Tunable high-index photonic glasses

Materials with extreme photonic properties such as maximum diffuse reflectance, high albedo, or tunable band gaps are essential in many current and future photonic devices and coatings. While photonic crystals, periodic anisotropic structures, are well established, their disordered counterparts, photonic glasses (PGs), are less understood despite their most interesting isotropic photonic properties. Here, we introduce a controlled high index model PG system. It is made of monodisperse spherical TiO$_2$ colloids to exploit strongly resonant Mie scattering for optimal turbidity. We report spectrally resolved combined measurements of turbidity and light energy velocity from large monolithic crack-free samples. This material class reveals pronounced resonances enabled by the possibility to tune both the refractive index of the extremely low polydisperse constituents and their radius. All our results are rationalized by a model based on the energy coherent potential approximation, which is free of any fitting parameter. Surprisingly good quantitative agreement is found even at high index and elevated packing fraction. This class of PGs may be the key to optimized tunable photonic materials and also central to understand fundamental questions such as isotropic structural colors, random lasing or strong light localization in 3D.Comment: Main text: 8 pages, 4 figures; Supporting Information: 5 pages, 5 figure

Nanoparticle shape anisotropy and photoluminescence properties : Europium containing ZnO as a model case

The precise control over electronic and optical properties of semiconductor (SC) materials is pivotal for a number of important applications like in optoelectronics, photocatalysis or in medicine. It is well known that the incorporation of heteroelements (doping as a classical case) is a powerful method for adjusting and enhancing the functionality of semiconductors. Independent from that, there already has been a tremendous progress regarding the synthesis of differently sized and shaped SC nanoparticles, and quantum-size effects are well documented experimentally and theoretically. Whereas size and shape control of nanoparticles work fairly well for the pure compounds, the presence of a heteroelement is problematic because the impurities interfere strongly with bottom up approaches applied for the synthesis of such particles, and effects are even stronger, when the heteroelement is aimed to be incorporated into the target lattice for chemical doping. Therefore, realizing coincident shape control of nanoparticle colloids and their doping still pose major difficulties. Due to a special mechanism of the emulsion based synthesis method presented here, involving a gelation of emulsion droplets prior to crystallization of shape-anisotropic ZnO nanoparticles, heteroelements can be effectively entrapped inside the lattice. Different nanocrystal shapes such as nanorods, -prisms, -plates, and -spheres can be obtained, determined by the use of certain emulsification agents. The degree of morphologic alterations depends on the type of incorporated heteroelement M, concentration, and it seems that some shapes are more tolerant against doping than others. Focus was then set on the incorporation of Eu³⁺ inside the ZnO particles, and it was shown that nanocrystal shape and aspect ratios could be adjusted while maintaining a fixed dopant level. Special PL properties could be observed implying energy transfer from ZnO excited near its band-gap (3.3 eV) to the Eu³⁺ states mediated by defect luminescence of the nanoparticles. Indications for an influence of shape on photoluminescence (PL) properties were found. Finally, rod-like Eu@ZnO colloids were used as tracers to investigate their uptake into biological samples like HeLa cells. The PL was sufficient for identifying green and red emission under visible light excitation

Evolution of particle composition in CLOUD nucleation experiments

Peer reviewe

Unexpectedly acidic nanoparticles formed in dimethylamine-ammonia-sulfuric-acid nucleation experiments at CLOUD

New particle formation driven by acid-base chemistry was initiated in the CLOUD chamber at CERN by introducing atmospherically relevant levels of gas-phase sulfuric acid and dimethylamine (DMA). Ammonia was also present in the chamber as a gas-phase contaminant from earlier experiments. The composition of particles with volume median diameters (VMDs) as small as 10 nm was measured by the Thermal Desorption Chemical Ionization Mass Spectrometer (TDCIMS). Particulate ammonium-to-dimethylaminium ratios were higher than the gas-phase ammonia-to-DMA ratios, suggesting preferential uptake of ammonia over DMA for the collected 10-30 nm VMD particles. This behavior is not consistent with present nanoparticle physicochemical models, which predict a higher dimethylaminium fraction when NH3 and DMA are present at similar gas-phase concentrations. Despite the presence in the gas phase of at least 100 times higher base concentrations than sulfuric acid, the recently formed particles always had measured base : acid ratios lower than 1 : 1. The lowest base fractions were found in particles below 15 nm VMD, with a strong size-dependent composition gradient. The reasons for the very acidic composition remain uncertain, but a plausible explanation is that the particles did not reach thermodynamic equilibrium with respect to the bases due to rapid heterogeneous conversion of SO2 to sulfate. These results indicate that sulfuric acid does not require stabilization by ammonium or dimethylaminium as acid-base pairs in particles as small as 10 nm.Peer reviewe

Molecular understanding of sulphuric acid-amine particle nucleation in the atmosphere

4 pages 359-363 in the print version, additional 7 pages online.Peer reviewe

The effect of acid-base clustering and ions on the growth of atmospheric nano-particles

The growth of freshly formed aerosol particles can be the bottleneck in their survival to cloud condensation nuclei. It is therefore crucial to understand how particles grow in the atmosphere. Insufficient experimental data has impeded a profound understanding of nano-particle growth under atmospheric conditions. Here we study nano-particle growth in the CLOUD (Cosmics Leaving OUtdoors Droplets) chamber, starting from the formation of molecular clusters. We present measured growth rates at sub-3 nm sizes with different atmospherically relevant concentrations of sulphuric acid, water, ammonia and dimethylamine. We find that atmospheric ions and small acid-base clusters, which are not generally accounted for in the measurement of sulphuric acid vapour, can participate in the growth process, leading to enhanced growth rates. The availability of compounds capable of stabilizing sulphuric acid clusters governs the magnitude of these effects and thus the exact growth mechanism. We bring these observations into a coherent framework and discuss their significance in the atmosphere.Peer reviewe

Effectiveness and safety of opicapone in Parkinson’s disease patients with motor fluctuations: the OPTIPARK open-label study

Background The efficacy and safety of opicapone, a once-daily catechol-O-methyltransferase inhibitor, have been established in two large randomized, placebo-controlled, multinational pivotal trials. Still, clinical evidence from routine practice is needed to complement the data from the pivotal trials. Methods OPTIPARK (NCT02847442) was a prospective, open-label, single-arm trial conducted in Germany and the UK under clinical practice conditions. Patients with Parkinson’s disease and motor fluctuations were treated with opicapone 50 mg for 3 (Germany) or 6 (UK) months in addition to their current levodopa and other antiparkinsonian treatments. The primary endpoint was the Clinician’s Global Impression of Change (CGI-C) after 3 months. Secondary assessments included Patient Global Impressions of Change (PGI-C), the Unified Parkinson’s Disease Rating Scale (UPDRS), Parkinson’s Disease Questionnaire (PDQ-8), and the Non-Motor Symptoms Scale (NMSS). Safety assessments included evaluation of treatment-emergent adverse events (TEAEs) and serious adverse events (SAEs). Results Of the 506 patients enrolled, 495 (97.8%) took at least one dose of opicapone. Of these, 393 (79.4%) patients completed 3 months of treatment. Overall, 71.3 and 76.9% of patients experienced any improvement on CGI-C and PGI-C after 3 months, respectively (full analysis set). At 6 months, for UK subgroup only (n = 95), 85.3% of patients were judged by investigators as improved since commencing treatment. UPDRS scores at 3 months showed statistically significant improvements in activities of daily living during OFF (mean ± SD change from baseline: − 3.0 ± 4.6, p < 0.0001) and motor scores during ON (− 4.6 ± 8.1, p < 0.0001). The mean ± SD improvements of − 3.4 ± 12.8 points for PDQ-8 and -6.8 ± 19.7 points for NMSS were statistically significant versus baseline (both p < 0.0001). Most of TEAEs (94.8% of events) were of mild or moderate intensity. TEAEs considered to be at least possibly related to opicapone were reported for 45.1% of patients, with dyskinesia (11.5%) and dry mouth (6.5%) being the most frequently reported. Serious TEAEs considered at least possibly related to opicapone were reported for 1.4% of patients. Conclusions Opicapone 50 mg was effective and generally well-tolerated in PD patients with motor fluctuations treated in clinical practice. Trial registration Registered in July 2016 at clinicaltrials.gov (NCT02847442)

Goal Orientations and Activation of Approach Versus Avoidance Motivation While Awaiting an Achievement Situation in the Laboratory

While some students try to give their best in an achievement situation, others show disengagement and just want to get the situation over and done with. The present study investigates the role of students’ tendencies for approach or avoidance motivation while anticipating tasks and the corresponding activation of the approach/avoidance motivational system as indicated by transient changes of EEG alpha asymmetry. Overall, 62 students (50 female; age: M = 23.8, SD = 3.5) completed a goal orientation questionnaire (learning goals, performance-approach, performance-avoidance, and work avoidance). They joined a laboratory experiment where EEG was recorded during resting condition as well as when students were anticipating tasks. Standard multiple regression analysis showed that higher values on performance-avoidance were related to a higher activation of the approach system whereas higher values on work avoidance were related to a higher activation of the avoidance system. Results question present assumptions about avoidance related goal orientations

EurOgels : A ferromagnetic semiconductor with a porous structure prepared via the assembly of hybrid nanorods

EuO is unique, because it belongs to the few solids combining semiconducting properties (Egap = 1.1 eV) with native ferromagnetism. For future applications of EuO, e.g. as spin-filters or for sensors, one has to learn how defined nanostructures can be prepared. Unlike other ceramic oxides, there are no established soft-chemistry routes (e.g. sol-gel) towards EuO nanomaterials e.g. porous materials. This is due to the labile nature of the oxidation state Eu(+ii). We present a particle-based method leading to a EuO aerogel. Instead of making the target material directly, we use nanoparticles of an organic-inorganic hybrid phase (Eu2O3-benzoate) and assemble those into an aerogel, followed by the transformation into phase-pure EuO. It is shown that organic aldehydes act as capping agents for controlling the morphogenesis of the hybrid particles. Depending on the steric demand of the aldehyde, one obtains plate-like particles or nanorods with increasing aspect ratio. The particles form a gel, when the aspect ratio is increased to >20. After supercritical drying, one receives a nanorod-based aerogel. Treatment of the latter with Eu-vapor leads to reduction of the Eu2O3 domains to EuO while retaining the aerogel structure. Proof of ferromagnetism in the resulting EuO aerogel was delivered by SQUID measurements.publishe

Mathematics Anxiety and Statistics Anxiety. Shared but Also Unshared Components and Antagonistic Contributions to Performance in Statistics

In many social science majors, e.g., psychology, students report high levels of statistics anxiety. However, these majors are often chosen by students who are less prone to mathematics and who might have experienced difficulties and unpleasant feelings in their mathematics courses at school. The present study investigates whether statistics anxiety is a genuine form of anxiety that impairs students' achievements or whether learners mainly transfer previous experiences in mathematics and their anxiety in mathematics to statistics. The relationship between mathematics anxiety and statistics anxiety, their relationship to learning behaviors and to performance in a statistics examination were investigated in a sample of 225 undergraduate psychology students (164 women, 61 men). Data were recorded at three points in time: At the beginning of term students' mathematics anxiety, general proneness to anxiety, school grades, and demographic data were assessed; 2 weeks before the end of term, they completed questionnaires on statistics anxiety and their learning behaviors. At the end of term, examination scores were recorded. Mathematics anxiety and statistics anxiety correlated highly but the comparison of different structural equation models showed that they had genuine and even antagonistic contributions to learning behaviors and performance in the examination. Surprisingly, mathematics anxiety was positively related to performance. It might be that students realized over the course of their first term that knowledge and skills in higher secondary education mathematics are not sufficient to be successful in statistics. Part of mathematics anxiety may then have strengthened positive extrinsic effort motivation by the intention to avoid failure and may have led to higher effort for the exam preparation. However, via statistics anxiety mathematics anxiety also had a negative contribution to performance. Statistics anxiety led to higher procrastination in the structural equation model and, therefore, contributed indirectly and negatively to performance. Furthermore, it had a direct negative impact on performance (probably via increased tension and worry in the exam). The results of the study speak for shared but also unique components of statistics anxiety and mathematics anxiety. They are also important for instruction and give recommendations to learners as well as to instructors.(VLID)309251