Synthesis and Properties of Dipyridylcyclopentenes

A short and general route to the substituted dipyridylcyclopentenes was explored and several new compounds belonging to this new group of diarylethenes were synthesized. The study of their photochromic and thermochromic properties shows that the rate of the thermal ring opening is strongly dependent on the polarity of the solvent.

Sensitivity of desert dust emissions to model horizontal grid spacing during the Bodélé Dust Experiment 2005

The impact of model horizontal grid spacing on meteorology and dust emissions in the Bodélé depression was investigated during the well-documented period of the Bodélé Dust Experiment 2005 (BoDEx 2005). Five horizontal grid spacing ranging from 100 km to 5 km were tested. The main conclusion of these sensitivity tests is that the meteorology of the Bodélé depression is quite insensitive to model horizontal grid spacing below 50 km in agreement with Todd et al.'s (2008b) results. Below 50 km, dust emissions also appear relatively insensitive to model mesh size, the influence of model horizontal grid spacing on dust emissions tending towards an asymptotic behavior as model mesh size is reduced

Plectin-controlled keratin cytoarchitecture affects MAP kinases involved in cellular stress response and migration

Plectin is a major intermediate filament (IF)–based cytolinker protein that stabilizes cells and tissues mechanically, regulates actin filament dynamics, and serves as a scaffolding platform for signaling molecules. In this study, we show that plectin deficiency is a cause of aberrant keratin cytoskeleton organization caused by a lack of orthogonal IF cross-linking. Keratin networks in plectin-deficient cells were more susceptible to osmotic shock–induced retraction from peripheral areas, and their okadaic acid–induced disruption (paralleled by stress-activated MAP kinase p38 activation) proceeded faster. Basal activities of the MAP kinase Erk1/2 and of the membrane-associated upstream protein kinases c-Src and PKCδ were significantly elevated, and increased migration rates, as assessed by in vitro wound-closure assays and time-lapse microscopy, were observed. Forced expression of RACK1, which is the plectin-binding receptor protein for activated PKCδ, in wild-type keratinocytes elevated their migration potential close to that of plectin-null cells. These data establish a link between cytolinker-controlled cytoarchitecture/scaffolding functions of keratin IFs and specific MAP kinase cascades mediating distinct cellular responses

Order and phase nucleation in nonequilibrium nanocomposite Fe-Pt thin films with perpendicular magnetic anisotropy

We report on the time evolution of mass transport upon annealing nonequilibrium Fe-Pt nanocomposite films, leading to nucleation of L1(0) chemically ordered phase. The nonequilibrium nanocomposite films were fabricated by applying Fe(+) ion implantation to epitaxial Pt films grown on (001) MgO substrates, yielding Fe nanoclusters embedded in a Pt matrix at a tailored penetration depth. Time-resolved x-ray diffraction studies were carried out using synchrotron radiation, allowing determination of the activation energy for nucleation of the FePt L1(0) phase within the segregated nanoclusters during annealing. The growth of the segregated L1(0) ordered phase was modeled using ideal grain-size law and found to be dominated by strain-driven surface nucleation. The activation energies were found to correlate with the nanocluster size. Magnetic characterization of selected annealed samples indicates perpendicular magnetic anisotropy with high coercive field coincident with high value of the chemical order parameter of the ordered phase within the magnetic nanoclusters

Real-time weather forecasting in the Western Mediterranean Basin: An application of the RAMS model

A regional forecasting system based on the Regional Atmospheric Modeling System (RAMS) is being run at the CEAM Foundation. The model is started twice daily with a forecast range of 72 h. For the period June 2007 to August 2010 the verification of the model has been done using a series of automatic meteorological stations from the CEAM network and located within the Valencia Region (Western Mediterranean Basin). Air temperature, relative humidity and wind speed and direction of the output of the model have been compared with observations. For these variables, an operational verification has been performed by computing different statistical scores for 18 weather stations. This verification process has been carried out for each season of the year separately. As a result, it has been revealed that the model presents significant differences in the forecast of the meteorological variables analysed throughout the year. Moreover, due to the physical complexity of the area of study, the model presents different degree of accuracy between coastal and inland stations. Precipitation has also been verified by means of yes/no contingency tables as well as scatter plots. These tables have been built using 4 specific thresholds that have permitted to compute some categorical statistics. From the results found, it is shown that the precipitation forecast in the area of study is in general over-predicted, but with marked differences between the seasons of the year. Finally, dividing the available data by season of the year, has permitted us to analyze differences in the observed patterns for the magnitudes mentioned above. These results have been used to better understand the behavior of the RAMS model within the Valencia Region

Raman scattering and FT-IR spectroscopic studies on dithienylethene switches—towards non-destructive optical readout

The non-destructive readout of photochromic memory materials based on the dithienylethene unit both by IR spectroscopy and Raman scattering is explored. A representative series of C5-substituted thienyl hexahydro- and hexafluoro-cyclopentene based photochromes was investigated to explore the effect and potential usefulness of substitution for the development of multicomponent memory materials. The effect of the deposition method on the photochemistry of solid materials containing photochromic dithienylcyclopentene switches was also explored. Photoconversion in the solid state to the closed form was found to be low when starting from the open form, but, in contrast, ring opening to the open state from the closed form was found to be complete. The effect was found to be due to inner filter rather than conformational phenomena. Characteristic vibrational bands for the central dithienyl core are assigned and a comparison made of the vibrational spectroscopic properties of the perhydro- and perfluoro switches. The data enable the determination of the photoconversion achievable in the solid state as well as some assessment of the influence of the deposition method on the photoconversion. The potential of Raman spectroscopy as a method of achieving non-destructive optical readout is demonstrated through the large differences in absolute Raman scattering intensity between the open and closed states, when monitored at wavelengths which do not result in photochemical ring opening.

High-Throughput Simulations Reveal Membrane-Mediated Effects of Alcohols on MscL Gating

The mechanosensitive channels of large conductance (MscL) are bacterial membrane proteins that serve as last resort emergency release valves in case of severe osmotic downshock. Sensing bilayer tension, MscL channels are sensitive to changes in the bilayer environment and are, therefore, an ideal test case for exploring membrane protein coupling. Here, we use high-throughput coarse-grained molecular dynamics simulations to characterize MscL gating kinetics in different bilayer environments under the influence of alcohols. We performed over five hundred simulations to obtain sufficient statistics to reveal the subtle effects of changes in the membrane environment on MscL gating. MscL opening times were found to increase with the addition of the straight-chain alcohols ethanol, octanol, and to some extent dodecanol but not with hexadecanol. Increasing concentration of octanol increased the impeding effect, but only up to 10–20 mol %. Our in silico predictions were experimentally confirmed using reconstituted MscL in a liposomal fluorescent efflux assay. Our combined data reveal that the effect of alcohols on MscL gating arises not through specific binding sites but through a combination of the alcohol-induced changes to a number of bilayer properties and their alteration of the MscL–bilayer interface. Our work provides a key example of how extensive molecular simulations can be used to predict the functional modification of membrane proteins by subtle changes in their bilayer environment

Ultrafast terahertz-field-driven ionic response in ferroelectric BaTiO3

The dynamical processes associated with electric field manipulation of the polarization in a ferroelectric remain largely unknown but fundamentally determine the speed and functionality of ferroelectric materials and devices. Here we apply subpicosecond duration, single-cycle terahertz pulses as an ultrafast electric field bias to prototypical BaTiO[subscript 3] ferroelectric thin films with the atomic-scale response probed by femtosecond x-ray-scattering techniques. We show that electric fields applied perpendicular to the ferroelectric polarization drive large-amplitude displacements of the titanium atoms along the ferroelectric polarization axis, comparable to that of the built-in displacements associated with the intrinsic polarization and incoherent across unit cells. This effect is associated with a dynamic rotation of the ferroelectric polarization switching on and then off on picosecond time scales. These transient polarization modulations are followed by long-lived vibrational heating effects driven by resonant excitation of the ferroelectric soft mode, as reflected in changes in the c-axis tetragonality. The ultrafast structural characterization described here enables a direct comparison with first-principles-based molecular-dynamics simulations, with good agreement obtained

Substitution of Met-38 to Ile in γ-synuclein found in two patients with amyotrophic lateral sclerosis induces aggregation into amyloid

α-, β-, and γ-Synuclein are intrinsically disordered proteins implicated in physiological processes in the nervous system of vertebrates. α-synuclein (αSyn) is the amyloidogenic protein associated with Parkinson’s disease and certain other neurodegenerative disorders. Intensive research has focused on the mechanisms that cause αSyn to form amyloid structures, identifying its NAC region as being necessary and sufficient for amyloid assembly. Recent work has shown that a 7-residue sequence (P1) is necessary for αSyn amyloid formation. Although γ-synuclein (γSyn) is 55% identical in sequence to αSyn and its pathological deposits are also observed in association with neurodegenerative conditions, γSyn is resilient to amyloid formation in vitro. Here, we report a rare single nucleotide polymorphism (SNP) in the SNCG gene encoding γSyn, found in two patients with amyotrophic lateral sclerosis (ALS). The SNP results in the substitution of Met38 with Ile in the P1 region of the protein. These individuals also had a second, common and nonpathological, SNP in SNCG resulting in the substitution of Glu110 with Val. In vitro studies demonstrate that the Ile38 variant accelerates amyloid fibril assembly. Contrastingly, Val110 retards fibril assembly and mitigates the effect of Ile38. Substitution of residue 38 with Leu had little effect, while Val retards, and Ala increases the rate of amyloid formation. Ile38 γSyn also results in the formation of γSyn-containing inclusions in cells. The results show how a single point substitution can enhance amyloid formation of γSyn and highlight the P1 region in driving amyloid formation in another synuclein family member