Thermodynamic interpretation of the scaling of the dynamics of supercooled liquids

The recently discovered scaling law for the relaxation times, tau=f(T,V^g), where T is temperature and V the specific volume, is derived by a revision of the entropy model of the glass transition dynamics originally proposed by Avramov [I. Avramov, J. Non-Cryst. Solids 262, 258 (2000).]. In this modification the entropy is calculated by an alternative route, while retaining the approximation that the heat capacity is constant with T and P. The resulting expression for the variation of the relaxation time with T and V is shown to accurately fit experimental data for several glass-forming liquids and polymers over an extended range encompassing the dynamic crossover. From this analysis, which is valid for any model in which the relaxation time is a function of the entropy. we find that the scaling exponent g can be identified with the Gruneisen constant.Comment: 24 pages, 7 figure

Characterisation of the pathogenic effects of the in vivo expression of an ALS-linked mutation in D-amino acid oxidase: Phenotype and loss of spinal cord motor neurons

Amyotrophic lateral sclerosis (ALS) is the most common adult-onset neuromuscular disorder characterised by selective loss of motor neurons leading to fatal paralysis. Current therapeutic approaches are limited in their effectiveness. Substantial advances in understanding ALS disease mechanisms has come from the identification of pathogenic mutations in dominantly inherited familial ALS (FALS). We previously reported a coding mutation in D-amino acid oxidase (DAOR199W) associated with FALS. DAO metabolises D-serine, an essential co-agonist at the N-Methyl-D-aspartic acid glutamate receptor subtype (NMDAR). Using primary motor neuron cultures or motor neuron cell lines we demonstrated that expression of DAOR199W, promoted the formation of ubiquitinated protein aggregates, activated autophagy and increased apoptosis. The aim of this study was to characterise the effects of DAOR199W in vivo, using transgenic mice overexpressing DAOR199W. Marked abnormal motor features, e.g. kyphosis, were evident in mice expressing DAOR199W, which were associated with a significant loss (19%) of lumbar spinal cord motor neurons, analysed at 14 months. When separated by gender, this effect was greater in females (26%; p< 0.0132). In addition, we crossed the DAOR199W transgenic mouse line with the SOD1G93A mouse model of ALS to determine whether the effects of SOD1G93A were potentiated in the double transgenic line (DAOR199W/SOD1G93A). Although overall survival was not affected, onset of neurological signs was significantly earlier in female double transgenic animals than their female SOD1G93A littermates (125 days vs 131 days, P = 0.0239). In summary, some significant in vivo effects of DAOR199W on motor neuron function (i.e. kyphosis and loss of motor neurons) were detected which were most marked in females and could contribute to the earlier onset of neurological signs in double transgenic females compared to SOD1G93A littermates, highlighting the importance of recognizing gender effects present in animal models of ALS

The Glass Transition Temperature of Water: A Simulation Study

We report a computer simulation study of the glass transition for water. To mimic the difference between standard and hyperquenched glass, we generate glassy configurations with different cooling rates and calculate the $T$ dependence of the specific heat on heating. The absence of crystallization phenomena allows us, for properly annealed samples, to detect in the specific heat the simultaneous presence of a weak pre-peak (``shadow transition''), and an intense glass transition peak at higher temperature. We discuss the implications for the currently debated value of the glass transition temperature of water. We also compare our simulation results with the Tool-Narayanaswamy-Moynihan phenomenological model.Comment: submitted to Phys. Re

Discovery of two new phases of zirconium tetrakis(8-hydroxyquinolinolate): synthesis, crystal structure and their electron transporting characteristics in organic light emitting diodes (OLEDs)

Two new phases of zirconium tetrakis(8-hydroxyquinolinolate) (Zrq4) have been synthesised and characterised by single crystal X-ray diffraction. Their electrical, electronic, optical and thermal properties have been studied. Their electron transporting characteristics have been investigated in organic light emitting devices where the two phases show remarkable differences in performance. One of the forms (designated a-Zrq4) gives significantly lower operating voltage, higher efficiencies and longer lifetime than the other (designated b-Zrq4) in organic light emitting devices.EPSR

Impact of the Ce 4f4f states in the electronic structure of the intermediate-valence superconductor CeIr3_3

The electronic structure of the $f$-based superconductor $\mathrm{CeIr_3}$ was studied by photoelectron spectroscopy. The energy distribution of the $\mathrm{Ce}~4f$ states were revealed by the $\mathrm{Ce}~3d-4f$ resonant photoelectron spectroscopy. The $\mathrm{Ce}~4f$ states were mostly distributed in the vicinity of the Fermi energy, suggesting the itinerant character of the $\mathrm{Ce}~4f$ states. The contribution of the $\mathrm{Ce}~4f$ states to the density of states (DOS) at the Fermi energy was estimated to be nearly half of that of the $\mathrm{Ir}~5d$ states, implying that the $\mathrm{Ce}~4f$ states have a considerable contribution to the DOS at the Fermi energy. The $\mathrm{Ce}~3d$ core-level and $\mathrm{Ce}~3d$ X-ray absorption spectra were analyzed based on a single-impurity Anderson model. The number of the $\mathrm{Ce}~4f$ states in the ground state was estimated to be $0.8-0.9$, which is much larger than the values obtained in the previous studies (i.e., $0-0.4$).Comment: 9 pages, 4 figures, accepted to Electronic Structur

Immunolocalization of dually phosphorylated MAPKs in dividing root meristem cells of Vicia faba, Pisum sativum, Lupinus luteus and Lycopersicon esculentum

Key message In plants, phosphorylated MAPKs display constitutive nuclear localization; however, not all studied plant species show co-localization of activated MAPKs to mitotic microtubules. Abstract The mitogen-activated protein kinase (MAPK) signaling pathway is involved not only in the cellular response to biotic and abiotic stress but also in the regulation of cell cycle and plant development. The role of MAPKs in the formation of a mitotic spindle has been widely studied and the MAPK signaling pathway was found to be indispensable for the unperturbed course of cell division. Here we show cellular localization of activated MAPKs (dually phosphorylated at their TXY motifs) in both interphase and mitotic root meristem cells of Lupinus luteus, Pisum sativum, Vicia faba (Fabaceae) and Lycopersicon esculentum (Solanaceae). Nuclear localization of activated MAPKs has been found in all species. Colocalization of these kinases to mitotic microtubules was most evident in L. esculentum, while only about 50 % of mitotic cells in the root meristems of P. sativum and V. faba displayed activated MAPKs localized to microtubules during mitosis. Unexpectedly, no evident immunofluorescence signals at spindle microtubules and phragmoplast were noted in L. luteus. Considering immunocytochemical analyses and studies on the impact of FR180204 (an inhibitor of animal ERK1/2) on mitotic cells, we hypothesize that MAPKs may not play prominent role in the regulation of microtubule dynamics in all plant species

Novel lithium Schiff-base cluster complexes as electron injectors: synthesis, crystal structure, thin film characterisation and their performance in OLEDs

This journal is © The Royal Society of Chemistry 2012A set of novel lithium Schiff base cluster compounds has been synthesised and characterised for the first time and tested as electron injectors in OLED devices. Their electrical, electronic, thermal and optical properties have been investigated and compared with the industry standards LiF and lithium quinolinolate (LiQ). Amongst the compounds tested, lithium 2-((o tolylimino)methyl) phenolate was found to enhance the efficiency of OLEDs by 69% compared to LiF and 15% compared to LiQ. The same electron injector was found to extend the lifetimes of OLEDs by six-fold compared to LiF and 4.3- fold compared to LiQ respectively. The crystal structure of the parent compound, lithium 2- ((phenylamino)methyl)phenolate reveals that the compound is tetrameric in contrast to hexameric LiQ. Substituting the methyl group with fluorine causes a remarkable depression of the HOMO and LUMO levels by up to 1.2 eV. Analysis of current density vs. voltage characteristics of single-layer devices for Li–Al/electron injector/Li–Al and Al/electron injector/Al reveals that both sets of devices are operating as electron-only devices indicating that the formation of free lithium is the cause of enhanced electron injection, but either the energetic aluminium atoms (as proposed previously by other workers) or energetic lithium complexes on an aluminium surface (as we have demonstrated in this paper) are all that is required for efficient electron injection

Novel composite organic-inorganic semiconductor sensors for the quantitative detection of target organic vapours

Composites of tin dioxide (an n-type semiconductor) and derivatives of the conducting polymer polypyrrole (a p-type semiconductor) gave reversible changes in electrical resistance at room temperature when exposed to a range of organic vapours. The optimum amount of polymer giving highest sensitivity was found by experiment to be 2.5% by mass for the polypyrrole chloride-tin dioxide composite. Composites containing 2.5% polymer by mass, but differing in polymer derivative, were fabricated and exposed to low concentrations of ethanol, methanol, acetone, methyl acetate and ethyl acetate. All were found to give significant and reversible decreases in electrical resistance. Direct comparison with sensors constructed solely of tin dioxide or polypyrrole at room temperature showed the composites to be more sensitive. The gas sensitivity of the composite materials depended on the type of polymer derivative incorporated and the dopant anion associated with the polymer. The composites were simple to fabricate and gave differing response profiles to a range of organic vapours

Suppression of Cdc27B expression induces plant defence responses

Non-host resistance is the most general form of disease resistance in plants because it is effective against most phytopathogens. The importance of hypersensitive responses (HRs) in non-host resistance of Nicotiana species to the oomycete Phytophthora is clear. INF1 elicitin, an elicitor obtained from the late-blight pathogen Phytophthora infestans, is sufficient to induce a typical HR in Nicotiana species. The molecular mechanisms that underlie the non-host resistance component of plant defence responses have been investigated using differential-display polymerase chain reaction (PCR) in a model HR system between INF1 elicitin and tobacco BY-2 cells. Differential-display PCR has revealed that Cdc27B is down-regulated in tobacco BY- 2 cells after treatment with INF1 elicitin. Cdc27B is one of 13 essential components of the anaphase- promoting complex or cyclosome ( APC/ C)-type E3 ubiquitin ligase complex in yeast. This APC/C-type E3 ubiquitin ligase complex regulates G2-to-M phase transition of the cell cycle by proteolytic degradation. In this study, we investigated the roles of this gene, NbCdc27B, in plant defence responses using virus-induced gene silencing. Suppression of NbCdc27B in Nicotiana benthamiana plants induced defence responses and a gain of resistance to Colletotrichum lagenarium fungus. Elicitin-induced hypersensitive cell death (HCD) was inhibited mildly in plants silenced with tobacco rattle virus:: Cdc27B. Cdc27B could manage the signalling pathways of plant defence responses as a negative regulator without HCD.</p