Mixed-Metal Tungsten Oxide Photoanode Materials Made by Pulsed-Laser in Liquids Synthesis

Globally scalable sunlight-driven devices that convert solar energy into storable fuels will require efficient light absorbers that are made of non-precious elements. Suitable photoanode materials are yet to be discovered. Here we utilised the timesaving nature of pulsed-laser in liquids synthesis and prepared a series of neat and mixed-metal tungsten oxide photoanode materials to investigate the effect of ad-metals on optical and photocurrent generation properties. We obtained sub-μm-sized materials with different colours from W, Al, Ta, or first-row transition metal targets in water or aqueous ammonium metatungstate solutions. We observed metastable polymorphs of WO3 and tungsten oxides with varying degrees of oxygen deficiency. Pulsed-laser in liquids synthesis of Ni in ammonium metatungstate solutions produced hollow spheres (with ≤ 6% Ni with respect to W). Photocurrent generation in strong aqueous acid was highest in mixed-metal tungsten oxide photoanode materials with around 5% of iron or nickel

Main phase transition in lipid bilayers: phase coexistence and line tension in a soft, solvent-free, coarse-grained model

We devise a soft, solvent-free, coarse-grained model for lipid bilayer membranes. The non-bonded interactions take the form of a weighted-density functional which allows us to describe the thermodynamics of self-assembly and packing effects of the coarse-grained beads in terms of a density expansion of the equation of state and the weighting functions that regularize the microscopic bead densities, respectively. Identifying the length and energy scales via the bilayer thickness and the thermal energy scale, kT, the model qualitatively reproduces key characteristics (e.g., bending rigidity, area per lipid molecules, and compressibility) of lipid membranes. We employ this model to study the main phase transition between the liquid and the gel phase of the bilayer membrane. We accurately locate the phase coexistence using free energy calculations and also obtain estimates for the bare and the thermodynamic line tension.Comment: 21 pages, 12 figures. Submitted to J. Chem. Phy

Nanolesions induced by heavy ions in human tissues: experimental and theoretical studies

The biological effects of energetic heavy ions are attracting increasing interest for their applications in cancer therapy and protection against space radiation. The cascade of events leading to cell death or late effects starts from stochastic energy deposition on the nanometer scale and the corresponding lesions in biological molecules, primarily DNA. We have developed experimental techniques to visualize DNA nanolesions induced by heavy ions. Nanolesions appear in cells as “streaks” which can be visualized by using different DNA repair markers. We have studied the kinetics of repair of these “streaks” also with respect to the chromatin conformation. Initial steps in the modeling of the energy deposition patterns at the micrometer and nanometer scale were made with MCHIT and TRAX models, respectively

Herbivorous reptiles and body mass: Effects on food intake, digesta retention, digestibility and gut capacity, and a comparison with mammals

Differences in the allometric scaling between gut capacity (with body mass, BM1.00) and food intake (with BM0.75) should theoretically result in a scaling of digesta retention time with BM0.25 and therefore a higher digestive efficiency in larger herbivores. This concept is an important part of the so-called ‘Jarman-Bell principle’ (JBP) that explains niche differentiation along a body size gradient in terms of digestive physiology. Empirical data in herbivorous mammals, however, do not confirm the scaling of retention time, or of digestive efficiency, with body mass. Here, we test these concepts in herbivorous reptiles, adding data of an experiment that measured food intake, digesta retention, digestibility and gut capacity in 23 tortoises (Testudo graeca, T. hermanni , Geochelone nigra, G. sulcata, Dipsochelys dussumieri) across a large BM range (0.5-180 kg) to a literature data collection. While dry matter gut fill scaled to BM1.07 and dry matter intake to BM0.76, digesta mean retention time (MRT) scaled to BM0.17; the scaling exponent was not significantly different from zero for species > 1 kg. Food intake level was a major determinant of MRT across reptiles and mammals. In contrast to dietary fibre level, BM was not a significant contributor to dry matter digestibility in a General Linear Model. Digestibility coefficients in reptiles depended on diet nutrient composition in a similar way as described in mammals. Although food intake is generally lower and digesta retention longer in reptiles than in mammals, digestive functions scale in a similar way in both clades, indicating universal principles in herbivore digestive physiology. The reasons why the theoretically derived JBP has little empirical support remain to be investigated. Until then, the JBP should not be evoked to explain niche differentiation along a body size axis in terms of digestive physiology

Comparing life expectancy of three deer species between captive and wild populations

Life in zoological gardens provides a number of benefits to captive animals, resulting in an artificial reduction of the “struggle for life” compared to their free-ranging counterparts. These advantages should result in a higher chance of surviving from one year to the next, and thus in longer average life expectancies for captive animals, given that the biological requirements of the species are adequately met. Here, we compare the life expectancy of captive and free-ranging populations of three deer species (reindeer Rangifer tarandus, red deer Cervus elaphus, and roe deer Capreolus capreolus). Whereas captive reindeer and red deer had life expectancies equal to or longer than free-ranging individuals, the life expectancy of captive roe deer was shorter than that of free-ranging animals. These results support the impression that roe deer are difficult to keep in zoos, whereas reindeer and red deer perform well under human care. We suggest that the mean life expectancy of captive populations relative to that of corresponding free-ranging populations is a reliable indicator to evaluate the husbandry success of a species in captivity

Spinodal Decomposition in a Binary Polymer Mixture: Dynamic Self Consistent Field Theory and Monte Carlo Simulations

We investigate how the dynamics of a single chain influences the kinetics of early stage phase separation in a symmetric binary polymer mixture. We consider quenches from the disordered phase into the region of spinodal instability. On a mean field level we approach this problem with two methods: a dynamical extension of the self consistent field theory for Gaussian chains, with the density variables evolving in time, and the method of the external potential dynamics where the effective external fields are propagated in time. Different wave vector dependencies of the kinetic coefficient are taken into account. These early stages of spinodal decomposition are also studied through Monte Carlo simulations employing the bond fluctuation model that maps the chains -- in our case with 64 effective segments -- on a coarse grained lattice. The results obtained through self consistent field calculations and Monte Carlo simulations can be compared because the time, length, and temperature scales are mapped onto each other through the diffusion constant, the chain extension, and the energy of mixing. The quantitative comparison of the relaxation rate of the global structure factor shows that a kinetic coefficient according to the Rouse model gives a much better agreement than a local, i.e. wave vector independent, kinetic factor. Including fluctuations in the self consistent field calculations leads to a shorter time span of spinodal behaviour and a reduction of the relaxation rate for smaller wave vectors and prevents the relaxation rate from becoming negative for larger values of the wave vector. This is also in agreement with the simulation results.Comment: Phys.Rev.E in prin

Generating multi-chain configurations of an inhomogeneous melt from the knowledge of single-chain properties

Mean-field techniques provide a rather accurate description of single-chain conformations in spatially inhomogeneous polymer systems containing interfaces or surfaces. Intermolecular correlations, however, are not described by the mean-field approach and information about the distribution of distance between different molecules is lost. Based on the knowledge of the exact equilibrium single-chain properties in contact with solid substrates, we generate multi-chain configurations that serve as nearly equilibrated starting configurations for molecular dynamics simulations by utilizing the packing algorithm of Auhl and co-workers [J. Chem. Phys. 119, 12718 (2003)] for spatially inhomogeneous systems, i.e., a thin polymer film confined between two solid substrates. The single-chain conformations are packed into the thin film conserving the single-chain properties and simultaneously minimizing local fluctuations of the density. The extent to which enforcing the near-incompressibility of a dense polymer liquid during the packing process is able to re-establish intermolecular correlations is investigated by monitoring intermolecular correlation functions and the structure function of density fluctuations as a function of the distance from the confining solid substrates.Comment: 10 pages, 8 figure

Mechanisms of change in psychotherapy for depression:An empirical update and evaluation of research aimed at identifying psychological mediators

We present a systematic empirical update and critical evaluation of the current status of research aimed at identifying a variety of psychological mediators in various forms of psychotherapy for depression. We summarize study characteristics and results of 35 relevant studies, and discuss the extent to which these studies meet several important requirements for mechanism research. Our review indicates that in spite of increased attention for the topic, advances in theoretical consensus about necessities for mechanism research, and sophistication of study designs, research in this field is still heterogeneous and unsatisfactory in methodological respect. Probably the biggest challenge in the field is demonstrating the causal relation between change in the mediator and change in depressive symptoms. The field would benefit from a further refinement of research methods to identify processes of therapeutic change. Recommendations for future research are discussed. However, even in the most optimal research designs, explaining psychotherapeutic change remains a challenge. Psychotherapy is a multi-dimensional phenomenon that might work through interplay of multiple mechanisms at several levels. As a result, it might be too complex to be explained in relatively simple causal models of psychological change

Superconductivity at 38 K in the iron arsenide (Ba1-xKx)Fe2As2

The ternary iron arsenide BaFe2As2 becomes superconducting by hole doping, which was achieved by partial substitution of the barium site with potassium. We have discovered bulk superconductivity up to Tc = 38 K in (Ba1-xKx)Fe2As2 with x = 0.4. The parent compound BaFe2As2 as well as KFe2As2 both crystallize in the tetragonal ThCr2Si2-type structure, which consists of (FeAs)- iron arsenide layers separated by barium or potassium ions. BaFe2As2 is a poor metal and exhibits a SDW anomaly at 140 K. By substituting Ba2+ for K+ ions we have introduced holes in the (FeAs)- layers, which suppress the SDW anomaly and induce superconductivity. This scenario is very similar to the recently discovered arsenide-oxide superconductors. The Tc of 38 K in (Ba1-xKx)Fe2As2 is the highest observed critical temperature in hole doped iron arsenide superconductors so far. Therefore, we were able to expand this class of superconductors by oxygen-free compounds with the ThCr2Si2-type structure. Our results suggest, that superconductivity in these systems essentially evolves from the (FeAs)- layers and may occur in other related compounds.Comment: 4 pages, 5 figures, submitted to Phys. Rev. Let