Cooperativity and Heterogeneity in Plastic Crystals Studied by Nonlinear Dielectric Spectroscopy

The glassy dynamics of plastic-crystalline cyclo-octanol and ortho-carborane, where only the molecular reorientational degrees of freedom freeze without long-range order, is investigated by nonlinear dielectric spectroscopy. Marked differences to canonical glass formers show up: While molecular cooperativity governs the glassy freezing, it leads to a much weaker slowing down of molecular dynamics than in supercooled liquids. Moreover, the observed nonlinear effects cannot be explained with the same heterogeneity scenario recently applied to canonical glass formers. This supports ideas that molecular relaxation in plastic crystals may be intrinsically non-exponential. Finally, no nonlinear effects were detected for the secondary processes in cyclo-octanol.Comment: Final version as accepted for publication in Phys. Rev. Lett. 6 pages, 5 figures (including 1 page and figure in Supplemental Material

Nonlinear dielectric response of Debye, alpha, and beta relaxation in 1-propanol

We present nonlinear dielectric measurements of glass-forming 1-propanol, a prototypical example for the monohydroxy alcohols that are known to exhibit unusual relaxation dynamics, namely an additional Debye relaxation, slower than the structural alpha relaxation. Applying high ac fields of 468 kV/cm allows for a detailed investigation of the nonlinear properties of all three relaxation processes occurring in 1-propanol, namely the Debye, alpha, and beta relaxation. Both the field-induced variations of dielectric constant and loss are reported. Polarization saturation and the absorption of field energy govern the findings in the Debye-relaxation regime, well consistent with the suggested cluster-like nature of the relaxing entities. The behavior of the alpha relaxation is in good accord with the expectations for a heterogeneous relaxation scenario. Finally, the Johari-Goldstein beta-relaxation in 1-propanol seems to exhibit no or only weak field dependence, in agreement with recent findings for the excess wing of canonical glass formers.Comment: 8 pages, 4 figure

Conductivity enhancement in plastic-crystalline solid-state electrolytes

Finding new ionic conductors that enable significant advancements in the development of energy-storage devices is a challenging goal of current material science. Aside of material classes as ionic liquids or amorphous ion conductors, the so-called plastic crystals (PCs) have been shown to be good candidates combining high conductivity and favourable mechanical properties. PCs are formed by molecules whose orientational degrees of freedom still fluctuate despite the material exhibits a well-defined crystalline lattice. Here we show that the conductivity of Li+ ions in succinonitrile, the most prominent molecular PC electrolyte, can be enhanced by several decades when replacing part of the molecules in the crystalline lattice by larger ones. Dielectric spectroscopy reveals that this is accompanied by a stronger coupling of ionic and reorientational motions. These findings, which can be understood in terms of an optimised "revolving door" mechanism, open a new path towards the development of better solid-state electrolytes.Comment: 5 pages, 4 figure + 2 pages, 2 figures in Supplemental Informatio

Fifth-order susceptibility unveils growth of thermodynamic amorphous order in glass-formers

Glasses are ubiquitous in daily life and technology. However the microscopic mechanisms generating this state of matter remain subject to debate: Glasses are considered either as merely hyper-viscous liquids or as resulting from a genuine thermodynamic phase transition towards a rigid state. We show that third- and fifth-order susceptibilities provide a definite answer to this longstanding controversy. Performing the corresponding high-precision nonlinear dielectric experiments for supercooled glycerol and propylene carbonate, we find strong support for theories based upon thermodynamic amorphous order. Moreover, when lowering temperature, we find that the growing transient domains are compact - that is their fractal dimension d_f = 3. The glass transition may thus represent a class of critical phenomena different from canonical second-order phase transitions for which d_f < 3.Comment: 9 pages, 3 figure

Development and application of the modelling system J2000-S for the EU-water framework directive

The scientific sound definition of measures to achieve the goals of the EU water framework directive (WFD) acquires spatially distributed analyses of the water and substance dynamics in meso- to macro-scale catchments. For this purpose, modelling tools or systems are needed which are robust and fast enough to be applied on such scales, but which are also able to simulate the impact of changes on single fields or small areas of a specific land use in the catchment. &lt;br&gt;&lt;br&gt; To face these challenges, we combined the fully-distributed hydrological model J2000 with the nitrogen transport routines of the Soil Water Assessment Tool SWAT model, which are normally applied in a semi-distributive approach. With this combination, we could extend the quantitative focus of J2000 with qualitative processes and could overcome the semi-distributed limitation of SWAT. For the implementation and combination of the components, we used the Jena Adaptable Modelling System JAMS (Kralisch and Krause, 2006) which helped tremendously in the relatively rapid and easy development of the new resultant model J2000-S (J2000-Substance). &lt;br&gt;&lt;br&gt; The modelling system was applied in the upper Gera watershed, located in Thuringia, Germany. The catchment has an area of 844 km&lt;sup&gt;2&lt;/sup&gt; and includes three of the typical landscape forms of Thuringia. The application showed, that the new modelling system was able to reproduce the daily hydrological as well as the nitrogen dynamics with a sufficient quality. The paper will describe the results of the new model and compare them with the results obtained with the original semi-distributed application of SWAT

Emerging concepts in pancreatic cancer medicine: targeting the tumor stroma

Pancreatic ductal adenocarcinoma is a stroma-rich and highly challenging cancer to treat. Over recent years, it has become increasingly evident that the complex network of soluble cytokines, growth factors, proteases, and components of the extracellular matrix collaboratively interact within the tumor microenvironment, sustaining and driving cancer cell proliferation, invasion, and early metastasis. More recently, the tumor microenvironment has also been appreciated to mediate therapeutic resistance in pancreatic ductal adenocarcinoma, thus opening numerous avenues for novel therapeutic explorations. Inert and soluble components of the tumor stroma have been targeted in order to break down the extracellular matrix scaffold, relieve vessel compression, and increase drug delivery to hypovascular tumors. Moreover, targeting of antiapoptotic, immunosuppressive, and pro-proliferative effects of the tumor stroma provides novel vantage points of attack. This review focuses on current and future developments in pancreatic cancer medicine, with a particular emphasis on biophysical and biochemical approaches that target the tumor microenvironment

Gearing motion in cogwheel pairs of molecular rotors: weak-coupling limit

Variable-​temp. (VT) crystal structures, VT 1H spin-​lattice relaxation in static crystals, and DFT modeling of the rotational barriers of BCP rotators in cryst. arrays of a rod-​like mol. contg. two 1,​3-​bis(ethynyl)​bicyclo[1.1.1]​pentane (BCP) units demonstrate that a correlated gearing motion occurs in the limit of a weak coupling between two rotors in a pair

Multiscale investigations in a mesoscale catchment ? hydrological modelling in the Gera catchment

International audienceThe application of the hydrological process-oriented model J2000 (J2K) is part of a cooperation project between the Thuringian Environmental Agency (Thüringer Landesanstalt für Umwelt und Geologie ? TLUG) and the Department of Geoinformatics of the Friedrich-Schiller-University Jena focussing on the implementation of the EU water framework directive (WFD). In the first project phase J2K was parametrised and calibrated for a mesoscale catchment to quantify if it can be used as hydrological part of a multi-objective tool-box needed for the implementation of the WFD. The main objectives for that pilot study were: The development and application of a suitable distribution concept which provide the spatial data basis for various tasks and which reflects the specific physiogeographical variability and heterogeneity of river basins adequately. This distribution concept should consider the following constraints: The absolute number of spatial entities, which forms the basis for any distributive modelling should be as small as possible, but the spatial distributed factors, which controls quantitative and qualitative hydrological processes should not be generalised to much. The distribution concept of hydrological response units HRUs (Flügel, 1995) was selected and enhanced by a topological routing scheme (Staudenrausch, 2001) for the simulation of lateral flow processes. J2K should be calibrated for one subbasin of the pilot watershed only. Then the parameter set should be used on the other subbasins (referred as transfer basins) to investigate and quantify the transferability of a calibrated model and potential spatial dependencies of its parameter set. In addition, potential structural problems in the process description should be identified by the transfer to basins which show a different process dominance as the one which was used for calibration does. Model calibration and selection of efficiency criteria for the quantification of the model quality should be based on a comprehensive sensitivity and uncertainty analysis (Bäse, 2005) and multi-response validations with independent data sets (Krause and Flügel, 2005) carried out in advance in the headwater part of the calibration basin. To obtain good results in the transfer basins the calibrated parameter set could be adjusted slightly. This step was considered as necessary because of specific constraints which were not of significant importance in the calibration basin. This readjustment should be carried out on parameters which show a sensitive reaction on the identified differences in the environmental setup. Potential scaling problems of the process description, distribution concept or model structure should be identified by the comparison of the modelling results obtained in a small headwater region of the calibration basin with observed streamflow to find out if the selected efficiency measures show a significant change

Staphylococcus aureus enterotoxin b down-regulates the expression of transforming growth factor-beta (TGF-β) signaling transducers in human glioblastoma

Background: It has been revealed that Staphylococcus aureus enterotoxin B (SEB) may feature anti-cancer and anti-metastatic advantages due to its ability to modify cell immunity processes and signaling pathways. Glioblastoma is one of the most aggressive human cancers; it has a high mortality nature, which makes it an attractive area for the development of novel therapies. Objectives: We examined whether the SEB could exert its growth inhibitory effects on glioblastoma cells partially through the manipulation of a key tumor growth factor termed transforming growth factor-beta (TGF-β). Materials and Methods: A human primary glioblastoma cell line, U87, was treated with different concentrations of SEB. The cell quantity was measured by the MTT assay at different exposure times. For molecular assessments, total ribonucleic acid (RNA) was extracted from either non-treated or SEB-treated cells. Subsequently, the gene expression of TGF-β transducers, smad2/3, at the messenger RNA (mRNA) level, was analyzed via a quantitative real-time polymerase chain reaction (qPCR) using the SYBR Green method. Significant differences between cell viability and gene expression levels were determined (Prism 5.0 software) using a one-way analysis of variance (ANOVA) test. Results: We reported that SEB could effectively down-regulate smad2/3 expression in glioblastoma cells at concentrations as quantity as 1 µg/mL and 2 µg/mL (P < 0.05 and P < 0.01, respectively). The SEB concentrations effective at regulating smad2/3 expression were correlated with those used to inhibit the proliferation of glioblastoma cells. Our results also showed that SEB was able to decrease smad2/3 expression at the mRNA level in a concentration- and time-dependent manner. Conclusions: We suggested that SEB could represent an agent that can significantly decrease smad2/3 expression in glioblastoma cells, leading to moderate TGF-β growth signaling and the reduction of tumor cell proliferation. © 2016, Ahvaz Jundishapur University of Medical Sciences

Effect of interchain coupling on conducting polymer luminescence: excimers in derivatives of poly(phenylene vinylene)

Optical excitation of a chain in a polymer film may result in formation of an excimer, a superposition of on-chain excitons and charge-transfer excitons on the originally excited chain and a neighboring chain. The excimer emission is red-shifted compared to that of an on-chain exciton by an amount depending on the interchain coupling $t_\perp$. Setting up the excimer wavefunction and calculating the red shift, we determine average $t_\perp$ values, referred to a monomer, of 0.52 eV and 0.16 eV for poly(2,5-hexyloxy $p$-phenylene cyanovinylene), CN-PPV, and poly[2-methoxy, 5-(2'-ethyl-hexyloxy)-1, 4 p-phenylene vinylene], MEH-PPV, respectively, and use them to determine the effect of interchain distance on the emission.Comment: 10 pages, RevTeX, 1 PS figure, replaced version of cond-mat/9707095, accepted for publication in Phys. Rev. B, Rapid Communicatio