Structural development of silicated films self-assembled at the air-water interface

The development of structure perpendicular to and in the plane of the interface has been studied for mesoporous silicate films self-assembled at the air/water interface. The use of constrained X-ray and neutron specular reflectometry has enabled a detailed study of the structural development perpendicular to the interface during the pre-growth phase. Off-specular neutron reflectometry and grazing incidence X-ray diffraction has enabled the in-plane structure to be probed with excellent time resolution. The growth mechanism under the surfactant to silicate source ratios used in this work is clearly due to the self-assembly of micellar and molecular species at the air/liquid interface, resulting in the formation of a planar mesoporous film that is tens of microns thick. (C) 2003 Elsevier Science B.V. All rights reserved.

Patterns of variation within self-incompatibility loci

Diverse self-incompatibility (SI) mechanisms permit flowering plants to inhibit fertilization by pollen that express specificities in common with the pistil. Characteristic of at least two model systems is greatly reduced recombination across large genomic tracts surrounding the S-locus, which regulates SI. In three angiosperm families, including the Solanaceae, the gene that controls the expression of gametophytic SI in the pistil encodes a ribonuclease (S-RNase). The gene that controls pollen SI expression is currently unknown, although several candidates have recently been proposed. Although each candidate shows a high level of polymorphism and complete allelic disequilibrium with the S-RNase gene, such properties may merely reflect tight linkage to the S-locus, irrespective of any functional role in SI. We analyzed the magnitude and nature of nucleotide variation, with the objective of distinguishing likely candidates for regulators of SI from other genes embedded in the S-locus region. We studied the S-RNase gene of the Solanaceae and 48A, a candidate for the pollen gene in this system, and we also conducted a parallel analysis of the regulators of sporophytic SI in Brassica, a system in which both the pistil and pollen genes are known. Although the pattern of variation shown by the pollen gene of the Brassica system is consistent with its role as a determinant of pollen specificity, that of 48A departs from expectation. Our analysis further suggests that recombination between 48A and S-RNase may have occurred during the interval spanned by the gene genealogy, another indication that 48A may not regulate SI expression in pollen.

A comparison of the self-association behavior of the plant cyclotides kalata B1 and kalata B2 via analytical ultracentrifugation

The recently discovered cyclotides kalata B1 and kalata B2 are miniproteins containing a head-to-tail cyclized backbone and a cystine knot motif, in which disulfide bonds and the connecting backbone segments form a ring that is penetrated by the third disulfide bond. This arrangement renders the cyclotides extremely stable against thermal and enzymatic decay, making them a possible template onto which functionalities can be grafted.We have compared the hydrodynamic properties of two prototypic cyclotides, kalata B1 and kalata B2, using analytical ultracentrifugation techniques. Direct evidence for oligomerization of kalata B2 was shown by sedimentation velocity experiments in which a method for determining size distribution of polydisperse molecules in solution was employed. The shape of the oligomers appears to be spherical. Both sedimentation velocity and equilibrium experiments indicate that in phosphate buffer kalata B1 exists mainly as a monomer, even at millimolar concentrations. In contrast, at 1.6 mM, kalata B2 exists as an equilibrium mixture of monomer (30%), tetramer (42%), octamer (25%), and possibly a small proportion of higher oligomers. The results from the sedimentation equilibrium experiments show that this self-association is concentration dependent and reversible. We link our findings to the three-dimensional structures of both cyclotides, and propose two putative interaction interfaces on opposite sides of the kalata B2 molecule, one involving a hydrophobic interaction with the Phe(6), and the second involving a charge-charge interaction with the Asp(25) residue. An understanding of the factors affecting solution aggregation is of vital importance for future pharmaceutical application of these molecules.

Reproductive biology of Cyrtopodium polyphyllum (Orchidaceae): a Cyrtopodiinae pollinated by deceit

The genus Cyrtopodium comprises about 42 species distributed from southern Florida to northern Argentina. Cyrtopodium polyphyllum occurs on rocks or in sandy soils, in restinga vegetation along the Brazilian coast. It flowers during the wet season and its inflorescences produce a high number of resupinate yellow flowers. Cyrtopodium polyphyllum offers no rewards to its pollinators, but mimics the yellow, reward-producing flowers of nearby growing Stigmaphyllon arenicola (oil) and Crotalaria vitellina (nectar) individuals. Several species of bee visit flowers of C. polyphyllum, but only two species of Centris (Centris tarsata and Centris labrosa) act as pollinators. Visits to flowers of C. polyphyllum were scarce and, as a consequence, low-fruit set was recorded under natural conditions. Such low-fruit production contrasts with the number of fruits each plant bears after manual pollination, suggesting deficient pollen transfer among plants. C. polyphyllum is self-compatible and has a high-fruit set in both manual self- and cross-pollinated flowers. Furthermore, fruits (2%) are formed by self-pollination assisted by rain. This facultative self-pollination mechanism is an important strategy to provide reproductive assurance to C. polyphyllum as rainfall restricts the foraging activity of its pollinating bees. Fruits derived from treatments and under natural conditions had a similar high rate of potentially viable seed. Moreover, these seeds had a low polyembryony rate, which did not exceed 5%. C. polyphyllum acts by deceit involving optical signals and exploits other yellow-flowered species within its habitat by attracting their pollinators. The low capsule production under natural conditions was expected, but its reproductive success is assured through self-pollination by rain and high seed viability.

Matching occupation and self: Does matching theory adequately model children's thinking?

The present exploratory-descriptive cross-national study focused on the career development of 11- to 14-yr.-old children, in particular whether they can match their personal characteristics with their occupational aspirations. Further, the study explored whether their matching may be explained in terms of a fit between person and environment using Holland's theory as an example. Participants included 511 South African and 372 Australian children. Findings relate to two items of the Revised Career Awareness Survey that require children to relate personal-social knowledge to their favorite occupation. Data were analyzed in three stages using descriptive statistics, i.e., mean scores, frequencies, and percentage agreement. The study indicated that children perceived their personal characteristics to be related to their occupational aspirations. However, how this matching takes place is not adequately accounted for in terms of a career theory such as that of Holland.

Er(3+) doped phosphoniobate glasses and planar waveguides: structural and optical properties

Phosphoniobate glasses with composition (mol%) (100-x) NaPO(3)-xNb(2)O(5) ( x varying from 11 to 33) were prepared and characterized by means of thermal analysis, Fourier transform infrared spectroscopy, Raman scattering and (31)P nuclear magnetic resonance. The addition of Nb(2)O(5) to the polyphosphate base glass leads to depolymerization of the metaphosphate structure. Different colors were observed and assigned as indicating the presence of Nb(4+) ions, as confirmed by electron paramagnetic resonance measurements. The color was observed to depend on the glass composition and melting temperature as well. Er(3+) containing samples were also prepared. Strong emission in the 1550 nm region was observed. The Er(3+4)I(15/2) emission quantum efficiency was observed to be 90% and the quenching concentration was observed to be 1.1 mol%( 1.45 x 10(20) ions cm(-3)). Planar waveguides were prepared by Na(+)-K(+)-Ag(+) ion exchange with Er(3+) containing samples. Optical parameters of the waveguides were measured at 632.8, 543.5 and 1550 nm by the prism coupling technique as a function of the ion exchange time and Ag(+) concentration. The optimized planar waveguides show a diffusion depth of 5.9 mu m and one propagating mode at 1550 nm.

Cerium-based phosphors: blue luminescent properties for applications in optical displays

In this paper, we describe the blue photoluminescence (PL) observed in the multi-component oxosalt phosphor GdVO(4)center dot Ce(3+). Different doping concentrations (0.25-1 mol%) and heat treatment (900-1100 degrees C) were used to evaluate which conditions would lead to the most suitable blue phosphor for optimal display performance. The cerium doping concentration influences the profile of the emission spectrum (broad peak at 412 nm under UV excitation at 330 nm), as reflected on the values of chromaticity coordinates. On the basis of luminescent properties, we can conclude that, among the phosphors prepared in this work the most adequate for a blue display is the one obtained via the combustion method using glycine as fuel, a 0.50 mol% cerium doping concentration, and heat treatment at 1000 degrees C.

Self-assembled naphthalenediimide derivative films for light-assisted electrochemical reduction of oxygen

This naphthalene diimide derivative, DC18, forms highly conjugated semiconducting stacked assemblies over electrodes after electrochemical conditioning. These molecular materials are very efficient towards electrochemical photoreduction of oxygen under visible light.

The nature of early self-recognition

In studies of mirror-self-recognition subjects are usually surreptitiously marked on their head, and then presented with a mirror. Scores of studies have established that by 18 to 24 months, children investigate their own head upon seeing the mark in the mirror. Scores of papers have debated what this means. Suggestions range from rich interpretations (e.g., the development of self-awareness) to lean accounts (e.g., the development of proprioceptivevisual matching), and include numerous more moderate proposals (e.g., the development of a concept of one's face). In Study 1, 18-24-monthold toddlers were given the standard test and a novel task in which they were marked on their legs rather than on their face. Toddlers performed equivalently on both tasks, suggesting that passing the test does not rely on information specific to facial features. In Study 2, toddlers were surreptitiously slipped into trouser legs that were prefixed to a highchair. Toddlers failed to retrieve the sticker now that their legs looked different from expectations. This finding, together with the findings from a third study which showed that self-recognition in live video feedback develops later than mirror selfrecognition, suggests that performance is not solely the result of proprioceptive-visual matching.

Signature of mott-insulator transition with ultracold fermions in a one-dimensional optical lattice

Using the exact Bethe ansatz solution of the Hubbard model and Luttinger liquid theory, we investigate the density profiles and collective modes of one-dimensional ultracold fermions confined in an optical lattice with a harmonic trapping potential. We determine a generic phase diagram in terms of a characteristic filling factor and a dimensionless coupling constant. The collective oscillations of the atomic mass density, a technique that is commonly used in experiments, provide a signature of the quantum phase transition from the metallic phase to the Mott-insulator phase. A detailed experimental implementation is proposed.

Er(3+)-doped silica-hafnia films for optical waveguides and spherical resonators

In this paper we present some result on sol-gel derived silica-hafnia systems. In particular we focus on fabrication, morphological and spectroscopic assessment of Er(3+)-activated thin films. Two examples of silica-hafnia-derived waveguiding glass ceramics, prepared by top-down and bottom-up techniques are reported, and the main optical properties are discussed. Finally, some properties of activated microspherical resonators, having a silica core, obtained by melting the end of a telecom fiber, coated with an Er(3+)-doped 70SiO(2)-30HfO(2) film, are presented. (C) 2009 Elsevier B.V. All rights reserved.

Solvent Effects in Optical Spectra of ortho-Aminobenzoic Acid Derivatives

We investigated three amino derivatives of ortho-aminobenzoic or anthranilic acid (o-Abz): a) 2-Amino-benzamide (AbzNH(2)); b) 2-Amino-N-methyl-benzamide (AbzNHCH(3)) and c) 2-Amino-N-N`-dimethyl-bezamide (AbzNH(CH(3))(2)), see Scheme 1. We describe the results of ab-initio calculations on the structural characteristics of the compounds and experimental studies about solvent effects in their absorption and steady-state and time-resolved emission properties. Ab-initio calculations showed higher stability for the rotameric conformation in which the oxygen of carbonyl is near to the nitrogen of ortho-amino group. The derivatives present decrease in the delocalization of pi electron, and absorption bands are blue shifted compared to the parent compound absorption, the extent of the effect increasing from to Abz-NH(2) to Abz-NHCH(3) Abz-NH(CH(3))(2). Measurements performed in several solvents have shown that the the dependence of Stokes shift of the derivatives with the orientational polarizability follows the Onsager-Lippert model for general effects of solvent. However deviation occurred in solvents with properties of Bronsted acids, or electron acceptor characteristics, so that hydrogen bonds formed with protic solvents predominates over intramolecular hydrogen bond. In most solvents the fluorescence decay of AbzNH(2) and AbzNHCH(3) was fitted to a single exponential with lifetimes around 7.0 ns and no correlation with polarity of the solvent was observed. The fluorescence decay of AbzN(CH(3))(2) showed lifetimes around 2.0 ns, consistent with low quantum yield of the compound. The spectroscopic properties of the monoamino derivative AbzNHCH(3) are representative of the properties presented by Abz labelled peptides and fatty acids previously studied.

Effects of Self-Assembled Materials Prepared from V(2)O(5) for Lithium Ion Electroinsertion

Self-assembled materials consisting of V(2)O(5), polyallylamine (PAR) and silver nanoparticles (AgNPs) were obtained by the layer-by-layer (LbL) method, aiming at their application as electrodes for lithium-ion batteries and electrochromic devices. The method employed herein allowed for linear growth of visually homogeneous films composed of V(2)O(5), V(2)O(5)/PAH, and V(2)O(5)/PAH/AgNP with 15 bilayers. According to the Fourier transform infrared spectra, interaction between the oxygen atom of the vanadyl group and the amino group should be responsible for the growth of these films. This interaction also enabled establishment of an electrostatic shield between the lithium ions and the sites with higher negative charge, thereby raising the ionic mobility and consequently increasing the energy storage capacity and reducing the response time. According to the site-saturation model and the electrochemical and spectroelectrochemical results, the presence of PAH in the self-assembled host matrix decreased the number of V(2)O(5) electroactive sites. Thus, AgNPs were stabilized in PAR and inserted into the nanoarchitecture, so as to enhance the specific capacity. This should provide new conducting pathways and connect isolated V(2)O(5) particles in the host matrix. Therefore, new nanoarchitectures for specific interactions were formed spontaneously and chosen as examples in this work, aiming to demonstrate the potentiality of the adopted self-assembled method for enhancing the charge transport rate into the host matrices. The obtained materials displayed suitable properties for use as electrodes in lithium batteries and electrochromic devices.