Pressure-Sensitive Adhesives under the Influence of Relative Humidity: Inner Structure and Failure Mechanisms.

Model pressure-sensitive adhesive (PSA) films of the statistical copolymer P(EHA-stat-20MMA), which comprises 80% ethylhexyl acrylate (EHA) and 20% methyl methacrylate (MMA), are studied. The PSA films are stored under different relative humidities from <2% to 96% for 24 h and subsequently investigated concerning the near-surface composition profile by measuring X-ray reflectivity (XRR) and tack performance. For both types of measurements, special custom-made sample environments are used, which ensure constant temperature and relative humidity during the XRR and tack measurements. Different failure mechanisms of the adhesive bond are found by adjusting the relative humidity. XRR measurements evidence enrichment layers in vicinity to and at the surface depending on the provided relative humidity during the postproduction treatment, which also influence the tack performance. This finding is supported by tack measurements using punches with different roughness.

Infiltration of polymer hole-conductor into mesoporous titania structures for solid-state dye-sensitized solar cells.

The degree of filling of titania nanostructures with a solid hole-conducting material is important for the performance of solid-state dye-sensitized solar cells (ssDSSCs). Different ways to infiltrate the hole-conducting polymer poly(3-hexylthiophene) (P3HT) into titania structures, both granular structures as they are already applied commercially and tailored sponge nanostructures, are investigated. The solar cell performance is compared to the morphology determined with scanning electron microscopy (SEM) and time-of-flight grazing incidence small-angle neutron scattering (TOF-GISANS). The granular titania structure, commonly used for ssDSSCs, shows a large distribution of particle and pore sizes, with porosities in the range from 41 to 67%, including even dense parts without pores. In contrast, the tailored sponge nanostructure has well-defined pore sizes of 25 nm with an all-over porosity of 54%. Filling of the titania structures with P3HT by solution casting results in a mesoscopic P3HT overlayer and consequently a bad solar cell performance, even though a filling ratio of 67% is observed. For the infiltration by repeated spin coating, only 57% pore filling is achieved, whereas filling by soaking in the solvent with subsequent spin coating yields filling as high as 84% in the case of the tailored titania sponge structures. The granular titania structure is filled less completely than the well-defined porous structures. The solar cell performance is increased with an increasing filling ratio for these two ways of infiltration. Therefore, filling by soaking in the solvent with subsequent spin coating is proposed.

Continental-scale effects of nutrient pollution on stream ecosystem functioning.

Excessive nutrient loading is a major threat to aquatic ecosystems worldwide that leads to profound changes in aquatic biodiversity and biogeochemical processes. Systematic quantitative assessment of functional ecosystem measures for river networks is, however, lacking, especially at continental scales. Here, we narrow this gap by means of a pan-European field experiment on a fundamental ecosystem process--leaf-litter breakdown--in 100 streams across a greater than 1000-fold nutrient gradient. Dramatically slowed breakdown at both extremes of the gradient indicated strong nutrient limitation in unaffected systems, potential for strong stimulation in moderately altered systems, and inhibition in highly polluted streams. This large-scale response pattern emphasizes the need to complement established structural approaches (such as water chemistry, hydrogeomorphology, and biological diversity metrics) with functional measures (such as litter-breakdown rate, whole-system metabolism, and nutrient spiraling) for assessing ecosystem health.

A global experiment suggests climate warming will not accelerate litter decomposition in streams but might reduce carbon sequestration.

The decomposition of plant litter is one of the most important ecosystem processes in the biosphere and is particularly sensitive to climate warming. Aquatic ecosystems are well suited to studying warming effects on decomposition because the otherwise confounding influence of moisture is constant. By using a latitudinal temperature gradient in an unprecedented global experiment in streams, we found that climate warming will likely hasten microbial litter decomposition and produce an equivalent decline in detritivore-mediated decomposition rates. As a result, overall decomposition rates should remain unchanged. Nevertheless, the process would be profoundly altered, because the shift in importance from detritivores to microbes in warm climates would likely increase CO(2) production and decrease the generation and sequestration of recalcitrant organic particles. In view of recent estimates showing that inland waters are a significant component of the global carbon cycle, this implies consequences for global biogeochemistry and a possible positive climate feedback.

Functional leaf traits and biodiversity effects on litter decomposition in a stream.

Rapid loss of biodiversity worldwide has raised concerns about the consequences to ecosystem functioning, including processes such as litter decomposition. Consequent experiments with litter mixtures to assess effects of changing tree composition and diversity on decomposition have given mixed results, but the causes are not clear. Reasoning that such conflicting accounts reported in the literature may be reconciled by considering differences in functional litter traits, we conducted a field experiment in a stream with leaf litter from nine deciduous tree species mixed in a total of 40 combinations. Fine-mesh and coarse-mesh litter bags were used to distinguish between potential effects mediated by microbial decomposers and detritivores. We hypothesized that diversity effects would emerge in species mixtures containing functionally dissimilar leaves but be absent in mixtures of functionally similar litter as assessed by determining proximate lignin, nitrogen, and phosphorus contents of the litter. Mean decomposition rates of litter mixtures did not lend support to our hypothesis for either microbial decomposition (as inferred from mass loss in fine-mesh litter bags) or decomposition caused by both microbes and detritivores (mass loss from coarse-mesh bags). Decomposition rates were largely controlled by litter lignin content, whereas P and especially N were not important. In line with our hypothesis, the most recalcitrant (slowly decomposing) and most labile (rapidly decomposing) species decomposed slower and faster, respectively, in litter mixtures comprising different decay categories than in homogenous mixtures composed of a single decay category or in single-species litter bags. However, across decay categories, evidence was weak in support of the idea that functional litter dissimilarity matters, in spite of plausible mechanisms that could cause such effects.

Placing biodiversity and ecosystem functioning in context: environmental perturbations and the effects of species richness in a stream field experiment.

Greater biodiversity is often associated with increased ecosystem process rates, and is expected to enhance the stability of ecosystem functioning under abiotic stress. However, these relationships might themselves be altered by environmental factors, complicating prediction of the effects of species loss in ecosystems subjected to abiotic stress. In boreal streams, we investigated effects of biodiversity and two abiotic perturbations on three related indices of ecosystem functioning: leaf decomposition, detritivore leaf processing efficiency (LPE) and detritivore growth. Replicate field enclosures containing leaves and detritivore assemblages were exposed to liming and nutrient enrichment, raising pH and nutrient levels. Both treatments constitute perturbations for our naturally acidic and nutrient-poor streams. We also varied detritivore species richness and density. The effects of the abiotic and diversity manipulations were similar in magnitude, but whereas leaf decomposition increased by 18% and 8% following liming and nutrient enrichment, respectively, increased detritivore richness reduced leaf decomposition (6%), detritivore LPE (19%) and detritivore growth (12%). The detritivore richness effect on growth was associated with negative trait-independent complementarity, indicating interspecific interference competition. These interactions were apparently alleviated in both enriched and limed enclosures, as trait-independent complementarity became less negative. LPE increased with detritivore density in the monocultures, indicating benefits of intra-specific aggregation that outweighed the costs of intra-specific competition, and dilution of these benefits probably contributed to lowered leaf decomposition in the species mixtures. Finally, the effects of liming were reduced in most species mixtures relative to the monocultures. These results demonstrate how environmental changes might regulate the consequences of species loss for functioning in anthropogenically perturbed ecosystems, and highlight potential influences of biodiversity on functional stability. Additionally, the negative effects of richness and positive effects of density in our field study were opposite to previous laboratory observations, further illustrating the importance of environmental context for biodiversity-ecosystem functioning relationships.

Temperature oscillation coupled with fungal community shifts can modulate warming effects on litter decomposition.

Diel temperature oscillations are a nearly ubiquitous phenomenon, with amplitudes predicted to change along with mean temperatures under global-warming scenarios. Impact assessments of global warming have largely disregarded diel temperature oscillations, even though key processes in ecosystems, such as decomposition, may be affected. We tested the effect of a 5 degrees C temperature increase with and without diel oscillations on litter decomposition by fungal communities in stream microcosms. Five temperature regimes with identical thermal sums (degree days) were applied: constant 3 degrees and 8 degrees C; diel temperature oscillations of 5 degrees C around each mean; and oscillations of 9 degrees C around 8 degrees C. Temperature oscillations around 8 degrees C (warming scenario), but not 3 degrees C (ambient scenario), accelerated decomposition by 18% (5 degrees C oscillations) and 31% (9 degrees C oscillations), respectively, compared to the constant temperature regime at 8 degrees C. Community structure was not affected by oscillating temperatures, although the rise in mean temperature from 3 degrees to 8 degrees C consistently shifted the relative abundance of species. A simple model using temperature-growth responses of the dominant fungal decomposers accurately described the experimentally observed pattern, indicating that the effect of temperature oscillations on decomposition in our warming scenario was caused by strong curvilinear responses of species to warming at low temperature, particularly of the species becoming most abundant at 8 degrees C (Tetracladium marchalianum). These findings underscore the need to consider species-specific temperature characteristics in concert with changes in communities when assessing consequences of global warming on ecosystem processes.

MRI volumetry for the preoperative diagnosis of trigeminal neuralgia.

To assess whether quantitative measuring methods can help improve the reliability of MRI-based evaluations of the pathological role of a neurovascular conflict between an artery and the trigeminal nerve. In a prospective study, magnetic resonance images were obtained from 62 patients with unilateral facial pain and 50 healthy test subjects. In coronal T1- and T2-weighted sequences volume measurements were performed by regions of interest and compared intraindividually (healthy versus affected side in the patient populations and right versus left side in the group of test subjects) and on the basis of the different clinical pictures (t test for dependent and independent samples, p<0.05). In patients with trigeminal neuralgia, the affected nerve showed a smaller volume than the trigeminal nerve on the healthy side (p<0.001). Such a volume difference was noted neither in the other patients nor in the healthy test subjects. Quantitative MRI measurements allow a pathological neurovascular conflict to be distinguished from a nonpathological condition where an artery is in close proximity to the trigeminal nerve. The measured volume difference between the healthy and the affected nerve in patients with neuralgia is indicative of trigeminal nerve atrophy resulting from damage to the nerve.