Tunable Molecular Electrodes for Bistable Polarization Screening

The polar discontinuity at any ferroelectric surface creates a depolarizing field that must be screened for the polarization to be stable. In capacitors, screening is done by the electrodes, while in bare ferroelectric surfaces it is typically accomplished by atmospheric adsorbates. Although chemisorbed species can have even better screening efficiency than conventional electrodes, they are subject to unpredictable environmental fluctuations and, moreover, dominant charged species favor one polarity over the opposite. This paper proposes a new screening concept, namely surface functionalization with resonance-hybrid molecules, which combines the predictability and bipolarity of conventional electrodes with the screening efficiency of adsorbates. Thin films of barium titanate (BaTiO₃) coated with resonant para-aminobenzoic acid (pABA) display increased coercivity for both signs of ferroelectric polarization irrespective of the molecular layer thickness, thanks to the ability of these molecules to swap between different electronic configurations and adapt their surface charge density to the screening needs of the ferroelectric underneath. Because electron delocalization is only in the vertical direction, unlike conventional metals, chemical electrodes allow writing localized domains of different polarity underneath the same electrode. In addition, hybrid capacitors composed of graphene/pABA/ferroelectric have been made with enhanced coercivity compared to pure graphene-electode capacitors.     

Structural and optical properties of tellurite thin film glasses deposited by pulsed laser deposition

Tellurite (TeO₂-TiO₂-Nb₂O₅) thin film glasses have been produced by pulsed laser deposition at room temperature at laser energy densities in the range of 0.8-1.5 J/cm² and oxygen pressures in the range of 3-11 Pa. The oxygen concentration in the films increases with laser energy density to reach values very close to that of the bulk glass at 1.5 J/cm², while films prepared at 1.5 J/cm² and pressures above 5 Pa show oxygen concentration in excess of 10% comparing to the glass. X-ray photoelectron spectroscopy shows the presence of elementary Te in films deposited at O₂ pressures ≤ 5 Pa that is not detected at higher pressures, while analysis of Raman spectra of the samples suggests a progressive substitution of TeO₃ trigonal pyramids by TeO₄ trigonal bipyramids in the films when increasing their oxygen content. Spectroscopic ellipsometry analysis combined with Cauchy and effective medium modeling demonstrates the influence of these compositional and structural modifications on the optical response of the films. Since the oxygen content determines their optical response through the structural modifications induced in the films, those can be effectively controlled by tuning the deposition conditions, and films having large n (2.08) and reduced k (< 10^− 4) at 1.5 μm have been produced using the optimum deposition conditions.     

An Unprecedented Stimuli‐Controlled Single‐Crystal Reversible Phase Transition of a Metal–Organic Framework and Its Application to a Novel Method of Guest Encapsulation

The flexibility and unexpected dynamic behavior of a third‐generation metal–organic framework are described for the first time. The synthetic strategy is based on the flexibility and spherical shape of dipyridyl‐based carborane linkers that act as pillars between rigid Co/BTB (BTB: 1,3,5‐benzenetricarboxylate) layers, providing a 3D porous structure ( 1 ). A phase transition of the solid can be induced to generate a new, nonporous 2D structure ( 2 ) without any loss of the carborane linkers. The structural transformation is visualized by snapshots of the multistep single‐crystal‐to‐single‐crystal transformation by single‐crystal and powder X‐ray diffraction. Poor hydrogen bond acceptors such as MeOH, CHCl₃ or supercritical CO₂ induce such a 3D to 2D transformation. Remarkably, the transformation is reversible and the 2D phase 2 is further converted back into 1 by heating in dimethylformamide. The energy requirements involved in such processes are investigated using periodic density functional theory calculations. As a proof of concept for potential applications, encapsulation of C₆₀ is achieved by trapping this molecule during the reversible 2D to 3D phase transition, whereas no adsorption is observed by straight solvent diffusion into the pores of the 3D phase.     

Effect of soil parameters on radon entry into a building by means of the transrad numerical model

High indoor radon concentration means an increased risk of developing lung cancer. When high radon levels are present in a dwelling, the major source is normally the soil. Therefore, it is useful to know the radon concentration field in the soil underneath a building. A steady-state two-dimensional radon transport model has been used to calculate the effect of a reference building on the soil radon concentration, and the influence of soil parameters on radon entry through a single crack in the basement. Both advective and diffusive flows are considered. Away from the building, the well-known undisturbed soil radon concentration profile has been obtained, while under the house the radon level is increased. A variability analysis around the reference site has shown that the most relevant soil parameters on the radon flux at the top of the crack are, in this case, effective diffusion coefficient, soil gas-permeability and deep soil radon concentration.     

Surface-enhanced micro-Raman detection and characterization of calix[4]arene-polycyclic aromatic hydrocarbon host-guest complexes

Surface-enhanced micro-Raman spectroscopy (micro-SERS) was used to detect traces of the hazardous pollutant polycyclic aromatic hydrocarbons (PAHs) pyrene and benzo[c]phenanthrene deposited onto a calix[4]arene-functionalized Ag colloidal surface. High spectral reproducibility and very low molecular detection limits (10(-8) M) were obtained by using 25,27-carboethoxy-26,28-hidroxy-p-tert-butylcalix[4]arene as host molecule. Films of immobilized aggregated Ag nanoparticles, obtained by chemical reduction with hydroxylamine, were prepared by direct adhesion on a glass surface. The influence of the aggregation degree of the initial Ag nanoparticles on the micro-SERS detection effectiveness was checked. Different relative concentrations of the host (calixarene receptor) and the guest (PAHs) were attempted in order to optimize detection of the pollutant. The obtained results indicated that the detection limit is much lower in the case of benzo[c]phenanthrene than in pyrene when exciting with the 785 nm line of a diode laser. A detailed interpretation of the Raman spectra was accomplished in order to obtain more information about the interaction mechanism of the host-guest complex, which could be useful in the future for the design of powerful detection systems.     

Comparative effects of the chelators sodium 4,5-dihydroxybenzene-1,3-disulfonate (Tiron) and diethylenetriaminepentaacetic acid (DTPA) on acute uranium nephrotoxicity in rats

The effect of transient, global cerebral ischemia on the distribution of endothelin (ET) in blood-brain barrier (BBB) in CA1 area of hippocampus long-time after ischemia was estimated using post-embedding immunogold technique. ET-like immunoreactivity as a gold particles was localized in all compartments of the blood-brain barrier e.g. in endothelial cells, in pericytes, in periendothelial space including basement membrane, and in astroglial processes. In control animal the density of labelling in all elements of BBB in CA1 area of hippocampus was moderate. ET-like immunoreactivity (ET-like IR) was estimated 1 week-12 months after ischemia. Intense ET-like IR in all elements of BBB was noted 2 and 6 months after ischemia. A potential pathophysiological role of endothelin in cerebral vasospasm in long-time after ischemia is well documented.     

Rapid selection in modified BHK-21 cells of a foot-and-mouth disease virus variant showing alterations in cell tropism

With persistent foot-and-mouth disease virus (FMDV) in BHK-21 cells, there is coevolution of the cells and the resident virus; the virulence of the virus for the parental BHK-21 cells is gradually increased, and the cells become partially resistant to FMDV. Here we report that variants of FMDV C3Arg/85 were selected in a single infection of partially resistant BHK-21 cells (termed BHK-Rb cells). Indirect immunofluorescence showed that the BHK-Rb cell population was heterogeneous with regard to susceptibility to C3Arg/85 infection. Infection of BHK-Rb cells with C3Arg/85 resulted in an early phase of partial cytopathology which was followed at 6 to 10 days postinfection by the shedding of mutant FMDVs, termed C3-Rb. The selected C3-Rb variants showed increased virulence for BHK-21 cells, were able to overcome the resistance of modified BHK-21 cells to infection, and had acquired the ability to bind heparin and to infect wild-type Chinese hamster ovary (CHO) cells. A comparison of the genomic sequences of the parental and modified viruses revealed only two amino acid differences, located at the surface of the particle, at the fivefold axis of the viral capsid (Asp-9-->Ala in VP3 and either Gly-110-->Arg or His-108-->Arg in VP1). The same phenotypic and genotypic modifications occurred in a highly reproducible manner; they were seen in a number of independent infections of BHK-Rb cells with viral preparation C3Arg/85 or with clones derived from it. Neither amino acid substitutions in other structural or nonstructural proteins nor nucleotide substitutions in regulatory regions were found. These results prove that infection of partially permissive cells can promote the rapid selection of virus variants that show alterations in cell tropism and are highly virulent for the same cells.     

Group B streptococcal meningitis in adults: report of twelve cases and review

Group B streptococcus (GBS) is the leading etiologic agent of bacterial meningitis and sepsis during the neonatal period, but it is an infrequent cause of meningitis in adults. We report 12 episodes of group B streptococcal meningitis in adults and review 52 cases reported in the literature. A total of 24 men and 40 women were included in the study; the mean age (+/- SD) was 49.2 +/- 20.5 years (range, 17-89 years). All the patients had cerebrospinal fluid cultures positive for GBS. Eighty-six percent of the patients had comorbid conditions, 50% had a distant focus of infection, and blood cultures yielded GBS for 78.7%. The overall case-fatality rate was 34.4% (22 patients). Factors associated with a poor outcome were advanced mean age (+/- SD) (61.5 +/- 17.4 years vs. 42.8 +/- 19.2 years; P = .0003) and the presence of complications on admission (P = .0001). Seven percent of survivors had neurological sequelae. Group B streptococcal meningitis in adults has become increasingly frequent in recent years; it tends to occur in patients with severe underlying conditions and is associated with a high case-fatality rate. Factors associated with a poor prognosis are advanced age and the occurrence of neurological and extraneurological complications.     

Large eddy simulation of forced ignition of an annular bluff-body burner

The optimization of the ignition process is a crucial issue in the design of many combustion systems. Large eddy simulation (LES) of a conical shaped bluff-body turbulent nonpremixed burner has been performed to study the impact of spark location on ignition success. This burner was experimentally investigated by Ahmed et al. [Combust. Flame 151 (2007) 366–385]. The present work focuses on the case without swirl, for which detailed measurements are available. First, cold-flow measurements of velocities and mixture fractions are compared with their LES counterparts, to assess the prediction capabilities of simulations in terms of flow and turbulent mixing. Time histories of velocities and mixture fractions are recorded at selected spots, to probe the resolved probability density function (pdf) of flow variables, in an attempt to reproduce, from the knowledge of LES-resolved instantaneous flow conditions, the experimentally observed reasons for success or failure of spark ignition. A flammability map is also constructed from the resolved mixture fraction pdf and compared with its experimental counterpart. LES of forced ignition is then performed using flamelet fully detailed tabulated chemistry combined with presumed pdfs. Various scenarios of flame kernel development are analyzed and correlated with typical flow conditions observed in this burner. The correlations between, velocities and mixture fraction values at the sparking time and the success or failure of ignition, are then further discussed and analyzed.