells and sodium transporters. Moreover, there is evidence that incretin-based therapy reduces albuminuria, glomerulosclerosis, oxidative stress, and fibrosis in the kidney, partially through GLP-1R-independent pathways. Molecular mechanisms by which incretins exert their renal effects are understood incompletely, thus further studies are needed.SummaryThe GLP-1R and DPP-4 are expressed in the kidney in various species. The kidney plays an important role in the excretion of incretin metabolites and most GLP-1R agonists and DPP-4 inhibitors, thus special attention is required when applying incretin-based therapy in renal impairment. Preclinical observations suggest direct renoprotective effects of incretin-based therapies in the setting of hypertension and other disorders of sodium retention, as well as in diabetic and nondiabetic nephropathy. Clinical studies are needed in order to confirm translational relevance from preclinical findings for treatment options of renal diseases.
A Co(II)-imidazolate-4-amide-5-imidate based MOF, IFP-5, is synthesized by using an imidazolate anion-based novel ionic liquid as a linker precursor under solvothermal conditions. IFP-5 shows significant amounts of gas (N-2, CO2, CH4 and H-2) uptake capacities. IFP-5 exhibits an independent high spin Co(II) centre and antiferromagnetic coupling.
We investigate nonlinear problems which appear as Euler-Lagrange equations for a variational problem. They include in particular variational boundary value problems for nonlinear elliptic equations studied by F. Browder in the 1960s. We establish a solvability criterion of such problems and elaborate an efficient orthogonal projection method for constructing approximate solutions.
The complementary advantages of GPS and seismic measurements are well recognized in seismotectonic monitoring studies. Therefore, integrated processing of the two data streams has been proposed recently in an attempt to obtain accurate and reliable information of surface displacements associated with earthquakes. A hitherto still critical issue in the integrated processing is real-time detection and precise estimation of the transient baseline error in the seismic records. Here, we report on a new approach by introducing the seismic acceleration corrected by baseline errors into the state equation system. The correction is performed and regularly updated in short epochs (with increments which may be as short as seconds), so that station position, velocity, and acceleration can be constrained very tightly and baseline error can be estimated as a random-walk process. With the adapted state equation system, our study highlights the use of a new approach developed for integrated processing of GPS and seismic data by means of sequential least-squares adjustment. The efficiency of our approach is demonstrated and validated using simulated, experimental, and real datasets. The latter were collected at collocated GPS and seismic stations around the 4 April 2010, E1 Mayor-Cucapah earthquake (Mw, 7.2). The results have shown that baseline errors of the strong-motion sensors are corrected precisely and high-precision seismic displacements are real-timely obtained by the new approach.
ResultsUnder conditions of elevated prenatal maternal stress, children carrying one or two DRD4 7r alleles were at increased risk of a diagnosis of CD/ODD. Moreover, homozygous carriers of the DRD4 7r allele displayed more externalizing behavior following exposure to higher levels of prenatal maternal stress, while homozygous carriers of the DRD4 4r allele turned out to be insensitive to the effects of prenatal stress.
ConclusionsThis study is the first to report a gene-environment interaction related to DRD4 and prenatal maternal stress using data from a prospective study, which extends earlier findings on the impact of prenatal maternal stress with respect to childhood antisocial behavior.
QuestionDoes eutrophication drive vegetation change in pine forests on nutrient deficient sites and thus lead to the homogenization of understorey species composition?
LocationForest area (1600ha) in the Lower Spreewald, Brandenburg, Germany.
MethodsResurvey of 77 semi-permanent plots after 45yr, including vascular plants, bryophytes and ground lichens. We applied multidimensional ordination of species composition, dissimilarity indices, mean Ellenberg indicator values and the concept of winner/loser species to identify vegetation change between years. Differential responses along a gradient of nutrient availability were analysed on the basis of initial vegetation type, reflecting topsoil N availability of plots.
ResultsSpecies composition changed strongly and overall shifted towards higher N and slightly lower light availability. Differences in vegetation change were related to initial vegetation type, with strongest compositional changes in the oligotrophic forest type, but strongest increase of nitrophilous species in the mesotrophic forest type. Despite an overall increase in species number, species composition was homogenized between study years due to the loss of species (mainly ground lichens) on the most oligotrophic sites.
ConclusionsThe response to N enrichment is confounded by canopy closure on the N-richest sites and probably by water limitation on N-poorest sites. The relative importance of atmospheric N deposition in the eutrophication effect is difficult to disentangle from natural humus accumulation after historical litter raking. However, the profound differences in species composition between study years across all forest types suggest that atmospheric N deposition contributes to the eutrophication, which drives understorey vegetation change and biotic homogenization in Central European Scots pine forests on nutrient deficient sites.
Not only the apples
(2014)
Focus sensitive particles highlight the relevance of contextual alternatives for the interpretation of a sentence. Two experiments tested whether this leads to better encoding and therefore, ultimately, better recall of focus alternatives. Participants were presented with auditory stimuli that introduced a set of elements ("context sentence") and continued in three different versions: the critical sentences either contained the exclusive particle nur ("only"), the inclusive particle sogar ("even"), or no particle (control condition). After being exposed to blocks of ten trials, participants were asked to recall the elements in the context sentence. The results show that both particles enhanced memory performance for the alternatives to the focused element, relative to the control condition. The results support the assumption that information-structural alternatives are better encoded in memory in the presence of a focus sensitive particle.
To assess the ecological and economic implications of the redistributive land reform in semi-arid Namibia, we investigated to what extent land reform beneficiaries adjust herd size and herd composition according to environmental (rainfall, vegetation) and economic variables (herd size, financial assets, running costs). We performed model-based role-plays with Namibian land reform beneficiaries, simulating 10 years of rangeland management.
Our study revealed that the farmers surveyed mainly manage their herds according to their economic situation (herd size and account balance) but do not take environmental variability (rainfall and vegetation) into account. Further, our results indicate that, due to financial pressure, farmers are not able to apply their desired management strategies, and that owners of small farms face a higher risk of economic failure. However, farmers apply rather conservative and constant stocking rates and will thus, given the current economic limitations, likely not contribute to semi-arid savanna degradation.
We conclude that land reform beneficiaries need support to be able to apply straightforward and efficient management strategies. This could be achieved by facilitating cooperation between small farming businesses and by supporting initial investment in productive cattle herds at the time of redistribution of the land.
In addition to sensory decline, age-related losses in auditory perception also reflect impairments in attentional modulation of perceptual saliency. Using an attention and intensity-modulated dichotic listening paradigm, we investigated electrophysiological correlates of processing conflicts between attentional focus and perceptual saliency in 25 younger and 26 older adults. Participants were instructed to attend to the right or left ear, and perceptual saliency was manipulated by varying the intensities of both ears. Attentional control demand was higher in conditions when attentional focus and perceptual saliency favored opposing ears than in conditions without such conflicts. Relative to younger adults, older adults modulated their attention less flexibly and were more influenced by perceptual saliency. Our results show, for the first time, that in younger adults a late negativity in the event-related potential (ERP) at fronto-central and parietal electrodes was sensitive to perceptual-attentional conflicts during auditory processing (N450 modulation effect). Crucially, the magnitude of the N450 modulation effect correlated positively with task performance. In line with lower attentional flexibility, the ERP waveforms of older adults showed absence of the late negativity and the modulation effect. This suggests that aging compromises the activation of the frontoparietal attentional network when processing the competing and conflicting auditory information.
The basin-scale spatial variability in lipid biomarker proxies in lacustrine sediments, which are established tools for studying continental environmental change, has rarely been examined. It is often implicitly assumed that a lake sediment core provides an average integral of catchment sources. Here we evaluated the distribution of lipid biomarkers in a modern ecosystem and compared it with the sedimentary record. We analyzed lipid biomarkers in terrestrial and aquatic organisms and in lake surface sediments from 17 locations within the saline-alkaline Lonar crater lake in central India. Terrestrial vegetation and lake surface sediments were characterized by relatively high average chain length (ACL) index values (29.6-32.8) of leaf wax n-alkanes, consistent with suggestions that plants in drier and warmer climates produce longer chain alkyl lipids than plants in cooler and humid areas. A heterogeneous spatial distribution of ACL values in lake surface sediments was found: at locations away from the shore, the values were highest (31 or more), possibly indicating different sources and/or transport of terrestrial biomarkers. In floating, benthic microbial mats and surface sediment, n-heptadecane, carotenoids, diploptene, phytol and tetrahymanol occurred in large amounts. Interestingly, these biomarkers of a unique bacterial community were found in substantially higher concentrations in nearshore sediment samples. We suggest that human influence and subsequent nutrient supply resulted in increased primary productivity, leading to an unusually high concentration of tetrahymanol in the nearshore sediments. In summary, the data showed that substantial heterogeneity existed within the lake, but leaf wax n-alkanes in a core from the center of the lake represented an integral of catchment conditions. However, lake level fluctuation may potentially affect aquatic lipid biomarker distributions in lacustrine sediments, in addition to source changes.
carriers on illumination. Efficient organic solar cells require a high yield for this process, combined with a minimum of energy losses. Here, we investigate the role of the lowest energy emissive interfacial charge-transfer state (CT1) in the charge generation process. We measure the quantum yield and the electric field dependence of charge generation on excitation of the charge-transfer (CT) state manifold viaweakly allowed, low-energy optical transitions. For a wide range of photovoltaic devices based on polymer: fullerene, small-molecule:C-60 and polymer: polymer blends, our study reveals that the internal quantum efficiency (IQE) is essentially independent of whether or not D, A or CT states with an energy higher than that of CT1 are excited. The best materials systems show an IQE higher than 90% without the need for excess electronic or vibrational energy.
Word features in parafoveal vision influence eye movements during reading. The question of whether readers extract semantic information from parafoveal words was studied in 3 experiments by using a gaze-contingent display change technique. Subjects read German sentences containing 1 of several preview words that were replaced by a target word during the saccade to the preview (boundary paradigm). In the 1st experiment the preview word was semantically related or unrelated to the target. Fixation durations on the target were shorter for semantically related than unrelated previews, consistent with a semantic preview benefit. In the 2nd experiment, half the sentences were presented following the rules of German spelling (i.e., previews and targets were printed with an initial capital letter), and the other half were presented completely in lowercase. A semantic preview benefit was obtained under both conditions. In the 3rd experiment, we introduced 2 further preview conditions, an identical word and a pronounceable nonword, while also manipulating the text contrast. Whereas the contrast had negligible effects, fixation durations on the target were reliably different for all 4 types of preview. Semantic preview benefits were greater for pretarget fixations closer to the boundary (large preview space) and, although not as consistently, for long pretarget fixation durations (long preview time). The results constrain theoretical proposals about eye movement control in reading.
This article addresses the transformation of a process model with an arbitrary topology into an equivalent structured process model. In particular, this article studies the subclass of process models that have no equivalent well-structured representation but which, nevertheless, can be partially structured into their maximally-structured representation. The transformations are performed under a behavioral equivalence notion that preserves the observed concurrency of tasks in equivalent process models. The article gives a full characterization of the subclass of acyclic process models that have no equivalent well-structured representation, but do have an equivalent maximally-structured one, as well as proposes a complete structuring method. Together with our previous results, this article completes the solution of the process model structuring problem for the class of acyclic process models.
In grape (Vitis vinifera), abscisic acid (ABA) accumulates during fruit ripening and is thought to play a pivotal role in this process, but the molecular basis of this control is poorly understood. This work characterizes ABSCISIC ACID RESPONSE ELEMENT-BINDING FACTOR2 (VvABF2), a grape basic leucine zipper transcription factor belonging to a phylogenetic subgroup previously shown to be involved in ABA and abiotic stress signaling in other plant species. VvABF2 transcripts mainly accumulated in the berry, from the onset of ripening to the harvesting stage, and were up-regulated by ABA. Microarray analysis of transgenic grape cells overexpressing VvABF2 showed that this transcription factor up-regulates and/or modifies existing networks related to ABA responses. In addition, grape cells overexpressing VvABF2 exhibited enhanced responses to ABA treatment compared with control cells. Among the VvABF2-mediated responses highlighted in this study, the synthesis of phenolic compounds and cell wall softening were the most strongly affected. VvABF2 overexpression strongly increased the accumulation of stilbenes that play a role in plant defense and human health (resveratrol and piceid). In addition, the firmness of fruits from tomato (Solanum lycopersicum) plants overexpressing VvABF2 was strongly reduced. These data indicate that VvABF2 is an important transcriptional regulator of ABA-dependent grape berry ripening.
Motivated by recent experimental observations of a rapid spontaneous DNA coil-globule transition on freestanding cationic lipid bilayers, we propose simple theoretical models for DNA condensation on cationic lipid membranes. First, for a single DNA rod, we examine the conditions of full wrapping of a cylindrical DNA-like semi-flexible polyelectrolyte by an oppositely charged membrane. Then, for two parallel DNA rods, we self-consistently analyze the shape and the extent of the membrane enveloping them, focusing on membrane elastic deformations and the membrane-DNA embracing angle, which enables us to compute the membrane-mediated DNA-DNA interactions. We examine the effects of the membrane composition and its charge density, which are the experimentally tunable parameters. We show that membrane-driven rod-rod attraction is more pronounced for higher charge densities and for smaller surface tensions of the membrane. Thus, we demonstrate that for a long DNA chain adhered to a cationic lipid membrane, such membrane-induced DNA-DNA attraction can trigger compaction of DNA.
The southern foreland basin of the Alborz Mountains of northern Iran is characterized by an approximately 7.3-km-thick sequence of Miocene sedimentary rocks, constituting three basin-wde coarsening-upward units spanning a period of 10(6)years. We assess available magnetostratigraphy, paleoclimatic reconstructions, stratal architecture, records of depositional environments, and sediment-provenance data to characterize the relationships between tectonically-generated accommodation space (A) and sediment supply (S). Our analysis allows an inversion of the stratigraphy for particular forcing mechanisms, documenting causal relationships, and providing a basis to decipher the relative contributions of tectonics and climate (inferred changes in precipitation) in controlling sediment supply to the foreland basin. Specifically, A/S>1, typical of each basal unit (17.5-16.0, 13.8-13.1 and 10.3-9.6Ma), is associated with sharp facies retrogradation and reflects substantial tectonic subsidence. Within these time intervals, arid climatic conditions, changes in sediment provenance, and accelerated exhumation in the orogen suggest that sediment supply was most likely driven by high uplift rates. Conversely, A/S<1 (13.8 and 13.8-11Ma, units 1, and 2) reflects facies progradation during a sharp decline in tectonic subsidence caused by localized intra-basinal uplift. During these time intervals, climate continued to be arid and exhumation active, suggesting that sediment supply was again controlled by tectonics. A/S<1, at 11-10.3Ma and 9-6-7.6Ma (and possibly 6.2; top of units 2 and 3), is also associated with two episodes of extensive progradation, but during wetter phases. The first episode appears to have been linked to a pulse in sediment supply driven by an increase in precipitation. The second episode reflects a balance between a climatically-induced increase in sediment supply and a reduction of subsidence through the incorporation of the proximal foreland into the orogenic wedge. This in turn caused an expansion of the catchment and a consequent further increase in sediment supply.
The present study proposes a General Probabilistic Framework (GPF) for uncertainty and global sensitivity analysis of deterministic models in which, in addition to scalar inputs, non-scalar and correlated inputs can be considered as well. The analysis is conducted with the variance-based approach of Sobol/Saltelli where first and total sensitivity indices are estimated. The results of the framework can be used in a loop for model improvement, parameter estimation or model simplification. The framework is applied to SWAP, a 113 hydrological model for the transport of water, solutes and heat in unsaturated and saturated soils. The sources of uncertainty are grouped in five main classes: model structure (soil discretization), input (weather data), time-varying (crop) parameters, scalar parameters (soil properties) and observations (measured soil moisture). For each source of uncertainty, different realizations are created based on direct monitoring activities. Uncertainty of evapotranspiration, soil moisture in the root zone and bottom fluxes below the root zone are considered in the analysis. The results show that the sources of uncertainty are different for each output considered and it is necessary to consider multiple output variables for a proper assessment of the model. Improvements on the performance of the model can be achieved reducing the uncertainty in the observations, in the soil parameters and in the weather data. Overall, the study shows the capability of the GPF to quantify the relative contribution of the different sources of uncertainty and to identify the priorities required to improve the performance of the model. The proposed framework can be extended to a wide variety of modelling applications, also when direct measurements of model output are not available.
We investigated whether 12-month-old infants rely on information about the certainty of goal selection in order to predict observed reaching actions. Infants' goal-directed gaze shifts were recorded as they observed action sequences in a multiple-goals design. We found that 12-month-old infants exhibited gaze shifts significantly earlier when the observed hand reached for the same goal object in all trials (frequent condition) compared with when the observed hand reached for different goal objects across trials (nonfrequent condition). Infants in the frequent condition were significantly more accurate at predicting the action goal than infants in the nonfrequent condition. In addition, findings revealed rapid learning in the case of certainty and no learning in the case of uncertainty of goal selection over the course of trials. Together, our data indicate that by the end of their first year of life, infants rely on information about the certainty of goal selection to make inferences about others' action goals.
There is much interest in the identification of the main drivers controlling changes in the microbial community that may be related to sustainable land use. We examined the influence of soil properties and land-use intensity (N fertilization, mowing, grazing) on total phospholipid fatty acid (PLFA) biomass, microbial community composition (PLFA profiles) and activities of enzymes involved in the C, N, and P cycle. These relationships were examined in the topsoil of grasslands from three German regions (Schorfheide-Chorin (SCH), Hainich-Dun (HAI), Schwabische Alb (ALB)) with different parent material. Differences in soil properties explained 60% of variation in PLFA data and 81% of variation in enzyme activities across regions and land-use intensities. Degraded peat soils in the lowland areas of the SCH with high organic carbon (OC) concentrations and sand content contained lower PLFA biomass, lower concentrations of bacterial, fungal, and arbuscular mycorrhizal PLFAs, but greater enzyme activities, and specific enzyme activities (per unit microbial biomass) than mineral soils in the upland areas of the HAI and ALB, which are finer textured, drier, and have smaller OC concentrations. After extraction of variation that originated from large-scale differences among regions and differences in land-use intensities between plots, soil properties still explained a significant amount of variation in PLFA data (34%) and enzyme activities (60%). Total PLFA biomass and all enzyme activities were mainly related to OC concentration, while relative abundance of fungi and fungal to bacterial ratio were mainly related to soil moisture. Land-use intensity (LUI) significantly decreased the soil C:N ratio. There was no direct effect of LUI on total PLFA biomass, microbial community composition, N and P cycling enzyme activities independent of study region and soil properties. In contrast, the activities and specific activities of enzymes involved in the C cycle increased significantly with LUI independent of study region and soil properties, which can have impact on soil organic matter decomposition and nutrient cycling. Our findings demonstrate that microbial biomass and community composition as well as enzyme activities are more controlled by soil properties than by grassland management at the regional scale.
In this opinion article we propose a scenario detailing how two crucial components have evolved simultaneously to ensure the transition of glycogen to starch in the cytosol of the Archaeplastida last common ancestor: (i) the recruitment of an enzyme from intracellular Chlamydiae pathogens to facilitate crystallization of alpha-glucan chains; and (ii) the evolution of novel types of polysaccharide (de)phosphorylating enzymes from preexisting glycogen (de)phosphorylation host pathways to allow the turnover of such crystals. We speculate that the transition to starch benefitted Archaeplastida in three ways: more carbon could be packed into osmotically inert material; the host could resume control of carbon assimilation from the chlamydial pathogen that triggered plastid endosymbiosis; and cyanobacterial photosynthate export could be integrated in the emerging Archaeplastida.
This study examined the relationship between ethnic identity, orientation toward the White mainstream culture, and psychological well-being among American Indians. In the light of the unique history of American Indians, we investigated the relationship between identification with the American Indian ingroup, orientation toward the dominant White American culture ( in terms of showing behavior typical for White mainstream culture as well as positive attitudes and feelings of belonging to White American culture), and self-efficacy and learned helplessness as indicators of psychological well-being. Structural equation analyses with an adolescent and an adult sample revealed a positive relationship between ethnic identity and self-efficacy but no link with learned helplessness. The tendency to show behavior typical for White mainstream culture was associated with higher self-efficacy in both samples and with lower helplessness in the adult subsample. White American orientation in the form of positive attitudes and sense of belonging were associated with higher helplessness in both samples and with lower self-efficacy among adults. The findings are discussed in terms of the role of both ethnic identity and the orientation toward the mainstream culture for well-being among American Indians, focusing on the distinct relations of White American behavior versus White American affiliation with well-being in American Indians.
On the role of fluoro-substituted nucleosides in DNA radiosensitization for tumor radiation therapy
(2014)
With the present theoretical study of the photochemical switching of E-methylfurylfulgide we contribute an important step towards the understanding of the photochemical processes in furylfulgide-related molecules. We have carried out large-scale, full-dimensional direct semiempirical configuration-interaction surface-hopping dynamics of the photoinduced ring-closure reaction. Simulated static and dynamical UV/Vis-spectra show good agreement with experimental data of the same molecule. By a careful investigation of our dynamical data, we were able to identify marked differences to the dynamics of the previously studied E-isopropylfurylfulgide. With our simulations we can not only reproduce the experimentally observed quantum yield differences qualitatively but we can also pinpoint two reasons for them: kinematics and pre-orientation. With our analysis, we thus offer straightforward molecular explanations for the high sensitivity of the photodynamics towards seemingly minor changes in molecular constitution. Beyond the realm of furylfulgides, these insights provide additional guidance to the rational design of photochemically switchable molecules.
In aquatic systems, natural organic matter (NOM) and in particular humic substances effectively absorb the ultraviolet (UV)/visible light spectrum of solar radiation and act as a photoprotective filter for organisms. Simultaneously, UV contributes to the generation of potentially harmful reactive oxygen species (ROS). Dose-response experiments were conducted on cyanobacteria and green algae with hydrogen peroxide (H2O2) as a long-lived representative of ROS. Delayed fluorescence (DF) decay kinetics was used as a non-invasive tool to follow changes of phytoplankton activity in real time. In order to investigate phototoxicity and photoprotection by NOM on phytoplankton, we exposed algae to UV-pre-irradiated NOM and direct UV excitation. Cyanobacteria responded to H2O2 concentrations as low as 10(-7) M, while green algae were 2 orders of magnitude less sensitive. UV irradiation of medium with NOM generated H2O2 concentrations of 1.5 x 10(-7) to 3.6 x 10(-7) M. When exposed to these concentrations, only the DF of cyanobacteria led to a measurable effect while that of green algae did not change. The addition of NOM protected all phytoplankton from direct UV irradiation, but cyanobacteria benefitted less. From this we conclude that UV-irradiated water enriched with NOM can adversely affect the physiology of cyanobacteria, but not of green algae, which might control phytoplankton composition and species-specific activities.
A method of real-time coseismic wave retrieving was proposed based on the tight integration of GPS, Glonass and strong-motion sensor observations, the validation and precision analysis have been made by an experimental data. The series of results have been shown that: by the integrated Kalman filter and multi-sensors, the coseismic waves can be optimally recovered by complement the advantages of each other, especially when the observation conditions are very bad. In additional, the results are not significantly effected by different receiver clock error processes for the integration solution.
Green algae are of great economic importance. Seaweed is consumed fresh or as seasoning in Japan. The commercial value is determined by quality, color, and flavor and is also strongly influenced by the production area. Our research, based on solid phase microextraction gas chromatography mass spectrometry (SPME-GC-MS), has revealed that volatile compounds differ intensely in the four varieties of commercial green algae. Accordingly, 41 major volatile compounds were identified. Heptadecene was the most abundant compound from Okayama (Ulva prolifera), Tokushima (Ulva prolifera), and Ehime prefecture (Ulva linza). Apocarotenoids, such as ionones, and their derivatives were prominent volatiles in algae from Okayama (Ulva prolifera) and Tokushima prefecture (Ulva prolifera). Volatile, short chained apocarotenoids are among the most potent flavor components and contribute to the flavor of fresh, processed algae, and algae-based products. Benzaldehyde was predominant in seaweed from Shizuoka prefecture (Monostroma nitidum). Multivariant statistical analysis (PCA) enabled simple discrimination of the samples based on their volatile profiles. This work shows the potential of SPME-GC-MS coupled with multivariant analysis to discriminate between samples of different geographical and botanical origins and form the basis for development of authentication methods of green algae products, including seasonings.
An atomistic molecular dynamics simulation approach is applied to model the influence of urethane linker units as well as the addition of water molecules on the simulated shape-memory properties of poly[(rac-lactide)-co-glycolide] (PLGA) and PLGA-based copolyester urethanes comprising different urethane linkers. The shape-memory performance of these amorphous packing models is explored in a simulated heating-deformation-cooling-heating procedure. Depending on the type of incorporated urethane linker, the mechanical properties of the dry copolyester urethanes are found to be significantly improved compared with PLGA, which can be attributed to the number of intermolecular hydrogen bonds between the urethane units. Good shape-memory properties are observed for all the modeled systems. In the dry state, the shape fixation is found to be improved by implementation of urethane units. After swelling of the copolymer models with water, which results in a reduction of their glass transition temperatures, the relaxation kinetics during unloading and shape recovery are found to be substantially accelerated.
Prokaryotic solute binding protein-dependent ATP-binding cassette import systems are divided into type land type II and mechanistic differences in the transport process going along with this classification are under intensive investigation. Little is known about the conformational dynamics during the catalytic cycle especially concerning the transmembrane domains. The type I transporter for positively charged amino acids from Salmonella enterica serovar Typhimurium (1A0-Hi5QMP2) was studied by limited proteolysis in detergent solution in the absence and presence of co-factors including ATP, ADP, LAO/arginine, and Mg2+ ions. Stable peptide fragments could be obtained and differentially susceptible cleavage sites were determined by mass spectrometry as Lys-258 in the nucleotide-binding subunit, HisP, and Arg-217/Arg-218 in the transmembrane subunit, HisQ In contrast, transmembrane subunit HisM was gradually degraded but no stable fragment could be detected. HisP and HisQ were equally resistant under pre- and post-hydrolysis conditions in the presence of arginine-loaded solute-binding protein LAO and ATP/ADP. Some protection was also observed with LAO/arginine alone, thus reflecting binding to the transporter in the apo-state and transmembrane signaling. Comparable digestion patterns were obtained with the transporter reconstituted into proteoliposomes and nanodiscs. Fluorescence lifetime spectroscopy confirmed the change of HisQ(R218) to a more apolar microenvironment upon ATP binding and hydrolysis. Limited proteolysis was subsequently used as a tool to study the consequences of mutations on the transport cycle. Together, our data suggest similar conformational changes during the transport cycle as described for the maltose ABC transporter of Escherichia coli, despite distinct structural differences between both systems.
Context. AMCVn systems are ultracompact binaries in which a (semi-) degenerate star transfers helium-dominated matter onto a white dwarf. They are effective gravitational-wave emitters and potential progenitors of Type Ia supernovae.
Aims. To understand the evolution of AMCVn systems it is necessary to determine their mass-loss rate through their radiation-driven accretion-disk wind. We constructed models to perform quantitative spectroscopy of P Cygni line profiles that were detected in UV spectra.
Methods. We performed 2.5D Monte Carlo radiative transfer calculations in hydrodynamic wind structures by making use of realistic NLTE spectra from the accretion disk and by accounting for the white dwarf as an additional photon source.
Results. We present first results from calculations in which LTE opacities are used in the wind model. A comparison with UV spectroscopy of the AMCVn prototype shows that the modeling procedure is potentially a good tool for determining mass-loss rates and abundances of trace metals in the helium-rich wind.
This article summarizes the latest results on the proton-to-electron mass ratio derived from H-2 observations at high redshift in the light of possible variations of fundamental physical constants. The focus lies on UVES observations of the past years as enormous progress was achieved since the first positive results on / were published. With the better understanding of systematics, dedicated observation runs, and numerous approaches to improve wavelength calibration accuracy, all current findings are in reasonable good agreement with no variation and provide an upper limit of / < 1 x 10(-5) for the redshift range of 2 < z < 3. ((
Miniaturized analytical chip devices like biosensors nowadays provide assistance in highly diverse fields of application such as point-of-care diagnostics and industrial bioprocess engineering. However, upon contact with fluids, the sensor requires a protective shell for its electrical components that simultaneously offers controlled access for the target analytes to the measuring units. We therefore developed a capsule that comprises a permeable and a sealed compartment consisting of variable polymers such as biocompatible and biodegradable polylactic acid (PLA) for medical applications or more economical polyvinyl chloride (PVC) and polystyrene (PS) polymers for bioengineering applications. Production of the sealed capsule compartments was performed by heat pressing of polymer pellets placed in individually designable molds. Controlled permeability of the opposite compartments was achieved by inclusion of NaCl inside the polymer matrix during heat pressing, followed by its subsequent release in aqueous solution. Correlating diffusion rates through the so made permeable capsule compartments were quantified for preselected model analytes: glucose, peroxidase, and polystyrene beads of three different diameters (1.4 mu m, 4.2 mu m, and 20.0 mu m). In summary, the presented capsule system turned out to provide sufficient shelter for small-sized electronic devices and gives insight into its potential permeability for defined substances of analytical interest.
We present and discuss the results of crystallographic and electron paramagnetic resonance (EPR) spectroscopic analyses of five tetrachloridocuprate(II) complexes to supply a useful tool for the structural characterisation of the [CuCl4](2-) moiety in the liquid state, for example in ionic liquids, or in solution. Bis(benzyltriethylammonium)-, bis(trimethylphenylammonium)-, bis(ethyltriphenylphosphonium)-, bis(benzyltriphenylphosphonium)-, and bis(tetraphenylarsonium) tetrachloridocuprate(II) were synthesised and characterised by elemental, IR, EPR and X-ray analyses. The results of the crystallographic analyses show distorted tetrahedral coordination geometry of all [CuCl4](2-) anions in the five complexes and prove that all investigated complexes are stabilised by hydrogen bonds of different intensities. Despite the use of sterically demanding ammonium, phosphonium and arsonium cations to obtain the separation of the paramagnetic Cu(II) centres for EPR spectroscopy no hyperfine structure was observed in the EPR spectra but the principal values of the electron Zeeman tensor, g(parallel to) and g(perpendicular to), could be determined. With these EPR data and the crystallographic parameters we were able to carry out a correlation study to anticipate the structural situation of tetrachloridocuprates in different physical states. This correlation is in good agreement with DFT calculations.
The development of self-adaptive software requires the engineering of an adaptation engine that controls the underlying adaptable software by feedback loops. The engine often describes the adaptation by runtime models representing the adaptable software and by activities such as analysis and planning that use these models. To systematically address the interplay between runtime models and adaptation activities, runtime megamodels have been proposed. A runtime megamodel is a specific model capturing runtime models and adaptation activities. In this article, we go one step further and present an executable modeling language for ExecUtable RuntimE MegAmodels (EUREMA) that eases the development of adaptation engines by following a model-driven engineering approach. We provide a domain-specific modeling language and a runtime interpreter for adaptation engines, in particular feedback loops. Megamodels are kept alive at runtime and by interpreting them, they are directly executed to run feedback loops. Additionally, they can be dynamically adjusted to adapt feedback loops. Thus, EUREMA supports development by making feedback loops explicit at a higher level of abstraction and it enables solutions where multiple feedback loops interact or operate on top of each other and self-adaptation co-exists with offline adaptation for evolution.
We study the thermal Markovian diffusion of tracer particles in a 2D medium with spatially varying diffusivity D(r), mimicking recently measured, heterogeneous maps of the apparent diffusion coefficient in biological cells. For this heterogeneous diffusion process (HDP) we analyse the mean squared displacement (MSD) of the tracer particles, the time averaged MSD, the spatial probability density function, and the first passage time dynamics from the cell boundary to the nucleus. Moreover we examine the non-ergodic properties of this process which are important for the correct physical interpretation of time averages of observables obtained from single particle tracking experiments. From extensive computer simulations of the 2D stochastic Langevin equation we present an in-depth study of this HDP. In particular, we find that the MSDs along the radial and azimuthal directions in a circular domain obey anomalous and Brownian scaling, respectively. We demonstrate that the time averaged MSD stays linear as a function of the lag time and the system thus reveals a weak ergodicity breaking. Our results will enable one to rationalise the diffusive motion of larger tracer particles such as viruses or submicron beads in biological cells.
We have used polarized confocal Raman microspectroscopy and scanning near-field optical microscopy with a resolution of 60 nm to characterize photoinscribed grating structures of azobenzene doped polymer films on a glass support. Polarized Raman microscopy allowed determining the reorientation of the chromophores as a function of the grating phase and penetration depth of the inscribing laser in three dimensions. We found periodic patterns, which are not restricted to the surface alone, but appear also well below the surface in the bulk of the material. Near-field optical microscopy with nanoscale resolution revealed lateral two-dimensional optical contrast, which is not observable by atomic force and Raman microscopy.
A novel perfluorinated magnesium phthalocyanine (MgPcF64) was synthesized and employed to probe nanodomains in hydrophobically modified, amphiphilic cationic polyelectrolytes bearing alkyl and/or fluoroalkyl side chains. MgPcF64 was found to be solubilized exclusively in the aqueous solutions of the fluorocarbon modified polycations, occupying the perfluorinated nanocompartments provided, while analogous polyelectrolytes with alkyl side chains forming hydrocarbon nanocompartments could not host the MgPcF64 dye. Multilayer films were fabricated by means of the layer-by-layer (LbL) deposition method using sodium poly(styrene sulfonate) as a polyanion. Linear multilayer growth was confirmed by UV-Vis spectroscopy and spectroscopic ellipsometry. Atomic force microscopy studies indicated that the micellar conformation of the polycations is preserved in the multilayer films. Fluorescence spectroscopy measurements confirmed that MgPcF64 stays embedded inside the fluorocarbon domains after the deposition process. This facile way of selectively incorporating water-insoluble, photoactive molecules into the structure of polyelectrolyte multilayers may be utilized for nanoengineering of ultrathin film-based optoelectronic devices.
Purpose: Mirror therapy can improve motor and sensory functions, but effects of the mirror illusion on primary motor and somatosensory cortex could not be established consistently.
Methods: Fifteen right handed healthy volunteers performed or observed a finger-thumb opposition task. Cerebral activations during normal movement (NOR), mirrored movement (MIR) and movement observation (OBS) by means of a video chain were recorded with functional magnetic resonance imaging (fMRI). Activation sizes in movement > static conditions were identified using SPM8 (p < 0.001, unc.) and attributed to predefined areas employing the Anatomy toolbox 1.8. Laterality indices for the responsive areas were calculated on the basis of the number of activated voxels.
Results: Relevant bilateral BOLD responses were found in primary motor (M1) and somatosensory (S1 - BA 2, 3b and 3a) cortex, premotor and parietal areas and V5. When comparing MIR to NOR, no significant change of contralateral activation in M1 was found, but clearly at S1 with differences between hands.
Conclusion: The mirror illusion does not elicit immediate changes in motor areas, yet there is a direct effect on somatosensory areas, especially for left hand movements. These results suggest different effects of mirror therapy on processing and rehabilitation of motor and sensory function.
The electromagnetic field in a typical geometry of the Casimir effect is described in the Schwinger-Keldysh formalism. The main result is the photon distribution function (Keldysh Green function) in any stationary state of the field. A two-plate geometry with a sliding interface in local equilibrium is studied in detail, and full agreement with the results of Rytov fluctuation electrodynamics is found.
As an engineering material derived from renewable resources, wood possesses excellent mechanical properties in view of its light weight but also has some disadvantages such as low dimensional stability upon moisture changes and low durability against biological attack. Polymerization of hydrophobic monomers in the cell wall is one of the potential approaches to improve the dimensional stability of wood. A major challenge is to insert hydrophobic monomers into the hydrophilic environment of the cell walls, without increasing the bulk density of the material due to lumen filling. Here, we report on an innovative and simple method to insert styrene monomers into tosylated cell walls (i.e. -OH groups from natural wood polymers are reacted with tosyl chloride) and carry out free radical polymerization under relatively mild conditions, generating low wood weight gains. In-depth SEM and confocal Raman microscopy analysis are applied to reveal the distribution of the polystyrene in the cell walls and the lumen. The embedding of polystyrene in wood results in reduced water uptake by the wood cell walls, a significant increase in dimensional stability, as well as slightly improved mechanical properties measured by nanoindentation.
This commentary argues that, rather than providing an "exhaustive review," Elson and Ferguson (2013) discuss a selective sample of empirical studies on violent video game use which corroborate their claim that there is no systematic evidence for a link between violent video game play and aggression. In evaluating the evidence, the authors portray a biased picture of the current state of knowledge about media violence effects. They fail to distinguish between aggression and violence and between everyday and clinical forms of aggression. Furthermore, they misrepresent key constructs, such as mediation, moderation, and external validity, to discredit methodologies used to assess aggression and media violence use. The paper moves the debate backward rather than forward, falling behind existing meta-analytic studies that consider a much wider and more balanced range of studies.
Intermediates in the formation and thermolysis of peroxides from oxidations with singlet oxygen
(2014)
Herein we describe the recent mechanistic understandings of the singlet oxygen ene reaction to give hydroperoxides and the [4+2] cycloaddition affording endoperoxides. Both experimental findings and theoretical work conclude in the formation of intermediates structurally similar to perepoxides during the ene reaction. Such intermediates mainly control the regio- and stereoselectivities of this reaction class. For the [4+2] cycloaddition, both a synchronous concerted reaction (benzene, naphthalenes) and a stepwise reaction with a non-symmetric zwitterionic intermediate (larger acenes) have been found. The thermolysis of endoperoxides derived from acenes proceeds stepwise for anthracenes, but in a concerted manner for less stable adducts such as naphthalene.
Diffusion of finite-size particles in two-dimensional channels with random wall configurations
(2014)
Diffusion of chemicals or tracer molecules through complex systems containing irregularly shaped channels is important in many applications. Most theoretical studies based on the famed Fick-Jacobs equation focus on the idealised case of infinitely small particles and reflecting boundaries. In this study we use numerical simulations to consider the transport of finite-size particles through asymmetrical two-dimensional channels. Additionally, we examine transient binding of the molecules to the channel walls by applying sticky boundary conditions. We consider an ensemble of particles diffusing in independent channels, which are characterised by common structural parameters. We compare our results for the long-time effective diffusion coefficient with a recent theoretical formula obtained by Dagdug and Pineda
A new functional luminescent lanthanide complex (LLC) has been synthesized with terbium as a central lanthanide ion and biotin as a functional moiety. Unlike in typical lanthanide complexes assembled via carboxylic moieties, in the presented complex, four phosphate groups are chelating the central lanthanide ion. This special chemical assembly enhances the complex stability in phosphate buffers conventionally used in biochemistry. The complex synthesis strategy and photophysical properties are described as well as the performance in time-resolved Forster Resonance Energy Transfer (FRET) assays. In those assays, this biotin-LLC transferred energy either to acceptor organic dyes (Cy5 or AF680) labelled on streptavidin or to quantum dots (QD655 or QD705) surfacefunctionalised with streptavidins. The permanent spatial donor-acceptor proximity is assured through strong and stable biotin-streptavidin binding. The energy transfer is evidenced from the quenching observed in donor emission and from a decrease in donor luminescence decay, both associated with simultaneous increase in acceptor intensity and in the decay time. The dye-based assays are realised in TRIS and in PBS, whereas QD-based systems are studied in borate buffer. The delayed emission analysis allows for quantifying the recognition process and for auto-fluorescence-free detection, which is particularly relevant for application in bioanalysis. In accordance with Forster theory, Forsterradii (R0) were found to be around 60 angstrom for organic dyes and around 105 angstrom for QDs. The FRET efficiency (Z) reached 80% and 25% for dye and QD acceptors, respectively. Physical donor-acceptor distances (r) have been determined in the range 45-60 angstrom for organic dye acceptors, while for acceptor QDs between 120 angstrom and 145 angstrom. This newly synthesised biotin-LLC extends the class of highly sensitive analytical tools to be applied in the bioanalytical methods such as time-resolved fluoroimmunoassays (TR-FIA), luminescent imaging and biosensing.
Object and action naming in Russian- and German- speaking monolingual and bilingual children*
(2014)
The present study investigates the influence of word category on naming performance in two populations: bilingual and monolingual children. The question is whether and, if so, to what extent monolingual and bilingual children differ with respect to noun and verb naming and whether a noun bias exists in the lexical abilities of bilingual children. Picture naming of objects and actions by Russian-German bilingual children (aged 4-7 years) was compared to age-matched monolingual children. The results clearly demonstrate a naming deficit of bilingual children in comparison to monolingual children that increases with age. Noun learning is more fragile in bilingual contexts than is verb learning. In bilingual language acquisition, nouns do not predominate over verbs as much as is seen in monolingual German and Russian children. The results are discussed with respect to semantic-conceptual aspects and language-specific features of nouns and verbs, and the impact of input on the acquisition of these word categories.
We report the results of our investigations on the catchment area, surface sediments, and hydrology of the monsoonal Lonar Lake, central India. Our results indicate that the lake is currently stratified with an anoxic bottom layer, and there is a spatial heterogeneity in the sensitivity of sediment parameters to different environmental processes. In the shallow (0-5 m) near shore oxic-suboxic environments the lithogenic and terrestrial organic content is high and spatially variable, and the organics show degradation in the oxic part. Due to aerial exposure resulting from lake level changes of at least 3m, the evaporitic carbonates are not completely preserved. In the deep water (>5 m) anoxic environment the lithogenics are uniformly distributed and the delta C-13 is an indicator not only for aquatic vs. terrestrial plants but also of lake pH and salinity. The isotopic composition of the evaporites is dependent not only on the isotopic composition of source water (monsoon rainfall and stream inflow) and evaporation, but is also influenced by proximity to the isotopically depleted stream inflow. We conclude that in the deep water environment lithogenic content, and isotopic composition of organic matter can be used for palaeoenvironmental reconstruction.
Biosensors representing the technological counterpart of living senses have found routine application in amperometric enzyme electrodes for decentralized blood glucose measurement, interaction analysis by surface plasmon resonance in drug development, and to some extent DNA chips for expression analysis and enzyme polymorphisms. These technologies have already reached a highly advanced level and need minor improvement at most. The dream of the "100-dollar' personal genome may come true in the next few years provided that the technological hurdles of nanopore technology or of polymerase-based single molecule sequencing can be overcome. Tailor-made recognition elements for biosensors including membrane-bound enzymes and receptors will be prepared by cell-free protein synthesis. As alternatives for biological recognition elements, molecularly imprinted polymers (MIPs) have been created. They have the potential to substitute antibodies in biosensors and biochips for the measurement of low-molecular-weight substances, proteins, viruses, and living cells. They are more stable than proteins and can be produced in large amounts by chemical synthesis. Integration of nanomaterials, especially of graphene, could lead to new miniaturized biosensors with high sensitivity and ultrafast response. In the future individual therapy will include genetic profiling of isoenzymes and polymorphic forms of drug-metabolizing enzymes especially of the cytochrome P450 family. For defining the pharmacokinetics including the clearance of a given genotype enzyme electrodes will be a useful tool. For decentralized online patient control or the integration into everyday "consumables' such as drinking water, foods, hygienic articles, clothing, or for control of air conditioners in buildings and cars and swimming pools, a new generation of "autonomous' biosensors will emerge.
Objectives. Recent work suggests that a genetic variation associated with increased dopamine metabolism in the prefrontal cortex (catechol-O-methyltransferase Val158Met; COMT) amplifies age-related changes in working memory performance. Research on younger adults indicates that the influence of dopamine-related genetic polymorphisms on working memory performance increases when testing the cognitive limits through training. To date, this has not been studied in older adults. Method. Here we investigate the effect of COMT genotype on plasticity in working memory in a sample of 14 younger (aged 24-30 years) and 25 older (aged 60-75 years) healthy adults. Participants underwent adaptive training in the n-back working memory task over 12 sessions under increasing difficulty conditions. Results. Both younger and older adults exhibited sizeable behavioral plasticity through training (P < .001), which was larger in younger as compared to older adults (P < .001). Age-related differences were qualified by an interaction with COMT genotype (P < .001), and this interaction was due to decreased behavioral plasticity in older adults carrying the Val/Val genotype, while there was no effect of genotype in younger adults. Discussion. Our findings indicate that age-related changes in plasticity in working memory are critically affected by genetic variation in prefrontal dopamine metabolism.
The importance of a careful choice of the appropriate scale for studying ecological phenomena has been stressed repeatedly. However, issues of spatial scale in metapopulation dynamics received much more attention compared to temporal scale. Moreover, multiple calls were made to carefully choose the appropriate model structure for Population Viability Analysis (PVA). We assessed the effect of using coarser resolution in time and model structure on population dynamics. For this purpose, we compared outcomes of two PVA models differing in their time step: daily individual-based model (dIBM) and yearly stage-based model (ySBM), loaded with empirical data on a well-known metapopulation of the butterfly Boloria eunomia. Both models included the same environmental drivers of population dynamics that were previously identified as being the most important for this species. Under temperature change scenarios, both models yielded the same qualitative scenario ranking, but they quite substantially differed quantitatively with dIBM being more pessimistic in absolute viability measures. We showed that these differences stemmed from inter-individual heterogeneity in dIBM allowing for phenological shifts of individual appearance. We conclude that a finer temporal resolution and an individual-based model structure allow capturing the essential mechanisms necessary to go beyond mere PVA scenario ranking. We encourage researchers to carefully chose the temporal resolution and structure of their model aiming at (1) depicting the processes important for (meta)population dynamics of the species and (2) implementing the environmental change scenarios expected for their study system in the future, using the temporal resolution at which such changes are predicted to operate.
In wetlands or riparian areas, water withdrawal by plants with access to groundwater or the capillary fringe often causes diurnal groundwater fluctuations. Various approaches use the characteristics of these fluctuations for estimation of daily groundwater evapotranspiration rates. The objective of this paper was to review the available methods, compare them with measured evapotranspiration and assess their recharge assumptions. For this purpose, we employed data of 85 rain-free days of a weighable groundwater lysimeter situated at a grassland site in the Spreewald wetland in north-east Germany. Measurements of hourly recharge and daily evapotranspiration rates were used to assess the different approaches. Our results showed that a maximum of 50% of the day to day variance of the daily evapotranspiration rates could be explained by the approaches based on groundwater fluctuations. Simple and more complex methods performed similarly. For some of the approaches, there were indications that erroneous assumptions compensated each other (e.g., when overestimated recharge counteracted underestimated storage change). We found that the usage of longer time spans resulted in improved estimates of the daily recharge rates and that the estimates were further enhanced by including two night averages. When derived from fitting estimates of recharge or evapotranspiration with according measurements the specific yield, needed to convert changes in water level to water volumes, differed considerably among the methods (from 0.022 to 0.064). Thus, the specific yield can be seen as correction factor that compensates for inadequate process descriptions.
Grain-size distributions offer powerful proxies of past environmental conditions that are related to sediment sorting processes. However, they are often of multimodal character because sediments can get mixed during deposition. To facilitate the use of grain size as palaeoenvironmental proxy, this study aims to distinguish the main detrital processes that contribute to lacustrine sedimentation across the Tibetan Plateau using grain-size end-member modelling analysis. Between three and five robust grain-size end-member subpopulations were distinguished at different sites from similarly-likely end-member model runs. Their main modes were grouped and linked to common sediment transport and depositional processes that can be associated with contemporary Tibetan climate (precipitation patterns and lake ice phenology, gridded wind and shear stress data from the High Asia Reanalysis) and local catchment configurations. The coarse sands and clays with grain-size modes > 250 mu m and < 2 mu m were probably transported by fluvial processes. Aeolian sands (similar to 200 mu m) and coarse local dust (similar to 60 mu m), transported by saltation and in near-surface suspension clouds, are probably related to occasional westerly storms in winter and spring. Coarse regional dust with modes similar to 25 mu m may derive from near-by sources that keep in longer term suspension. The continuous background dust is differentiated into two robust end members (modes: 5-10 and 2-5 mu m) that may represent different sources, wind directions and/or sediment trapping dynamics from long-range, upper-level westerly and episodic northerly wind transport. According to this study grain-size end members of only fluvial origin contribute small amounts to mean Tibetan lake sedimentation (19 +/- 5%), whereas local to regional aeolian transport and background dust deposition dominate the clastic sedimentation in Tibetan lakes (contributions: 42 +/- 14% and 51 +/- 11%). However, fluvial and alluvial reworking of aeolian material from nearby slopes during summer seems to limit end-member interpretation and should be cross-checked with other proxy information. If not considered as a stand-alone proxy, a high transferability to other regions and sediment archives allows helpful reconstructions of past sedimentation history.
Pollen records from large lakes have been used for quantitative palaeoclimate reconstruction, but the influences that lake size (as a result of species-specific variations in pollen dispersal patterns that smaller pollen grains are more easily transported to lake centre) and taphonomy have on these climatic signals have not previously been systematically investigated. We introduce the concept of pollen source area to pollen-based climate calibration using the north-eastern Tibetan Plateau as our study area. We present a pollen data set collected from large lakes in the arid to semi-arid region of central Asia. The influences that lake size and the inferred pollen source areas have on pollen compositions have been investigated through comparisons with pollen assemblages in neighbouring lakes of various sizes. Modern pollen samples collected from different parts of Lake Donggi Cona (in the north-eastern part of the Tibetan Plateau) reveal variations in pollen assemblages within this large lake, which are interpreted in terms of the species-specific dispersal and depositional patterns for different types of pollen, and in terms of fluvial input components. We have estimated the pollen source area for each lake individually and used this information to infer modern climate data with which to then develop a modern calibration data set, using both the multivariate regression tree (MRT) and weighted-averaging partial least squares (WA-PLS) approaches. Fossil pollen data from Lake Donggi Cona have been used to reconstruct the climate history of the north-eastern part of the Tibetan Plateau since the Last Glacial Maximum (LGM). The meanannual precipitation was quantitatively reconstructed using WA-PLS: extremely dry conditions are found to have dominated the LGM, with annual precipitation of around 100 mm, which is only 32% of present-day precipitation. A gradually increasing trend in moisture conditions during the Late Glacial is terminated by an abrupt reversion to a dry phase that lasts for about 1000 yr and coincides with "Heinrich event 1" in the North Atlantic region. Subsequent periods corresponding to the Bolling/Allerod interstadial, with annual precipitation (P-ann) of about 350 mm, and the Younger Dryas event (about 270 mm P-ann) are followed by moist conditions in the early Holocene, with annual precipitation of up to 400 mm. A drier trend after 9 cal. ka BP is followed by a second wet phase in the middle Holocene, lasting until 4.5 cal. ka BP. Relatively steady conditions with only slight fluctuations then dominate the late Holocene, resulting in the present climatic conditions. The climate changes since the LGM have been primarily driven by deglaciation and fluctuations in the intensity of the Asian summer monsoon that resulted from changes in the Northern Hemisphere summer solar insolation, as well as from changes in the North Atlantic climate through variations in the circulation patterns and intensity of the westerlies.
Dissolved organic carbon (DOC) concentrations - mainly of terrestrial origin - are increasing worldwide in inland waters. Heterotrophic bacteria are the main consumers of DOC and thus determine DOC temporal dynamics and availability for higher trophic levels. Our aim was to study bacterial carbon (C) turnover with respect to DOC quantity and chemical quality using both allochthonous and autochthonous DOC sources. We incubated a natural bacterial community with allochthonous C (C-13-labeled beech leachate) and increased concentrations and pulses (intermittent occurrence of organic matter input) of autochthonous C (phytoplankton lysate). We then determined bacterial C consumption, activities, and community composition together with the C flow through bacteria using stable C isotopes. The chemical analysis of single sources revealed differences in aromaticity and low-and high-molecular-weight substance fractions (LMWS and HMWS, respectively) between allochthonous and autochthonous C sources. Both DOC sources (allochthonous and autochthonous DOC) were metabolized at a high bacterial growth efficiency (BGE) around 50%. In treatments with mixed sources, rising concentrations of added autochthonous DOC resulted in a further, significant increase in bacterial DOC consumption of up to 68% when nutrients were not limiting. This rise was accompanied by a decrease in the humic substance (HS) fraction and an increase in bacterial biomass. Changes in DOC concentration and consumption in mixed treatments did not affect bacterial community composition (BCC), but BCC differed in single vs. mixed incubations. Our study highlights that DOC quantity affects bacterial C consumption but not BCC in nutrient-rich aquatic systems. BCC shifted when a mixture of allochthonous and autochthonous C was provided simultaneously to the bacterial community. Our results indicate that chemical quality rather than source of DOC per se (allochthonous vs. autochthonous) determines bacterial DOC turnover.
Zooplankton support distinct bacterial communities in high concentrations relative to the surrounding water, but little is known about how the compositions and functionalities of these bacterial communities change through time in relation to environmental conditions. We conducted a year-long field study of bacterial communities associated with common zooplankton groups as well as free-living bacterial communities in the York River, a tributary of Chesapeake Bay. Bacterial community genetic fingerprints and their carbon substrate usage were examined by denaturing gradient gel electrophoresis (DGGE) of amplified 16S rDNA and by Biolog EcoPlates, respectively. Zooplankton-associated communities were genetically distinct from free-living bacterial communities but utilized a similar array of carbon substrates. On average, bacteria associated with different zooplankton groups were genetically more similar to each other within each month (65.4% similarity) than to bacterial communities of the same zooplankton group from different months (28 to 30% similarity), which suggests the importance of ambient environmental conditions in shaping resident zooplankton-associated bacterial communities. Monthly changes in carbon substrate utilization were less variable for zooplankton-associated bacteria than for free-living bacteria, suggesting that the zooplankton microhabitat is more stable than the surrounding water and supports specific bacterial groups in the otherwise unfavorable conditions in the water column.
Herein, we report the chain-growth tin-free room temperature polymerization method to synthesize n-type perylene diimide-dithiophene-based conjugated polymers (PPDIT2s) suitable for solar cell and transistor applications. The palladium/electron-rich tri-tert-butylphosphine catalyst is effective to enable the chain-growth polymerization of anion-radical monomer Br-TPDIT-Br/Zn to PPDIT2 with a molecular weight up to M-w approximate to 50 kg mol(-1) and moderate polydispersity. This is the second example of the polymerization of unusual anion-radical aromatic complexes formed in a reaction of active Zn and electron-deficient diimide-based aryl halides. As such, the discovered polymerization method is not a specific reactivity feature of the naphthalene-diimide derivatives but is rather a general polymerization tool. This is an important finding, given the significantly higher maximum external quantum efficiency that can be reached with PDI-based copolymers (32-45%) in all-polymer solar cells compared to NDI-based materials (15-30%). Our studies revealed that PPDIT2 synthesized by the new method and the previously published polymer prepared by step-growth Stille polycondensation show similar electron mobility and all-polymer solar cell performance. At the same time, the polymerization reported herein has several technological advantages as it proceeds relatively fast at room temperature and does not involve toxic tin-based compounds. Because several chain-growth polymerization reactions are well-suited for the preparation of well-defined multi-functional polymer architectures, the next target is to explore the utility of the discovered polymerization in the synthesis of end-functionalized polymers and block copolymers. Such materials would be helpful to improve the nanoscale morphology of polymer blends in all-polymer solar cells.
BACKGROUND: The aim of occupational health care management programs (OHMP) is to improve the health status of employees, increase work ability and reduce absence time. This includes better coping abilities, work-related self-efficacy and self-management which are important abilities that should be trained within OHMPs.
OBJECTIVES: To study the effectiveness of an OHMP including special interventions to enhance self-efficacy and self-management.
PARTICIPANTS: Employees from the German Federal Pension Agency.
METHODS: Effects of an OHMP on sickness absence was studied by comparing an intervention group (N = 159) and two control groups (N = 450). A core feature of the OHMP were group sessions with all members of working teams, focussing on self-efficacy and self management of the individual participant as well as the team as a group (focus groups). Participants in the OHMP were asked for their subjective evaluation of the focus groups. Rates of sickness absence were taken from the routine data of the employer.
RESULTS: Participants of the OHMP indicated that they had learned better ways of coping and communication and that they had generated intentions to make changes in their working situation. The rate of sickness absence in the intervention group decreased from 9.26% in the year before the OHMP to 7.93% in the year after the program, while there was in the same time an increase of 7.9% and 10.7% in the two control groups.
CONCLUSIONS: The data suggest that OHMP with focus on self-efficacy and self management of individuals and teams are helpful in reducing work absenteeism.
Arsenic-containing hydrocarbons are one group of fat-soluble organic arsenic compounds (arsenolipids) found in marine fish and other seafood. A risk assessment of arsenolipids is urgently needed, but has not been possible because of the total lack of toxicological data. In this study the cellular toxicity of three arsenic-containing hydrocarbons was investigated in cultured human bladder (UROtsa) and liver (HepG2) cells. Cytotoxicity of the arsenic-containing hydrocarbons was comparable to that of arsenite, which was applied as the toxic reference arsenical. A large cellular accumulation of arsenic, as measured by ICP-MS/MS, was observed after incubation of both cell lines with the arsenolipids. Moreover, the toxic mode of action shown by the three arsenic-containing hydrocarbons seemed to differ from that observed for arsenite. Evidence suggests that the high cytotoxic potential of the lipophilic arsenicals results from a decrease in the cellular energy level. This first in vitro based risk assessment cannot exclude a risk to human health related to the presence of arsenolipids in seafood, and indicates the urgent need for further toxicity studies in experimental animals to fully assess this possible risk.
This study aims to compare impacts of climate change on streamflow in four large representative African river basins: the Niger, the Upper Blue Nile, the Oubangui and the Limpopo. We set up the eco-hydrological model SWIM (Soil and Water Integrated Model) for all four basins individually. The validation of the models for four basins shows results from adequate to very good, depending on the quality and availability of input and calibration data.
For the climate impact assessment, we drive the model with outputs of five bias corrected Earth system models of Coupled Model Intercomparison Project Phase 5 (CMIP5) for the representative concentration pathways (RCPs) 2.6 and 8.5. This climate input is put into the context of climate trends of the whole African continent and compared to a CMIP5 ensemble of 19 models in order to test their representativeness. Subsequently, we compare the trends in mean discharges, seasonality and hydrological extremes in the 21st century. The uncertainty of results for all basins is high. Still, climate change impact is clearly visible for mean discharges but also for extremes in high and low flows. The uncertainty of the projections is the lowest in the Upper Blue Nile, where an increase in streamflow is most likely. In the Niger and the Limpopo basins, the magnitude of trends in both directions is high and has a wide range of uncertainty. In the Oubangui, impacts are the least significant. Our results confirm partly the findings of previous continental impact analyses for Africa. However, contradictory to these studies we find a tendency for increased streamflows in three of the four basins (not for the Oubangui). Guided by these results, we argue for attention to the possible risks of increasing high flows in the face of the dominant water scarcity in Africa. In conclusion, the study shows that impact intercomparisons have added value to the adaptation discussion and may be used for setting up adaptation plans in the context of a holistic approach.
Many mountain belts sustain prolonged snow cover for parts of the year, although enquiries into rates of erosion in these landscapes have focused almost exclusively on the snow-free periods. This raises the question of whether annual snow cover contributes significantly to modulating rates of erosion in high-relief terrain. In this context, the sudden release of snow avalanches is a frequent and potentially relevant process, judging from the physical damage to subalpine forest ecosystems, and the amount of debris contained in avalanche deposits. To quantitatively constrain this visual impression and to expand the sparse literature, we sampled sediment concentrations of n = 28 river-spanning snow-avalanche deposits (snow bridges) in the area around Davos, eastern Swiss Alps, and inferred an orders-of-magnitude variability in specific fine sediment and organic carbon yields (1.8 to 830 t km(-2) yr(-1), and 0.04 to 131 tC km(-2) yr(-1), respectively). A Monte Carlo simulation demonstrates that, with a minimum of free parameters, such variability is inherent to the geometric scaling used for computing specific yields. Moreover, the widely applied method of linearly extrapolating plot scale sample data may be prone to substantial under- or overestimates. A comparison of our inferred yields with previously published work demonstrates the relevance of wet snow avalanches as prominent agents of soil erosion and transporters of biogeochemical constituents to mountain rivers. Given that a number of snow bridges persisted below the insulating debris cover well into the summer months, snow-avalanche deposits also contribute to regulating in-channel sediment and organic debris storage on seasonal timescales. Finally, our results underline the potential shortcomings of neglecting erosional processes in the winter and spring months in mountainous terrain subjected to prominent snow cover.
Floating ice shelves can exert a retentive and hence stabilizing force onto the inland ice sheet of Antarctica. However, this effect has been observed to diminish by the dynamic effects of fracture processes within the protective ice shelves, leading to accelerated ice flow and hence to a sea-level contribution. In order to account for the macroscopic effect of fracture processes on large-scale viscous ice dynamics (i.e., ice-shelf scale) we apply a continuum representation of fractures and related fracture growth into the prognostic Parallel Ice Sheet Model (PISM) and compare the results to observations. To this end we introduce a higher order accuracy advection scheme for the transport of the two-dimensional fracture density across the regular computational grid. Dynamic coupling of fractures and ice flow is attained by a reduction of effective ice viscosity proportional to the inferred fracture density. This formulation implies the possibility of non-linear threshold behavior due to self-amplified fracturing in shear regions triggered by small variations in the fracture-initiation threshold. As a result of prognostic flow simulations, sharp across-flow velocity gradients appear in fracture-weakened regions. These modeled gradients compare well in magnitude and location with those in observed flow patterns. This model framework is in principle expandable to grounded ice streams and provides simple means of investigating climate-induced effects on fracturing (e. g., hydro fracturing) and hence on the ice flow. It further constitutes a physically sound basis for an enhanced fracture-based calving parameterization.
Prevention and anthropology
(2014)
Screening is an important issue in medicine and is used to early identify unrecognised diseases in persons who are apparently in good health. Screening strongly relies on the concept of "normal values". Normal values are defined as values that are frequently observed in a population and usually range within certain statistical limits. Screening for obesity should start early as the prevalence of obesity consolidates already at early school age. Though widely practiced, measuring BMI is not the ultimate solution for detecting obesity. Children with high BMI may be "robust" in skeletal dimensions. Assessing skeletal robustness and in particularly assessing developmental tempo in adolescents are also important issues in health screening.
Yet, in spite of the necessity of screening investigations, appropriate reference values are often missing. Meanwhile, new concepts of growth diagrams have been developed. Stage line diagrams are useful for tracking developmental processes over time. Functional data analyses have efficiently been used for analysing longitudinal growth in height and assessing the tempo of maturation. Convenient low-cost statistics have also been developed for generating synthetic national references.
Charge transport and structural dynamics in low molecular weight and polymerized 1-vinyl-3-pentylimidazolium bis(trifluoromethylsulfonyl) imide ionic liquids (ILs) are investigated by a combination of broadband dielectric spectroscopy, dynamic mechanical spectroscopy and differential scanning calorimetry. While the dc conductivity and fluidity exhibit practically identical temperature dependence for the non-polymerized IL, a significant decoupling of ionic conduction from structural dynamics is observed for the polymerized IL. In addition, the dc conductivity of the polymerized IL exceeds that of its molecular counterpart by four orders of magnitude at their respective calorimetric glass transition temperatures. This is attributed to the unusually high mobility of the anions especially at lower temperatures when the structural dynamics is significantly slowed down. A simple physical explanation of the possible origin of the remarkable decoupling of ionic conductivity from structural dynamics is proposed.
A feasible approach to construct multilayer films of sulfonated polyanilines - PMSA1 and PABMSA1 containing different ratios of aniline, 2-methoxyaniline-5-sulfonic acid (MAS) and 3-aminobenzoic acid (AB), with the entrapped redox enzyme pyrroloquinoline quinone-dependent glucose dehydrogenase (PQQ-GDH) on Au and ITO electrode surfaces, is described. The formation of layers has been followed and confirmed by electrochemical impedance spectroscopy (EIS), which demonstrates that the multilayer assembly can be achieved in a progressive and uniform manner. The gold and ITO electrodes subsequently modified with PMSA1:PQQ-GDH and PABMSA1 films are studied by cyclic voltammetry (CV) and UV-Vis spectroscopy which show a significant direct bioelectrocatalytical response to the oxidation of the substrate glucose without any additional mediator. This response correlates linearly with the number of deposited layers. Furthermore, the constructed polymer/enzyme multilayer system exhibits a rather good long-term stability, since the catalytic current response is maintained for more than 60% of the initial value even after two weeks of storage. This verifies that a productive interaction of the enzyme embedded in the film of substituted polyaniline can be used as a basis for the construction of bioelectronic units, which are useful as indicators for processes liberating glucose and allowing optical and electrochemical transduction.
Making confident statements about the evolution of an ice-sheet shelf system with a numerical model requires the capability to reproduce the migration of the grounding line. Here we show that the shallow-ice approximation/shallow-shelf approximation hybrid-type Parallel Ice Sheet Model (PISM), with its recent improvements, is capable of modeling the grounding line motion in a perturbed ice-sheet shelf system. The model is set up according to the three-dimensional Marine Ice-Sheet Model Intercomparison Project (MISMIP3d), and simulations are carried out across a broad range of spatial resolutions. Using (1) a linear interpolation of the grounding line with locally interpolated basal friction and (2) an improved driving-stress computation across the grounding line, the reversibility of the grounding line (i.e. its retreat after an advance forced by a local perturbation of basal resistance) is captured by the model even at medium and low resolutions (Delta x > 10 km). The transient model response is qualitatively similar to that of higher-order models but reveals a higher initial sensitivity to perturbations on very short timescales. Our findings support the application of PISM to the Antarctic ice sheet from regional up to continental scales and on relatively low spatial resolutions.
We have isolated a cDNA coding for a putative invertebrate-type dopamine receptor (Peadop2) from P. americana brain by using a PCR-based strategy. The mRNA is present in samples from brain and salivary glands. We analyzed the distribution of the PeaDOP2 receptor protein with specific affinity-purified polyclonal antibodies. On Western blots, PeaDOP2 was detected in protein samples from brain, subesophageal ganglion, thoracic ganglia, and salivary glands. In immunocytochemical experiments, we detected PeaDOP2 in neurons with their somata being located at the anterior edge of the medulla bilaterally innervating the optic lobes and projecting to the ventro-lateral protocerebrum. In order to determine the functional and pharmacological properties of the cloned receptor, we generated a cell line constitutively expressing PeaDOP2. Activation of PeaDOP2-expressing cells with dopamine induced an increase in intracellular cAMP. In contrast, a C-terminally truncated splice variant of this receptor did not exhibit any functional property by itself. The molecular and pharmacological characterization of the first dopamine receptor from P. americana provides the basis for forthcoming studies focusing on the significance of the dopaminergic system in cockroach behavior and physiology.
Materials derived from renewable resources are highly desirable in view of more sustainable manufacturing. Among the available natural materials, wood is one of the key candidates, because of its excellent mechanical properties. However, wood and wood-based materials in engineering applications suffer from various restraints, such as dimensional instability upon humidity changes. Several wood modification treatments increase water repellence, but the insertion of hydrophobic polymers can result in a composite material which cannot be considered as renewable anymore. In this study, we report on the grafting of the fully biodegradable poly(epsilon-caprolactone) (PCL) inside the wood cell walls by Sn(Oct)(2) catalysed ring-opening polymerization (ROP). The presence of polyester chains within the wood cell wall structure is monitored by confocal Raman imaging and spectroscopy as well as scanning electron microscopy. Physical tests reveal that the modified wood is more hydrophobic due to the bulking of the cell wall structure with the polyester chains, which results in a novel fully biodegradable wood material with improved dimensional stability.
Differential exhumation in the Puna Plateau and Eastern Cordillera of NW Argentina is controlled by inherited paleostructures and resulting paleotopography related to the Cretaceous Salta Rift paleomargins. The Ceno zoic deformation front related to the development of the Andean retro-arc orogenic system is generally associated with >4 km of exhumation, which is recorded by Cenozoic apatite fi ssion-track (AFT) and (U-Th-[Sm])/He ages (He ages) in the Eastern Cordillera of NW Argentina. New AFT ages from the top of the Nevado de Cachi document Oligocene (ca. 28 Ma) cooling, which, combined with existing data, indicates exhumation of this range between ca. 28 Ma and ca. 14 Ma. However, some of the highest ranges in the Eastern Cordillera preserve Cretaceous ages indicative of limited Cenozoic exhumation. Samples collected from an similar to 3-km-elevation transect along the northern part of the Sierra de Quilmes paleorift fl ank (Laguna Brava) show AFT ages between ca. 80 and ca. 50 Ma and He ages between ca. 45 and ca. 10 Ma. Another set of samples from an similar to 1-km-elevation transect farther to the southwest (La Quebrada) shows Cretaceous AFT ages between ca. 116 Ma and ca. 76 Ma, and mainly Cretaceous He ages, in agreement with AFT data. Analysis of existing AFT and He ages from the area once occupied by the Salta Rift reveals a pattern characterized by Cretaceous ages along paleorift highs and Cenozoic ages within paleorift hanging-wall basins and later foreland basin depocenters. This pattern is interrupted by the Sierras Pampeanas at similar to 28 degrees S, which record mid-Cenozoic ages. Our data are consistent with a complex inherited pattern of pre-Andean paleostructures, likely associated with paleotopography, which was beveled by the Cenozoic regional foreland basin and reactivated during the late Neogene (ca. <10 Ma), strongly controlling the magnitude of Cenozoic uplift and exhumation and thus cooling age distribution. This, combined with variable lithologic erodibility, resulted in an irregular distribution of themochronological ages.
Background: DNA-methylation is a common epigenetic tool which plays a crucial role in gene regulation and is essential for cell differentiation and embryonic development. The placenta is an important organ where gene activity can be regulated by epigenetic DNA modifications, including DNA methylation. This is of interest as, the placenta is the interface between the fetus and its environment, the mother. Exposure to environmental toxins and nutrition during pregnancy may alter DNA methylation of the placenta and subsequently placental function and as a result the phenotype of the offspring. The aim of this study was to develop a reliable method to quantify DNA methylation in large clinical studies. This will be a tool to analyze the degree of DNA methylation in the human placenta in relationship to clinical readouts. Methods: Liquid chromatography-electrospray ionization/multi-stage mass spectrometry (LC-ESI/MS/MS) technique was used for the quantification of the 5dmC/dG ratio in placentas from 248 healthy pregnancies. We were able to demonstrate that this method is a reliable and stable way to determine global placental DNA methylation in large clinical trials. Results/Conclusion: The degree of placental DNA methylation seen in our pilot study varies substantially from 2% to 5%. The clinical implications of this variation need to be demonstrated in adequately powered large studies.
Hemocompatible materials are needed for internal and extracorporeal biomedical applications, which should be realizable by reducing protein and thrombocyte adhesion to such materials. Polyethers have been demonstrated to be highly efficient in this respect on smooth surfaces. Here, we investigate the grafting of oligo- and polyglycerols to rough poly(ether imide) membranes as a polymer relevant to biomedical applications and show the reduction of protein and thrombocyte adhesion as well as thrombocyte activation. It could be demonstrated that, by performing surface grafting with oligo-and polyglycerols of relatively high polydispersity (>1.5) and several reactive groups for surface anchoring, full surface shielding can be reached, which leads to reduced protein adsorption of albumin and fibrinogen. In addition, adherent thrombocytes were not activated. This could be clearly shown by immunostaining adherent proteins and analyzing the thrombocyte covered area. The presented work provides an important strategy for the development of application relevant hemocompatible 3D structured materials.
Polyelectrolytes are macromolecules composed of charged monomers and exhibit unique properties due to the interplay of their flexibility and electrostatic interactions. In solution, they are attracted to oppositely charged surfaces and interfaces and exhibit a transition to an adsorbed state when certain conditions are met concerning the charge densities of the polymer and surface and the properties of the solution. In this review, we discuss two limiting cases for adsorption of flexible polyelectrolytes on curved surfaces: weak and strong adsorption. In the first case, adsorption is strongly influenced by the entropic degrees of freedom of a flexible polyelectrolyte. By contrast, in the strong adsorption limit, electrostatic interactions dominate, which leads to particular adsorption patterns, specifically on spherical surfaces. We discuss the corresponding theoretical approaches, applying a mean-field description for the polymer and the polymer-surface interaction. For weak adsorption, we discuss the critical adsorption behavior by exactly solvable models for planar and spherical geometries and a generic approximation scheme, which is additionally applied to cylindrical surfaces. For strong adsorption, we investigate various polyelectrolyte patterns on cylinders and spheres and evaluate their stability. The results are discussed in the light of experimental results, mostly of DNA adsorption experiments.
Photoinduced excitation energy transfer and accompanying charge separation are elucidated for a supramolecular system of a single fullerene covalently linked to six pyropheophorbide-a dye molecules. Molecular dynamics simulations are performed to gain an atomistic picture of the architecture and the surrounding solvent. Excitation energy transfer among the dye molecules and electron transfer from the excited dyes to the fullerene are described by a mixed quantum-classical version of the Forster rate and the semiclassical Marcus rate, respectively. The mean characteristic time of energy redistribution lies in the range of 10 ps, while electron transfer proceeds within 150 ps. In between, on a 20 to 50 ps time-scale, conformational changes take place in the system. This temporal hierarchy of processes guarantees efficient charge separation, if the structure is exposed to a solvent. The fast energy transfer can adopt the dye excitation to the actual conformation. In this sense, the probability to achieve charge separation is large enough since any dominance of unfavorable conformations that exhibit a large dye-fullerene distance is circumvented. And the slow electron transfer may realize an averaging with respect to different conformations. To confirm the reliability of our computations, ensemble measurements on the charge separation dynamics are simulated and a very good agreement with the experimental data is obtained.
Background: Research on language comprehension in aphasia has primarily focused on comprehension of isolated words and sentences. Even though previous studies have provided insights into comprehension abilities of individuals with aphasia at the word and grammatical level, our understanding of the nature and extent of their language comprehension (dis)abilities is not yet complete. In contrast to the highly restricted semantic and syntactic interpretation of sentences, discourse comprehension requires additional pragmatic and non-linguistic skills.Aims: The purpose of this study was to assess language comprehension in individuals with and without aphasia at the discourse level. In particular, it addressed the question of whether the use of direct speech, compared to indirect speech, affects comprehension of narrative discourse in Dutch aphasic and non-brain-damaged (NBD) listeners.Methods & Procedures: The Direct Speech Comprehension (DISCO) test was developed to examine the effects of manipulating direct vs. indirect speech on discourse comprehension. Twenty-three individuals with aphasia and 20 NBD participants were presented with spoken narratives that contained either direct or indirect speech reports. The narratives were presented audio-visually on an iPad, and comprehension was assessed with yes/no questions.Outcomes & Results: The performance of the participants with aphasia was significantly poorer than that of the NBD participants. Moreover, a main effect for condition type was found, indicating that narratives with direct speech reports were better understood than narratives with indirect speech reports by listeners with and without aphasia. There was no interaction between group and condition type indicating that this main effect held for both the aphasic and the NBD listeners. However, for the participants with aphasia, there was an interaction between condition and Token Test error score indicating that the positive effect of direct speech constructions diminishes for individuals with poorer comprehension.Conclusions: Direct speech constructions facilitate language comprehension in listeners with and without aphasia. One explanation for this finding is the occurrence of additional layers of communication, such as intonation and facial expression, often accompanying direct speech constructions. An alternative account is the degree of grammatical complexity: In Dutch, the syntactic construction of indirect speech requires embedding, whereas in direct speech the introductory sentence and the quote are both main clauses. The finding that the beneficial effect of direct speech on language comprehension diminishes for individuals with severe aphasia may indicate that the DISCO is too difficult for them to reveal an effect of a subtle manipulation such as that of condition type.
The standard procedure in the lab for plasmid isolation usually involves a 2-mL, 16 h over-night cultivation in 15-mL bioreaction tubes in LB medium. This is time consuming, and not suitable for high-throughput applications. This study shows that it is possible to produce plasmid DNA (pDNA) in a 1.5-mL microcentrifuge tube with only 100 L cultivation volume in less than 7 h with a simple protocol. Compared with the standard LB cultivation for pDNA production reaching a final pDNA concentration range of 1.5-4 mu g mL(-1), a 6- to 10-fold increase in plasmid concentration (from 10 up to 25 mu g mL(-1) cultivation volume) is achieved using an optimized medium with an internal substrate delivery system (EnBase (R)). Different strains, plasmids, and the applicability of different inoculation tools (i.e. different starting ODs) were compared, demonstrating the robustness of the system. Additionally, dissolved oxygen was monitored in real time online, indicating that under optimized conditions oxygen limitation can be avoided. We developed a simple protocol with a significantly decreased procedure time, enabling simultaneous handling of more samples, while a consistent quality and a higher final pDNA concentration are ensured.
Recently, C K-edge Near Edge X-ray Absorption Fine Structure (NEXAFS) spectra of graphite (HOPG) surfaces have been measured for the pristine material, and for HOPG treated with either bromine or krypton plasmas (Lippitz et al., Surf. Sci., 2013, 611, L1). Changes of the NEXAFS spectra characteristic for physical (krypton) and/or chemical/physical modifications of the surface (bromine) upon plasma treatment were observed. Their molecular origin, however, remained elusive. In this work we study by density functional theory, the effects of selected point and line defects as well as chemical modifications on NEXAFS carbon K-edge spectra of single graphene layers. For Br-treated surfaces, also Br 3d X-ray Photoelectron Spectra (XPS) are simulated by a cluster approach, to identify possible chemical modifications. We observe that some of the defects related to plasma treatment lead to characteristic changes of NEXAFS spectra, similar to those in experiment. Theory provides possible microscopic origins for these changes.