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Aggregate formation in poly(3-hexylthiophene) depends on molecular weight, solvent, and synthetic method. The interplay of these parameters thus largely controls device performance. In order to obtain a quantitative understanding on how these factors control the resulting electronic properties of P3HT, we measured absorption in solution and in thin films as well as the resulting field effect mobility in transistors. By a detailed analysis of the absorption spectra, we deduce the fraction of aggregates formed, the excitonic coupling within the aggregates, and the conjugation length within the aggregates, all as a function of solvent quality for molecular weights from 5 to 19 kDa. From this, we infer in which structure the aggregated chains pack. Although the 5 kDa samples form straight chains, the 11 and 19 kDa chains are kinked or folded, with conjugation lengths that increase as the solvent quality reduces. There is a maximum fraction of aggregated chains (about 55 +/- 5%) that can be obtained, even for poor solvent quality. We show that inducing aggregation in solution leads to control of aggregate properties in thin films. As expected, the field-effect mobility correlates with the propensity to aggregation. Correspondingly, we find that a well-defined synthetic approach, tailored to give a narrow molecular weight distribution, is needed to obtain high field effect mobilities of up to 0.01 cm2/Vs for low molecular weight samples (=11 kDa), while the influence of synthetic method is negligible for samples of higher molecular weight, if low molecular weight fractions are removed by extraction.
Drought and the availability of mineable phosphorus minerals used for fertilization are two of the important issues agriculture is facing in the future. High phosphorus availability in soils is necessary to maintain high agricultural yields. Drought is one of the major threats for terrestrial ecosystem performance and crop production in future. Among the measures proposed to cope with the upcoming challenges of intensifying drought stress and to decrease the need for phosphorus fertilizer application is the fertilization with silica (Si). Here we tested the importance of soil Si fertilization on wheat phosphorus concentration as well as wheat performance during drought at the field scale. Our data clearly showed a higher soil moisture for the Si fertilized plots. This higher soil moisture contributes to a better plant performance in terms of higher photosynthetic activity and later senescence as well as faster stomata responses ensuring higher productivity during drought periods. The plant phosphorus concentration was also higher in Si fertilized compared to control plots. Overall, Si fertilization or management of the soil Si pools seem to be a promising tool to maintain crop production under predicted longer and more serve droughts in the future and reduces phosphorus fertilizer requirements.
Silicon (Si) speciation and availability in soils is highly important for ecosystem functioning, because Si is a beneficial element for plant growth. Si chemistry is highly complex compared to other elements in soils, because Si reaction rates are relatively slow and dependent on Si species. Consequently, we review the occurrence of different Si species in soil solution and their changes by polymerization, depolymerization, and condensation in relation to important soil processes. We show that an argumentation based on thermodynamic endmembers of Si dependent processes, as currently done, is often difficult, because some reactions such as mineral crystallization require months to years (sometimes even centuries or millennia). Furthermore, we give an overview of Si reactions in soil solution and the predominance of certain solid compounds, which is a neglected but important parameter controlling the availability, reactivity, and function of Si in soils. We further discuss the drivers of soil Si cycling and how humans interfere with these processes. The soil Si cycle is of major importance for ecosystem functioning; therefore, a deeper understanding of drivers of Si cycling (e.g., predominant speciation), human disturbances and the implication for important soil properties (water storage, nutrient availability, and micro aggregate stability) is of fundamental relevance.
The influence of Pavlovian conditioned stimuli on ongoing behavior may contribute to explaining how alcohol cues stimulate drug seeking and intake. Using a Pavlovian-instrumental transfer task, we investigated the effects of alcohol-related cues on approach behavior (i.e., instrumental response behavior) and its neural correlates, and related both to the relapse after detoxification in alcohol-dependent patients. Thirty-one recently detoxified alcohol-dependent patients and 24 healthy controls underwent instrumental training, where approach or non-approach towards initially neutral stimuli was reinforced by monetary incentives. Approach behavior was tested during extinction with either alcohol-related or neutral stimuli (as Pavlovian cues) presented in the background during functional magnetic resonance imaging (fMRI). Patients were subsequently followed up for 6 months. We observed that alcohol-related background stimuli inhibited the approach behavior in detoxified alcohol-dependent patients (t = -3.86, p < .001), but not in healthy controls (t = -0.92, p = .36). This behavioral inhibition was associated with neural activation in the nucleus accumbens (NAcc) (t((30)) = 2.06, p < .05). Interestingly, both the effects were only present in subsequent abstainers, but not relapsers and in those with mild but not severe dependence. Our data show that alcohol-related cues can acquire inhibitory behavioral features typical of aversive stimuli despite being accompanied by a stronger NAcc activation, suggesting salience attribution. The fact that these findings are restricted to abstinence and milder illness suggests that they may be potential resilience factors.
The hummocky ground moraine soil landscape forms a spatial continuum of more or less eroded and depositional soils developed from glacial till under intensive agricultural cultivation. Measurements of soil hydraulic properties in the laboratory on soil cores are mostly limited to some characteristic horizons. However, these horizons can vary in thickness or structural and pedological development depending on relief position. This paper compares soil hydraulic properties of the same soil horizons sampled at different relief positions in a single field representing various degrees of soil erosion/deposition. Water retention curves were determined from undisturbed core samples using sand and kaolin beds with hanging water column and pressure chambers, and the unsaturated hydraulic conductivity using the double-membrane apparatus. Data were fitted to the van Genuchten-Mualem function (VGM) using the nonlinear curve fitting program RETC. The desorption water retention curves for the soil horizons were different and depended on the soil structural development that could be related with the intensity of erosion history at each landscape position. The greatest differences in hydraulic functions were found for the E, Bt, and C horizons. The fitted soil water retention curves reflected these differences mainly in the values of the VGM curve parameters n and theta(s). The landscape features that have the strongest differentiating effect are related to erosion and distance towards the water table. The results can help improving pedotransfer approaches for the estimation of spatially distributed hydraulic parameters for modelling the water movement in hummocky soil landscapes as basis for establishing landscape scale water and element balances.
Leaching of dissolved C in arable hummocky ground moraine soil landscapes is characterized by a spatial continuum of more or less erosion-affected Luvisols, Calcaric Regosols at exposed positions, and Colluvic Regosols in depressions. Our objective was to estimate the fluxes of dissolved C in four differently eroded soils as affected by erosion-induced pedological and soil structural alterations. In this model study, we considered landscape position effects by adapting the water table as the bottom boundary condition and erosion effects by using pedon-specific soil hydraulic properties. The one-dimensional vertical water movement was described with the Richards equation using HYDRUS-1D. Solute fluxes were obtained by combining calculated water fluxes with concentrations of dissolved organic and inorganic C (DOC and DIC, respectively) measured from soil solution extracted by suction cups at biweekly intervals. In the 3-yr period (2010-2012), DOC fluxes in the 2-m soil depth were similar at the three non-colluvic locations with -0.8 +/- 0.1 g m(-2) yr(-1) (i.e., outflow) but were 0.4 g m(-2) yr(-1) (i.e., input) in the depression. The DIC fluxes ranged from -10.2 g m(-2) yr(-1) for the eroded Luvisol, -9.2 g m(-2) yr(-1) for the Luvisol, and -6.1 g m(-2) yr(-1) for the Calcaric Regosol to 3.2 g m(-2) yr(-1) for the Colluvic Regosol. The temporal variations in DOC and DIC fluxes were controlled by water fluxes. The spatially distributed leaching results corroborate the hypothesis that the effects of soil erosion influence fluxes through modified hydraulic and transport properties and terrain-dependent boundary conditions.
Intensive grazing leads to land degradation and desertification of grassland ecosystems followed by serious environmental and social problems. The Xilingol steppe grassland in Inner Mongolia, China, which has been a sink area for dust for centuries, is strongly affected by the negative effects of overgrazing and wind erosion. The aim of this study is the provision of a wind erosion risk map with a spatial high resolution of 25 m to identify actual source and sink areas. In an integrative approach, field measurements of vegetation features and surface roughness length z0 were combined with Advanced Spaceborne Thermal Emission and Reflection Radiometer (ASTER) image data for a land use classification. To determine the characteristics of the different land use classes, a field observation (ground truth) was performed in April 2009. The correlation of vegetation height and z0 (R2 = 0.8, n = 55) provided the basis for a separation of three main classes, grassland, non-vegetation and other. The integration of the soil-adjusted vegetation index (SAVI) and the spectral information from the atmospheric corrected ASTER bands 1, 2 and 3 (visible to near-infrared) led to a classification of the overall accuracy (OA) of 0.79 with a kappa () statistic of 0.74, respectively. Additionally, a digital elevation model (DEM) was used to identify topographical effects in relation to the main wind direction, which enabled a qualitative estimation of potential dust deposition areas. The generated maps result in a significantly higher description of the spatial variability in the Xilingol steppe grassland reflecting the different land use intensities on the current state of the grassland less, moderately and highly degraded. The wind erosion risk map enables the identification of characteristic mineral dust sources, sinks and transition zones.
The dataset in the present article provides information on protozoic silicon (Si) pools represented by euglyphid testate amoebae (TA) in soils of initial and forested biogeosystems. Protozoic Si pools were calculated from densities of euglyphid TA shells and corresponding Si contents. The article also includes data on potential annual biosilicification rates of euglyphid TA at the examined sites. Furthermore, data on selected soil parameters (e.g., readily-available Si, soil pH) and site characteristics (e.g., soil groups, climate data) can be found. The data might be interesting for researchers focusing on biological processes in Si cycling in general and euglyphid TA and corresponding protozoic Si pools in particular.
The dataset in the present article provides information on protozoic silicon (Si) pools represented by euglyphid testate amoebae (TA) in soils of initial and forested biogeosystems. Protozoic Si pools were calculated from densities of euglyphid TA shells and corresponding Si contents. The article also includes data on potential annual biosilicification rates of euglyphid TA at the examined sites. Furthermore, data on selected soil parameters (e.g., readily-available Si, soil pH) and site characteristics (e.g., soil groups, climate data) can be found. The data might be interesting for researchers focusing on biological processes in Si cycling in general and euglyphid TA and corresponding protozoic Si pools in particular.
Silicon (Si) is considered as a quasiessential element for higher plants as its uptake increases plant growth and resistance against abiotic as well as biotic stresses. Foliar application of fertilizers generally is assumed to be a comparably environment-friendly form of fertilization because only small quantities are needed. The interest in foliar fertilization and the use of Si as a fertilizer in general increased significantly within the last decades, but there are only few publications dealing with the foliar application of Si at all. In the present review, the effects of Si foliar fertilization, including nano-Si fertilizers, on the three most important crops on a global scale, that is, maize, rice, and wheat, are summarized. Additionally, different pathways (i.e., cuticular pathways, stomata, and trichomes) of foliar uptake and functioning of Si foliar fertilizers against biotic (i.e., fungal diseases and harmful insects), as well as abiotic (i.e., water stress, macronutrient imbalance, and heavy metal toxicity) stressors are discussed. Future research should especially focus on (1) the gathering of empirical data from field and greenhouse experiments, (2) the intensification of co-operations between practitioners and scientists, (3) interdisciplinary research, and (4) the analysis of results from multiple studies (meta-analysis, big data) to fully understand effects, uptake, and functioning of Si foliar fertilizers and to evaluate their potential in modern sustainable agriculture concepts.