2017, Szwed, Małgorzata, Pin´skwar, Iwona, Kundzewicz, Zbigniew W., Graczyk, Dariusz, Mezghani, Abdelkader

The present paper examines variability of characteristics of snow cover (snow cover depth, number of days with snow cover and dates of beginning and end of snow cover) in Poland. The study makes use of a set of 43 long time series of observation records from the stations in Poland, from 1952 to 2013. To describe temporal changes in snow cover characteristics, the intervals of 1952–1990 and of 1991–2013 are compared and trends in analysed data are sought (e.g., using the Mann–Kendall test). Observed behaviour of time series of snow-related variables is complex and not easy to interpret, for instance because of the location of the research area in the zone of transitional moderate climate, where strong variability of climate events is one of the main attributes. A statistical link between the North Atlantic Oscillation (NAO) index and the snow cover depth, as well as the number of snow cover days is found.

2017, Nagendra, Baku, Rosely, C. V. Sijla, Leuteritz, Andreas, Reuter, Uta, Gowd, E. Bhoje

Sonication-assisted delamination of layered double hydroxides (LDHs) resulted in smaller-sized LDH nanoparticles (∼50-200 nm). Such delaminated Co-Al LDH, Zn-Al LDH, and Co-Zn-Al LDH solutions were used for the preparation of highly dispersed isotactic polypropylene (iPP) nanocomposites. Transmission electron microscopy and wide-angle X-ray diffraction results revealed that the LDH nanoparticles were well dispersed within the iPP matrix. The intention of this study is to understand the influence of the intralayer metal composition of LDH on the various properties of iPP/LDH nanocomposites. The sonicated LDH nanoparticles showed a significant increase in the crystallization rate of iPP; however, not much difference in the crystallization rate of iPP was observed in the presence of different types of LDH. The dynamic mechanical analysis results indicated that the storage modulus of iPP was increased significantly with the addition of LDH. The incorporation of different types of LDH showed no influence on the storage modulus of iPP. But considerable differences were observed in the flame retardancy and thermal stability of iPP with the type of LDH used for the preparation of nanocomposites. The thermal stability (50% weight loss temperature (T0.5)) of the iPP nanocomposite containing three-metal LDH (Co-Zn-Al LDH) is superior to that of the nanocomposites made of two-metal LDH (Co-Al LDH and Zn-Al LDH). Preliminary studies on the flame-retardant properties of iPP/LDH nanocomposites using microscale combustion calorimetry showed that the peak heat release rate was reduced by 39% in the iPP/Co-Zn-Al LDH nanocomposite containing 6 wt % LDH, which is higher than that of the two-metal LDH containing nanocomposites, iPP/Co-Al LDH (24%) and iPP/Zn-Al LDH (31%). These results demonstrated that the nanocomposites prepared using three-metal LDH showed better thermal and flame-retardant properties compared to the nanocomposites prepared using two-metal LDH. This difference might be due to the better char formation capability of three-metal LDH compared to that of two-metal LDH.

2017, Morimoto, Daichi, Walinda, Erik, Iwakawa, Naoto, Nishizawa, Mayu, Kawata, Yasushi, Yamamoto, Akihiko, Shirakawa, Masahiro, Scheler, Ulrich, Sugase, Kenji

Shear stress can induce structural deformation of proteins, which might result in aggregate formation. Rheo-NMR spectroscopy has the potential to monitor structural changes in proteins under shear stress at the atomic level; however, existing Rheo-NMR methodologies have insufficient sensitivity to probe protein structure and dynamics. Here we present a simple and versatile approach to Rheo-NMR, which maximizes sensitivity by using a spectrometer equipped with a cryogenic probe. As a result, the sensitivity of the instrument ranks highest among the Rheo-NMR spectrometers reported so far. We demonstrate that the newly developed Rheo-NMR instrument can acquire high-quality relaxation data for a protein under shear stress and can trace structural changes in a protein during fibril formation in real time. The described approach will facilitate rheological studies on protein structural deformation, thereby aiding a physical understanding of shear-induced amyloid fibril formation.

2017, Ruser, Reiner, Fuß, Roland, Andres, Monique, Hegewald, Hannes, Kesenheimer, Katharina, Köbke, Sarah, Räbiger, Thomas, Quinones, Teresa Suarez, Augustin, Jürgen, Christen, Olaf, Dittert, Klaus, Kage, Henning, Lewandowski, Iris, Prochnow, Annette, Stichnothe, Heinz, Flessa, Heinz

Winter oilseed rape (Brassica napus L., WOSR) is the major oil crop cultivated in Europe. Rapeseed oil is predominantly used for production of biodiesel. The framework of the European Renewable Energy Directive requires that use of biofuels achieves GHG savings of at least 50% compared to use of fossil fuel starting in 2018. However, N2O field emissions are estimated using emission factors that are not specific for the crop and associated with strong uncertainty. N2O field emissions are controlled by N fertilization and dominate the GHG balance of WOSR cropping due to the high global warming potential of N2O. Thus, field experiments were conducted to increase the data basis and subsequently derive a new WOSR-specific emission factor. N2O emissions and crop yields were monitored for three years over a range of N fertilization intensities at five study sites representative of German WOSR production. N2O fluxes exhibited the typical high spatial and temporal variability in dependence on soil texture, weather and nitrogen availability. The annual N2O emissions ranged between 0.24 kg and 5.48 kg N2O-N ha−1 a−1. N fertilization increased N2O emissions, particularly with the highest N treatment (240 kg N ha−1). Oil yield increased up to a fertilizer amount of 120 kg N ha−1, higher N-doses increased grain yield but decreased oil concentrations in the seeds. Consequently oil yield remained constant at higher N fertilization. Since, yield-related emission also increased exponentially with N surpluses, there is potential for reduction of the N fertilizer rate, which offers perspectives for the mitigation of GHG emissions. Our measurements double the published data basis of annual N2O flux measurements in WOSR. Based on this extended dataset we modeled the relationship between N2O emissions and fertilizer N input using an exponential model. The corresponding new N2O emission factor was 0.6% of applied fertilizer N for a common N fertilizer amount under best management practice in WOSR production (200 kg N ha−1 a−1). This factor is substantially lower than the linear IPCC Tier 1 factor (EF1) of 1.0% and other models that have been proposed. © 2017

2017, Piniewski, Mikołaj, Meresa, Hadush Kidane, Romanowicz, Renata, Osuch, Marzena, Szczes´niak, Mateusz, Kardel, Ignacy, Okruszko, Tomasz, Mezghani, Abdelkader, Kundzewicz, Zbigniew W.

River flow projections for two future time horizons and RCP 8.5 scenario, generated by two projects (CHASE-PL and CHIHE) in the Polish-Norwegian Research Programme, were compared. The projects employed different hydrological models over different spatial domains. The semi-distributed, process-based, SWAT model was used in the CHASE-PL project for the entire Vistula and Odra basins area, whilst the lumped, conceptual, HBV model was used in the CHIHE project for eight Polish catchments, for which the comparison study was made. Climate projections in both studies originated from the common EURO-CORDEX dataset, but they were different, e.g. due to different bias correction approaches. Increases in mean annual and seasonal flows were projected in both studies, yet the magnitudes of changes were largely different, in particular for the lowland catchments in the far future. The HBV-based increases were significantly higher in the latter case than the SWAT-based increases in all seasons except winter. Uncertainty in projections is high and creates a problem for practitioners.

2017, Wang, Tao, Li, Peining, Chigrin, Dmitry N., Giles, Alexander J., Bezares, Francisco J., Glembocki, Orest J., Caldwell, Joshua D., Taubner, Thomas

A conventional thermal emitter exhibits a broad emission spectrum with a peak wavelength depending upon the operation temperature. Recently, narrowband thermal emission was realized with periodic gratings or single microstructures of polar crystals supporting distinct optical modes. Here, we exploit the coupling of adjacent phonon-polaritonic nanostructures, demonstrating experimentally that the nanometer-scale gaps can control the thermal emission frequency while retaining emission line widths as narrow as 10 cm-1. This was achieved by using deeply subdiffractional bowtie-shaped silicon carbide nanoantennas. Infrared far-field reflectance spectroscopy, near-field optical nanoimaging, and full-wave electromagnetic simulations were employed to prove that the thermal emission originates from strongly localized surface phonon-polariton resonances of nanoantenna structures. The observed narrow emission line widths and exceptionally small modal volumes provide new opportunities for the user-design of near- and far-field radiation patterns for advancements in infrared spectroscopy, sensing, signaling, communications, coherent thermal emission, and infrared photodetection. © 2017 American Chemical Society.

2017, Bragaglia, Valeria, Mio, Antonio M., Calarco, Raffaella

A high degree of vacancy ordering is obtained by annealing amorphous GeTe-Sb2Te3 (GST) alloys deposited on a crystalline substrate, which acts as a template for the crystallization. Under annealing the material evolves from amorphous to disordered rocksalt, to ordered rocksalt with vacancies arranged into (111) oriented layers, and finally converts into the stable trigonal phase. The role of the interface in respect to the formation of an ordered crystalline phase is studied by comparing the transformation stages of crystalline GST with and without a capping layer. The capping layer offers another crystallization interface, which harms the overall crystalline quality.

2017, Liu, Kai, Ma, Chao, Göstl, Robert, Zhang, Lei, Herrmann, Andreas

ConspectusBiomacromolecules, such as nucleic acids, proteins, and virus particles, are persistent molecular entities with dimensions that exceed the range of their intermolecular forces hence undergoing degradation by thermally induced bond-scission upon heating. Consequently, for this type of molecule, the absence of a liquid phase can be regarded as a general phenomenon. However, certain advantageous properties usually associated with the liquid state of matter, such as processability, flowability, or molecular mobility, are highly sought-after features for biomacromolecules in a solvent-free environment. Here, we provide an overview over the design principles and synthetic pathways to obtain solvent-free liquids of biomacromolecular architectures approaching the topic from our own perspective of research. We will highlight the milestones in synthesis, including a recently developed general surfactant complexation method applicable to a large variety of biomacromolecules as well as other synthetic principles granting access to electrostatically complexed proteins and DNA.These synthetic pathways retain the function and structure of the biomacromolecules even under extreme, nonphysiological conditions at high temperatures in water-free melts challenging the existing paradigm on the role of hydration in structural biology. Under these conditions, the resulting complexes reveal their true potential for previously unthinkable applications. Moreover, these protocols open a pathway toward the assembly of anisotropic architectures, enabling the formation of solvent-free biomacromolecular thermotropic liquid crystals. These ordered biomaterials exhibit vastly different mechanical properties when compared to the individual building blocks. Beyond the preparative aspects, we will shine light on the unique potential applications and technologies resulting from solvent-free biomacromolecular fluids: From charge transport in dehydrated liquids to DNA electrochromism to biocatalysis in the absence of a protein hydration shell. Moreover, solvent-free biological liquids containing viruses can be used as novel storage and process media serving as a formulation technology for the delivery of highly concentrated bioactive compounds. We are confident that this new class of hybrid biomaterials will fuel further studies and applications of biomacromolecules beyond water and other solvents and in a much broader context than just the traditional physiological conditions. © 2017 American Chemical Society.

2017, Riedel, Tomáš, Hageneder, Simone, Surman, František, Pop-Georgievski, Ognen, Noehammer, Christa, Hofner, Manuela, Brynda, Eduard, Rodriguez-Emmenegger, Cesar, Dostálek, Jakub

A biosensor for the detection of hepatitis B antibodies in clinical saliva was developed. Compared to conventional analysis of blood serum, it offers the advantage of noninvasive collection of samples. Detection of biomarkers in saliva imposes two major challenges associated with the low analyte concentration and increased surface fouling. The detection of minute amounts of hepatitis B antibodies was performed by plasmonically amplified fluorescence sandwich immunoassay. To have access to specific detection, we prevented the nonspecific adsorption of biomolecules present in saliva by brushes of poly[(N-(2-hydroxypropyl) methacrylamide)-co-(carboxybetaine methacrylamide)] grafted from the gold sensor surface and post modified with hepatitis B surface antigen. Obtained results were validated against the response measured with ELISA at a certified laboratory using serum from the same patients. © 2017

2017-9-13, Jarvis, Amanda G., Obrecht, Lorenz, Deuss, Peter J., Laan, Wouter, Gibson, Emma K., Wells, Peter P., Kamer, Paul C. J.

Artificial metalloenzymes (ArMs) are hybrid catalysts that offer a unique opportunity to combine the superior performance of natural protein structures with the unnatural reactivity of transition-metal catalytic centers. Therefore, they provide the prospect of highly selective and active catalytic chemical conversions for which natural enzymes are unavailable. Herein, we show how by rationally combining robust site-specific phosphine bioconjugation methods and a lipid-binding protein (SCP-2L), an artificial rhodium hydroformylase was developed that displays remarkable activities and selectivities for the biphasic production of long-chain linear aldehydes under benign aqueous conditions. Overall, this study demonstrates that judiciously chosen protein-binding scaffolds can be adapted to obtain metalloenzymes that provide the reactivity of the introduced metal center combined with specifically intended product selectivity.