Molecular‐Level Switching of Polymer/Nanocrystal Non‐Covalent Interactions and Application in Hybrid Solar Cells

Hybrid composites obtained upon blending conjugated polymers and colloidal semiconductor nanocrystals are regarded as attractive photo­active materials for optoelectronic applications. Here it is demonstrated that tailoring nanocrystal surface chemistry permits to control non‐covalent and electronic interactions between organic and inorganic components. The pending moieties of organic ligands at the nanocrystal surface are shown to not merely confer colloidal stability while hindering charge separation and transport, but drastically impact morphology of hybrid composites during formation from blend solutions. The relevance of this approach to photovoltaic applications is demonstrated for composites based on poly(3‐hexylthiophene) and lead sulfide nanocrystals, considered as inadequate until this report, which enable the fabrication of hybrid solar cells displaying a power conversion efficiency that reaches 3%. By investigating (quasi)steady‐state and time‐resolved photo‐induced processes in the nanocomposites and their constituents, it is ascertained that electron transfer occurs at the hybrid interface yielding long‐lived separated charge carriers, whereas interfacial hole transfer appears hindered. Here a reliable alternative aiming to gain control over macroscopic optoelectronic properties of polymer/nanocrystal composites by mediating their non‐covalent interactions via ligands' pending moieties is provided, thus opening new possibilities towards efficient solution‐processed hybrid solar cells.     

Anti-Platelet Effect Induced by Iron Oxide Nanoparticles: Correlation with Conformational Change in Fibrinogen

Iron oxide nanoparticles are developed for various biomedical applications, however, there is limited understanding regarding their effects and toxicity on blood components. The particles traveling in circulation inevitably interact with blood cells and plasma proteins and may interfere with hemostasis. Specifically, this study focuses on the influence of superparamagnetic iron oxide nanoparticles (SPIONs) coated with a biocompatible polymer, polyvinyl alcohol (PVA), on platelet function. Here, engineered SPIONs that are functionalized with various PVA coatings to provide these particles with different surface charges and polymer packing are described. These formulations are assessed for any interference with human platelet functions and coagulation, ex vivo. Positively charged SPIONs induce a significant change in platelet GPIIb-IIIa conformation, indicative of platelet activation at the dose of 500 µg mL⁻¹. Remarkably, engineered PVA(polyvinyl alcohol)-SPIONs all display a robust dose-dependent anti-platelet effect on platelet aggregation, regardless of the PVA charge and molecular weight. After assessing hypotheses involving SPION-induced steric hindrance in platelet–platelet bridging, as well as protein corona involvement in the antiplatelet effect, the study concludes that the presence of PVA-SPIONs induces fibrinogen conformational change, which correlates with the observed dose-dependent anti-platelet effect.     

Evaluation of different approaches for modeling effects of acid rain on soils in China

Acid deposition is an environmental problem of increasing concern in China. Acidic soils are common in the southern part of the country and soil acidification caused by acid deposition is expected to occur. Here we test and apply two different approaches for modeling effects of acid deposition and compare results with observed data from sites throughout southern China. The dynamic model MAGIC indicates that, during the last few decades, soil acidification rates have increased considerably due to acid deposition. This acidification will continue if sulfur deposition is not reduced, and if reduced more rapidly than base cation deposition. With the Steady State Mass Balance model (SSMB), and assuming that a molar ratio of Ca2+/Al3+ < 1 in soil water is harmful to vegetation, we estimate a slight probability for exceedance of the critical load for present deposition rates. Results from both modeling approaches show a strong dependence with deposition of base cations as well as sulfur. Hence, according to the models, changes in emission control of alkaline particulate matter prior to sulfur dioxide will be detrimental to the environment. Model calculations are, however, uncertain, particularly because available data on base cation deposition fluxes are scarce, and that model formulation of aluminum chemistry does not fully reproduce observations. An effort should be made to improve our present knowledge regarding deposition fluxes. Improvements to the model are suggested. Our work indicates that the critical loads presented in the regional acid deposition assessment model RAINS-Asia are too stringent. We find weaknesses in the SSMB approach, developed for northern European conditions, when applying it to Chinese conditions. We suggest an improved effort to revise the risk parameters for use in critical load estimates in China.     

High-Frequency Diel Dissolved Oxygen Stream Data Modeled for Variable Temperature and Scale

Diel dissolved oxygen (DO) concentrations and temperature were sensed at high-frequency and modeled in an eastern Iowan stream, Clear Creek, in an agricultural setting. The magnitude of the diel changes in DO and temperature were largest at the upstream (headwater) station. Inclusion of temperature change factors increased the accuracy of modeling results and yielded estimates of the reaeration rate constant, primary production rate, and respiration rate. The DO modeling of the high-frequency measurements (15-min intervals) revealed a temperature-driven nonlinear reaeration process that led to increases in nighttime DO concentrations. The DO modeling results from three sensing stations in the watershed revealed decreasing trends in primary productivity, respiration, and the reaeration rate constant with increasing drainage area. Light extinction from suspended solids was the main factor limiting net primary production. As a result, the P/R ratio also decreased with increasing drainage area. High-frequency sensor data and DO modeling revealed the effects of temperature and watershed scale on the primary factors that dictate diel DO dynamics in a stream setting.     

Assessing the Use of the sGC Stimulator BAY-747, as a Potential Treatment for Duchenne Muscular Dystrophy

Duchenne muscular dystrophy (DMD) is a severe and progressive muscle wasting disorder, affecting one in 3500 to 5000 boys worldwide. The NO-sGC-cGMP pathway plays an important role in skeletal muscle function, primarily by improving blood flow and oxygen supply to the muscles during exercise. In fact, PDE5 inhibitors have previously been investigated as a potential therapy for DMD, however, a large-scale Phase III clinical trial did not meet its primary endpoint. Since the efficacy of PDE5i is dependent on sufficient endogenous NO production, which might be impaired in DMD, we investigated if NO-independent sGC stimulators, could have therapeutic benefits in a mouse model of DMD. Male mdx/mTR^G2 mice aged six weeks were given food supplemented with the sGC stimulator, BAY-747 (150 mg/kg of food) or food alone (untreated) ad libitum for 16 weeks. Untreated C57BL6/J mice were used as wild type (WT) controls. Assessments of the four-limb hang, grip strength, running wheel and serum creatine kinase (CK) levels showed that mdx/mTR^G2 mice had significantly reduced skeletal muscle function and severe muscle damage compared to WT mice. Treatment with BAY-747 improved grip strength and running speed, and these mice also had reduced CK levels compared to untreated mdx/mTR^G2 mice. We also observed increased inflammation and fibrosis in the skeletal muscle of mdx/mTR^G2 mice compared to WT. While gene expression of pro-inflammatory cytokines and some pro-fibrotic markers in the skeletal muscle was reduced following BAY-747 treatment, there was no reduction in infiltration of myeloid immune cells nor collagen deposition. In conclusion, treatment with BAY-747 significantly improves several functional and pathological parameters of the skeletal muscle in mdx/mTR^G2 mice. However, the effect size was moderate and therefore, more studies are needed to fully understand the potential treatment benefit of sGC stimulators in DMD.     

Reconstruction of pristine morphology,flow, nutrient conditions and submerged vegetation of lowland river spree (Germany) from palaeomeanders

The European Water Framework Directive requires the definition of reference conditions for each type of surface waters as a base to establish a classification system in which deviations from this high quality status must be determined. In order to reconstruct pristine conditions in the lower river Spree we investigated palaeomeanders using palaeohydrological and palaeolimnological methods. The settlement history of this region suggests low anthropogenic impact for all periods before ～700 cal AD. Three palaeomeanders representing the conditions of the late Sub‐boreal/early Sub‐atlantic were investigated. River width and depth at bankfull stage were reconstructed using cross‐sections of the meanders. Based on these data and experiments on the recent river, a parametric model was developed to calculate the bankfull palaeodischarge. Reconstructions show narrower and shallower channels for the undisturbed lower Spree (～20 m mean width and 0.8 m mean depth at bankfull stage) as compared to recent conditions (35 m and 1.6 m, respectively). Flow velocities and discharge at bankfull stage have been smaller in reconstructed sub‐fossil channels (0.5 m s^?1 and 8 m³ s^?1 in the pristine lower Spree as compared to 0.9 m s^?1 and 52 m³ s^?1 in the recent lower Spree) and flow variability was higher. The increase in bankfull discharge was mainly attributed to deforestation and drainage of the catchment as well as channelization, bank protection and river regulation measures. The organic silt at the base of the sediment cores contained well‐preserved fossil diatom assemblages. Diatom‐inferred total phosphorus (DI‐TP) concentrations of 59–73 µg L^?1 (median 62 µg L^?1) indicate eutrophic to hypertrophic conditions and suggest naturally slightly lower nutrient levels than today. These past nutrient conditions, morphology and large numbers of macrofossil remains indicate optimum growth conditions for submerged macrophytes growth. The combination of palaeohydrological and palaeolimnological parameters proved to be a useful approach for the determination of pristine conditions in a lowland river. Copyright © 2008 John Wiley & Sons, Ltd.     

Comparison of Long-Term Observed Sediment Trap Efficiency with Empirical Equations for Coralville Reservoir, Iowa

Trapping efficiency (TE) is defined as the percent of particles that are retained within an impoundment. TE can vary from ? 0% indicating no sediment is retained or is lost, to 100% where all the sediment is retained. In this paper a high quality, long-term data set (32?years) was used to demonstrate that annual sediment trap efficiencies for a run of the river impoundment are variable. For water years 1973–2005, annual trap efficiencies for Coralville Reservoir ranged from 5.6 to 95.8%, with a mean of 74.7% and a median of 79.9%. Overall trap efficiency for the entire period was determined to be 80.3% and a detention time of 12.4?days. A comparison of the observed long-term TE was done against different empirical TE equations that are commonly used (Brown, Brune, Churchill, Dendy, Heinemann, & USDA/Summit Co., Water District). The Churchill equation provided the best fit of the empirical trap efficiency equations (TEC = 79.1%); all other empirical TE relationships underestimated the observed trap efficiency with errors ranging from 13.7 to 33.1%. Bathymetric data show that since 1958 the reservoir has lost 11% of its flood storage capacity, and over 62% of its normal pool capacity. For the time studied (1973–2005) the loss of storage is estimated to correspond to 16.9×109?kg of sediment deposited in the reservoir, resulting in an annual sedimentation rate of 5.3×108?kg?year?1.