Awaking the vacuum with spheroidal shells

It has been shown that well-behaved spacetimes may induce the vacuum fluctuations of some nonminimally coupled free scalar fields to go through a phase of exponential growth. Here, we discuss this mechanism in the context of spheroidal thin shells emphasizing the consequences of deviations from spherical symmetry. © 2013 American Physical Society.

Local electronic structure, optical bandgap and photoluminescence (PL) properties of Ba(Zr0.75Ti0.25)O3 powders

Ba(Zr0.75Ti0.25)O3 (BZT-75/25) powders were synthesized by the polymeric precursor method. Samples were structurally characterized by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) techniques. Their electronic structures were evaluated by first-principle quantum mechanical calculations based on density functional theory at the B3LYP level. Their optical properties were investigated by ultraviolet-visible (UV-Vis) spectroscopy and photoluminescence (PL) measurements at room temperature. XRD patterns and Rietveld refinement data indicate that the samples have a cubic structure. XANES spectra confirm the presence of pyramidal [TiO5] clusters and octahedral [TiO6] clusters in the disordered BZT-75/25 powders. EXAFS spectra indicate distortion of Ti-O and Ti-O-Ti bonds the first and second coordination shells, respectively. UV-Vis absorption spectra confirm the presence of different optical bandgap values and the band structure indicates an indirect bandgap for this material. The density of states demonstrates that intermediate energy levels occur between the valence band (VB) and the conduction band (CB). These electronic levels are due to the predominance of 4d orbitals of Zr atoms in relation to 3d orbitals of Ti atoms in the CB, while the VB is dominated by 2p orbitals related to O atoms. There was good correlation between the experimental and theoretical optical bandgap values. When excited at 482 nm at room temperature, BZT-75/25 powder treated at 500 C for 2 h exhibited broad and intense PL emission with a maximum at 578 nm in the yellow region. © 2013 Elsevier Ltd. All rights reserved.

A continuous multi-millennial record of surficial bivalve mollusk shells from the Sao Paulo Bight, Brazilian shelf

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

STOWING AWAY ON SHIPS THAT PASS IN THE NIGHT: SCLEROBIONT ASSEMBLAGES ON INDIVIDUALLY DATED BIVALVE AND BRACHIOPOD SHELLS FROM A SUBTROPICAL SHELF

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Lattice effects in the quasi-two-dimensional valence-bond-solid Mott insulator EtMe3P[Pd(dmit)(2)](2)

The organic charge-transfer salt EtMe3P[Pd(dmit)(2)](2) is a quasi-two-dimensional Mott insulator with localized spins S = 1/2 residing on a distorted triangular lattice. Here we report measurements of the uniaxial thermal expansion coefficients alpha(i) along the in-plane i = a and c axis as well as along the out-of-plane b axis for temperatures 1.4 K <= T <= 200 K. Particular attention is paid to the lattice effects around the phase transition at T-VBS = 25 K into a low-temperature valence-bond-solid phase and the paramagnetic regime above where effects of short-range antiferromagnetic correlations can be expected. The salient results of our study include (i) the observation of strongly anisotropic lattice distortions accompanying the formation of the valence-bond-solid phase, and (ii) a distinct anomaly in the thermal expansion coefficients in the paramagnetic regime around 40 K. Our results demonstrate that upon cooling through T-VBS the in-plane c axis, along which the valence bonds form, contracts while the second in-plane a axis elongates by the same relative amount. Surprisingly, the dominant effect is observed for the out-of-plane b axis which shrinks significantly upon cooling through T-VBS. The pronounced anomaly in alpha(i) around 40 K is attributed to short-range magnetic correlations. It is argued that the position of this maximum, relative to that in the magnetic susceptibility around 70 K, speaks in favor of a more anisotropic triangular-lattice scenario for this compound than previously thought.

GASTROPOD SHELLS USED BY Dardanus insignis (Decapoda, Anomura) NEAR ISLANDS IN THE UBATUBA REGION, SAO PAULO, BRAZIL

The use of gastropod shells by hermit crabs is determined by the availability of shells in the environment or through selection for size and volume. This study analyzed patterns in the use of shells by Dardanus insignis (Saussure, 1858). From January 1998 to December 1999, 386 individuals were collected from two islands at Ubatuba, Sao Paulo. The crabs were measured for cephalothoracic shield length (CSL) and wet weight (CWW). The gastropod shells occupied by hermit crabs were identified, and the shell aperture width (SAW), dry weight (SDW) and internal volume (STY) were measured. The relationships between the dimensions of the gastropod shell and the hermit crabs were evaluated by linear regression analysis. Among the 11 species of gastropod shells used by D. insignis, the most often used was Olivancillaria urceus (31%), followed by Strombus pugilis (22%) and Siratus tenuivaricosus (18%). The shell of O. urceus was used most probably due to its high availability on Couves and Mar Virado islands. The most significant biometric parameter was shell aperture width (F=18.231; p<0.0001), highlighting the importance of this variable for the shell choice by D. insignis at both sites.

Multistep taphonomic alterations in fluvial mollusk shells: a case study in the touro passo formation (pleistocene–holocene), Southern Brazil

Accurate paleoenvironmental reconstruction relies on the correct interpretation of the postmortem history of skeletal remains in shelly assemblages. In contrast to marine settings, actualistic taphonomic studies are lacking for shell-rich concentrations in freshwater riverine systems. In particular, the taphonomic pathways and the origins of taphonomic signatures that are recorded in bioclasts from fluvial settings are poorly known. In this study, we addressed this issue by comparing the taphonomic signatures and shell-damage profiles among shells of freshwater mollusks recorded both in death and in fossil assemblages from the same fluvial environment. Our data indicated that dissolution was the most pervasive taphonomic process leading to the destruction of the shells. The loss of taphonomic information extended beyond shell dissolution in the riverbed, or the early diagenesis in the sedimentary record. The loss of biological information from the living community through the death assemblage, until the incorporation of shells as fossils, mainly occurred during the time the shells were in the sediment-water interface. Though this destruction affected primarily dead shells, reworked fossils also became vulnerable because they were carried out into the river load again by channel avulsion. A model that included the main taphonomic pathways followed by the molluscan shells in the fluvial Touro Passo Formation (Pleistocene-Holocene) is discussed. In this model, two main destructive domains were recognized, which were the biological, physical, and chemical processes operating at the taphonomically active zone (= TAZ domain) and the pedogenetic domain.

Are the preference and selection patterns of hermit crabs for gastropod shells species- or site-specific?

Experimental analyses of hermit crabs and their preferences for shells are essential to understand the intrinsic relationship of the crabs` dependence on shells, and may be useful to explain their shell use pattern in nature. The aim of this study was to evaluate the effect of crab species and site on the pattern of shell use, selection, and preference in the south-western Atlantic hermit crabs Pagurus brevidactylus and Pagurus criniticornis, comparing sympatric and allopatric populations. Differently from the traditional approach to evaluate shell preference by simply determining the shell selection pattern (i.e., the number of shells of each type selected), preference was defined (according to [Liszka, D., Underwood, AJ., 1990. An experimental design to determine preferences for gastropod shells by a hermit-crab. J. Exp. Mar. Biol. Ecol., 137(1), 47-62]) by the comparison of the number of crabs changing for a particular shell type when three options were given (Cerithium atratum, Morula nodulosa, and Tegula viridula) with the number of crabs changing for this same type when only this type was offered. The effect of crab species was tested at Cabelo Gordo Beach, where P. brevidacrylus was found occupying shells of C. atratum, M. nodulosa, and T viridula in similar frequencies, whereas P. criniticornis occupied predominantly shells of C atratum. In laboratory experiments the selection patterns of the two hermit-crab species for these three gastropods were different, with P criniticornis selecting mainly shells of C atratum, and R brevidactylus selecting more shells of M. nodulosa. The shell preference was also dependent on crab species, with P. criniticornis showing a clear preference for shells of C atratum, whereas P. brevidactylus did not show a preference for any of the tested shells. The effect of site was tested for the two species comparing data from Cabelo Gordo to Preta (P brevidactylus) and Araca beaches (P. criniticornis). The pattern of shell use, selection, and preference was demonstrated to be dependent on site only for P. brevidactylus. The results also showed that the shell use pattern of P criniticornis can be explained by its preference at both sites, whereas for P. brevidactylus it occurred only at Cabelo Gordo, where the absence of preference was correlated with the similar use of the three gastropod species studied. Finally, the results showed that the shell selection pattern cannot be considered as a measure of shell preference, since it overestimates crab selectivity. (C) 2009 Elsevier B.V. All rights reserved.

Valence band tail states in disordered superlattices embedded in wide parabolic AlGaAs well

Optical properties of intentionally disordered multiple quantum well (QW) system embedded in a wide AlGaAs parabolic well were investigated by photoluminescence (PL) measurements as functions of the laser excitation power and the temperature. The characterization of the carriers localized in the individual wells was allowed due to the artificial disorder that caused spectral separation of the photoluminescence lines emitted by different wells. We observed that the photoluminescence peak intensity from each quantum well shifted to high energy as the excitation power was increased. This blue-shift is associated with the filling of localized states in the valence band tail. We also found that the dependence of the peak intensity on the temperature is very sensitive to the excitation power. The temperature dependence of the photoluminescence peak energy from each QW was well fitted using a model that takes into account the thermal redistribution of the localized carriers. Our results demonstrate that the band tails in the studied structures are caused by alloy potential fluctuations and the band tail states dominate the emission from the peripheral wells. (C) 2012 American Institute of Physics. [http://dx.doi.org/10.1063/1.4730769]

Mixed-valence state of symmetric diruthenium complexes: synthesis, characterization, and electron transfer investigation

Complexes of the type {[(pyS)Ru(NH3)(4)](2)-mu-L}(n), where pyS = 4-mercaptopyridine, L = 4,4'-dithiodipyridine (pySSpy), pyrazine (pz) and 1,4-dicyanobenzene (DCB), and n = +4 and +5 for fully reduced and mixed-valence complexes, respectively, were synthesized and characterized. Electrochemical data showed that there is electron communication between the metal centers with comproportionation constants of 33.2, 1.30 x 10(8) and 5.56 x 10(5) for L = pySSpy, pz and DCB, respectively. It was also observed that the electronic coupling between the metal centers is affected by the p-back-bonding interaction toward the pyS ligand. Raman spectroscopy showed a dependence of the intensity of the vibrational modes on the exciting radiations giving support to the assignments of the electronic transitions. The degree of electron communication between the metal centers through the bridging ligands suggests that these systems can be molecular wire materials.

Recycling of the high valence states of heme proteins by cysteine residues of thimet-oligopeptidase

The peptidolytic enzyme THIMET-oligopeptidase (TOP) is able to act as a reducing agent in the peroxidase cycle of myoglobin (Mb) and horseradish peroxidase (HRP). The TOP-promoted recycling of the high valence states of the peroxidases to the respective resting form was accompanied by a significant decrease in the thiol content of the peptidolytic enzyme. EPR (electron paramagnetic resonance) analysis using DBNBS spin trapping revealed that TOP also prevented the formation of tryptophanyl radical in Mb challenged by H2O2. The oxidation of TOP thiol groups by peroxidases did not promote the inactivating oligomerization observed in the oxidation promoted by the enzyme aging. These findings are discussed towards a possible occurrence of these reactions in cells.

Fe valence fluctuations and magnetoelastic coupling in Pb-based multiferroics perovskites

Lead-based multiferroics perovskites with nominal compositions Pb(Fe1/2Nb1/2)O3 and Pb(Fe2/3W1/3)O3 were synthesized following a two-stage method. Magnetic proprieties were investigated and correlated to anelastic proprieties, measured by the conventional pulse-echo method. The discussions are focused in the region around 250 K, where magnetoelectroelastic instabilities have been observed. X-ray absorption nearedge structure (XANES) study further indicates that the edge position varies with temperature revealing a fluctuation on the valence of iron ions with the temperature, which can be related to a variation in anelastic and magnetic proprieties.

Core-shell macromolecules with dendritic polyphenylene core and polymer shells

Core-shell macromolecules with dendritic polyphenylene core and polymer shell Zusammenfassung / Abstract Core-shell macromolecular structures have become of great interest in materials science because they gave an opportunity to combine a large variety of chemical and physical properties in the single molecule, by combination of different (in terms of chemistry and physics) cores and shells. The interest in such complex structures was provoked by their potential applications in the coating and painting industry (latexes), as supports for catalysts in polymer industry, or as nano-containers and transporters for genes or drug delivery. The aim of this study was the synthesis, characterization and further application of core-shell macromolecules possessing a hydrophobic stiff core (polyphenylene dendrimers) surrounded with a hydrophilic, soft, covalently bonded polymer shell (poly(ethylene oxide) and its copolymers). The requirements for such complex substances were that they should be well-defined in terms of molecular weight (narrow molecular weight distribution) and in molecular structure. The preparation of core-shell molecules containing dendrimer as a core was possible via two synthetic routs: “grafting-onto” and “grafting-from”. The resulting core-shell macromolecules possessed narrow polydispersity as guaranteed by the excellent structural and functional definition of the dendrimer and the narrow polydispersity of the PEO, PS-b-PEO and PI-b-PEO attached to the dendrimer surface. Additional investigation of the size of the particles indicated a relation between both the length and the number of the polymer chains and the hydrodynamic radius determined by Dynamic Light Scattering and Fluorescent Correlation Spectroscopy. Core-shell nano-particles were applied as metallocene supports in heterogeneous olefin polymerizations. Our results indicate that such catalyst systems, that have a size of at least one order of magnitude smaller than the used by now organic supports, could be very useful as model compounds for investigations on catalyst fragmentation and its influence on the product parameters.

Determination of trace elemental species in periostracum of Cypraea shells

n this work, three Cypraea species (C. talpa, C. tigris and C. zebra) were exhaustively studied. The shells have been separated in the structural layers. The mineralogy, ultra- and micro-structure of each layer were analyzed by Confocal Laser Scanning Microscopy (CLSM), Scanning Electron Microscopy (SEM), X-Ray Diffractometry (XRD) and Raman Spectroscopy (RS). The presence of biologically relevant trace metals (Mn, Co, Fe, Zn, Cr, etc.) has been investigated using Instrumental Neutron Activation Analysis (INAA) and Inductively Coupled Plasma – Mass Spectrometry (ICP-MS) as detection tool. A new method has been developed and optimized to extract and analyze the soluble organic matrix (SOM) of the shell. Although the molecular nature of the SOM is not really known, it contains at least large protein fraction, if not only consists of proteins. The extracted matrices were compared between layers and species using Size Exclusion High Performance Liquid Chromatography coupled with Ultra Violet Spectrometry (SE-HPLC-UV), Gel electrophoresis (GE) and protein quantification tests. For the first time to our knowledge the association of trace elements to the protein in the SOM of the shell was studied using hyphenated on line as well as combined off line techniques and validated through inter-comparison tests between the different methods applied. Interesting correlations between the trace element concentration, the microstructure and the protein content were directly and indirectly detected. The metals Cu, Ni, Co and Zn have shown to bind to the SOM extracted from C. talpa, C. tigris and C. zebra shells. Within the conclusions of this work it was demonstrated that these protein-metal-complexes (or metal containing proteins) change from one layer to the other and are different between the three snails analyzed. In addition, the complexes are clearly related only to certain protein fractions of the SOM, and not to the whole SOM observed. These fractions and show not to be very metal-specific (i.e. some of these fractions bind two or three different metals).

Tuning the structural and magnetic properties of Sr 2 FeReO 6 by substituting Fe and Re with valence invariant metals

In the course of this work the effect of metal substitution on the structural and magnetic properties of the double perovskites Sr2MM’O6 (M = Fe, substituted by Cr, Zn and Ga; M’ = Re, substituted by Sb) was explored by means of X-ray diffraction, magnetic measurements, band structure calculations, Mößbauer spectroscopy and conductivity measurements. The focus of this study was the determination of (i) the kind and structural boundary conditions of the magnetic interaction between the M and M’ cations and (ii) the conditions for the principal application of double perovskites as spintronic materials by means of the band model approach. Strong correlations between the electronic, structural and magnetic properties have been found during the study of the double perovskites Sr2Fe1-xMxReO6 (0 < x < 1, M = Zn, Cr). The interplay between van Hove-singularity and Fermi level plays a crucial role for the magnetic properties. Substitution of Fe by Cr in Sr2FeReO6 leads to a non-monotonic behaviour of the saturation magnetization (MS) and an enhancement for substitution levels up to 10 %. The Curie temperatures (TC) monotonically increase from 401 to 616 K. In contrast, Zn substitution leads to a continuous decrease of MS and TC. The diamagnetic dilution of the Fe-sublattice by Zn leads to a transition from an itinerant ferrimagnetic to a localized ferromagnetic material. Thus, Zn substitution inhibits the long-range ferromagnetic interaction within the Fe-sublattice and preserves the long-range ferromagnetic interaction within the Re-sublattice. Superimposed on the electronic effects is the structural influence which can be explained by size effects modelled by the tolerance factor t. In the case of Cr substitution, a tetragonal – cubic transformation for x > 0.4 is observed. For Zn substituted samples the tetragonal distortion linearly increases with increasing Zn content. In order to elucidate the nature of the magnetic interaction between the M and M’ cations, Fe and Re were substituted by the valence invariant main group metals Ga and Sb, respectively. X-ray diffraction reveals Sr2FeRe1-xSbxO6 (0 < x < 0.9) to crystallize without antisite disorder in the tetragonal distorted perovskite structure (space group I4/mmm). The ferrimagnetic behaviour of the parent compound Sr2FeReO6 changes to antiferromagnetic upon Sb substitution as determined by magnetic susceptibility measurements. Samples up to a doping level of 0.3 are ferrimagnetic, while Sb contents higher than 0.6 result in an overall antiferromagnetic behaviour. 57Fe Mößbauer results show a coexistence of ferri- and antiferromagnetic clusters within the same perovskite-type crystal structure in the Sb substitution range 0.3 < x < 0.8, whereas Sr2FeReO6 and Sr2FeRe0.9Sb0.1O6 are “purely” ferrimagnetic and Sr2FeRe0.1Sb0.9O6 contains antiferromagnetically ordered Fe sites only. Consequently, a replacement of the Re atoms by a nonmagnetic main group element such as Sb blocks the double exchange pathways Fe–O–Re(Sb)–O–Fe along the crystallographic axis of the perovskite unit cell and destroys the itinerant magnetism of the parent compound. The structural and magnetic characterization of Sr2Fe1-xGaxReO6 (0 < x < 0.7) exhibit a Ga/Re antisite disorder which is unexpected because the parent compound Sr2FeReO6 shows no Fe/Re antisite disorder. This antisite disorder strongly depends on the Ga content of the sample. Although the X-ray data do not hint at a phase separation, sample inhomogeneities caused by a demixing are observed by a combination of magnetic characterization and Mößbauer spectroscopy. The 57Fe Mößbauer data suggest the formation of two types of clusters, ferrimagnetic Fe- and paramagnetic Ga-based ones. Below 20 % Ga content, Ga statistically dilutes the Fe–O–Re–O–Fe double exchange pathways. Cluster formation begins at x = 0.2, for 0.2 < x < 0.4 the paramagnetic Ga-based clusters do not contain any Fe. Fe containing Ga-based clusters which can be detected by Mößbauer spectroscopy firstly appear for x = 0.4.