252 research outputs found
First principles calculation of vibrational Raman spectra in large systems: signature of small rings in crystalline SiO2
We present an approach for the efficient calculation of vibrational Raman
intensities in periodic systems within density functional theory. The Raman
intensities are computed from the second order derivative of the electronic
density matrix with respect to a uniform electric field. In contrast to
previous approaches, the computational effort required by our method for the
evaluation of the intensities is negligible compared to that required for the
calculation of vibrational frequencies. As a first application, we study the
signature of 3- and 4-membered rings in the the Raman spectra of several
polymorphs of SiO2, including a zeolite having 102 atoms per unit cell.Comment: 4 pages, 2 figures, revtex4 Minor corrections; accepted in Phys. Rev.
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Phase diagram for diblock copolymer melts under cylindrical confinement
We extensively study the phase diagram of a diblock copolymer melt confined
in a cylindrical nanopore using real-space self-consistent mean-field theory.
We discover a rich variety of new two-dimensional equilibrium structures that
have no analog in the unconfined system. These include non-hexagonally
coordinated cylinder phases and structures intermediate between lamellae and
cylinders. We map the stability regions and phase boundaries for all the
structures we find. As the pore radius is decreased, the pore accommodates
fewer cylindrical domains and structural transitions occur as cylinders are
eliminated. Our results are consistent with experiments, but we also predict
phases yet to be observed.Comment: 12 pages, 3 figures. submitted to Physical Review Letter
Large well-relaxed models of vitreous silica, coordination numbers and entropy
A Monte Carlo method is presented for the simulation of vitreous silica.
Well-relaxed networks of vitreous silica are generated containing up to 300,000
atoms. The resulting networks, quenched under the BKS potential, display
smaller bond-angle variations and lower defect concentrations, as compared to
networks generated with molecular dynamics. The total correlation functions
T(r) of our networks are in excellent agreement with neutron scattering data,
provided that thermal effects and the maximum inverse wavelength used in the
experiment are included in the comparison. A procedure commonly used in
experiments to obtain coordination numbers from scattering data is to fit peaks
in rT(r) with a gaussian. We show that this procedure can easily produce
incorrect results. Finally, we estimate the configurational entropy of vitreous
silica.Comment: 7 pages, 4 figures (two column version to save paper
A symmetric polymer blend confined into a film with antisymmetric surfaces: interplay between wetting behavior and phase diagram
We study the phase behavior of a symmetric binary polymer blend which is
confined into a thin film. The film surfaces interact with the monomers via
short range potentials. We calculate the phase behavior within the
self-consistent field theory of Gaussian chains. Over a wide range of
parameters we find strong first order wetting transitions for the semi-infinite
system, and the interplay between the wetting/prewetting behavior and the phase
diagram in confined geometry is investigated. Antisymmetric boundaries, where
one surface attracts the A component with the same strength than the opposite
surface attracts the B component, are applied. The phase transition does not
occur close to the bulk critical temperature but in the vicinity of the wetting
transition. For very thin films or weak surface fields one finds a single
critical point at . For thicker films or stronger surface fields
the phase diagram exhibits two critical points and two concomitant coexistence
regions. Only below a triple point there is a single two phase coexistence
region. When we increase the film thickness the two coexistence regions become
the prewetting lines of the semi-infinite system, while the triple temperature
converges towards the wetting transition temperature from above. The behavior
close to the tricritical point, which separates phase diagrams with one and two
critical points, is studied in the framework of a Ginzburg-Landau ansatz.
Two-dimensional profiles of the interface between the laterally coexisting
phases are calculated, and the interfacial and line tensions analyzed. The
effect of fluctuations and corrections to the self-consistent field theory are
discussed.Comment: Phys.Rev.E in prin
Adaptação do inventário parental “Language Use Inventory (LUI)” para crianças entre 18 e 47 meses para o português europeu : estudo piloto
Language acquisition and development takes in account the child’s interaction with the surrounding environment. Daily social interactions with people and communication with others allow the child to acquire language being pragmatics considered a system of rules that support the communicative use of language. Identification and assessment of children at risk for language disorders are crucial in order to carry out an effective early intervention. This study was carried out taking into account first, the relevance of pragmatics as a component of language, and second the lack of assessment tools in Portugal to assess these abilities. Therefore, the aim of this study consists on the translation, adaptation and validation of the inventory “Language Use Inventory” (LUI), to European Portuguese. The LUI is a standardized parent report measure designed to assess pragmatic language development in children within 18- to 47-month-old.Objetivo: A aquisição e o desenvolvimento da linguagem resultam
da interação da criança com o meio ambiente. As interações sociais
cotidianas com as pessoas e a comunicação com outros permitem que a
criança adquira linguagem, sendo a pragmática o sistema de regras que
suporta o uso comunicativo da linguagem. A identificação e a avaliação
de crianças em risco de desenvolverem transtornos de linguagem são
cruciais, tendo em vista a intervenção precoce eficaz. Tendo em vista a
relevância da pragmática como componente da linguagem e a escassez,
em Portugal, de instrumentos de avaliação da linguagem validados
para idades precoces, a finalidade deste estudo consistiu na tradução,
adaptação e validação do instrumento Language Use Inventory (LUI),
para o português europeu. O LUI é um inventário parental que avalia o
desenvolvimento da pragmática entre os 18 e os 47 meses. Métodos:
Foram adotados todos os procedimentos recomendados pelas diretrizes
internacionais sobre a adaptação de testes, culminando em estudo piloto
com uma amostra de 120 inventários, respondidos pelos pais/cuidadores
de crianças portuguesas da referida faixa etária. Resultados: Os
coeficientes de consistência interna (Alfa de Cronbach) para a versão
portuguesa do LUI situaram-se em 0,97 para a escala total e entre 0,71
e 0,96 para as subescalas. Conclusão: Os resultados preliminares dos
estudos de adaptação e de validação do LUI-Pt para crianças portuguesas
são promissores e asseguram a validade interna desta escala em termos
da sua dimensionalidade e consistência interna
Organization of Block Copolymers using NanoImprint Lithography: Comparison of Theory and Experiments
We present NanoImprint lithography experiments and modeling of thin films of
block copolymers (BCP). The NanoImprint lithography is used to align
perpendicularly lamellar phases, over distances much larger than the natural
lamellar periodicity. The modeling relies on self-consistent field calculations
done in two- and three-dimensions. We get a good agreement with the NanoImprint
lithography setups. We find that, at thermodynamical equilibrium, the ordered
BCP lamellae are much better aligned than when the films are deposited on
uniform planar surfaces
Block Copolymer at Nano-Patterned Surfaces
We present numerical calculations of lamellar phases of block copolymers at
patterned surfaces. We model symmetric di-block copolymer films forming
lamellar phases and the effect of geometrical and chemical surface patterning
on the alignment and orientation of lamellar phases. The calculations are done
within self-consistent field theory (SCFT), where the semi-implicit relaxation
scheme is used to solve the diffusion equation. Two specific set-ups, motivated
by recent experiments, are investigated. In the first, the film is placed on
top of a surface imprinted with long chemical stripes. The stripes interact
more favorably with one of the two blocks and induce a perpendicular
orientation in a large range of system parameters. However, the system is found
to be sensitive to its initial conditions, and sometimes gets trapped into a
metastable mixed state composed of domains in parallel and perpendicular
orientations. In a second set-up, we study the film structure and orientation
when it is pressed against a hard grooved mold. The mold surface prefers one of
the two components and this set-up is found to be superior for inducing a
perfect perpendicular lamellar orientation for a wide range of system
parameters
Refining a questionnaire to assess breast cancer knowledge and barriers to screening in Kenya: Psychometric assessment of the BCAM
Staphylococcus aureus RNAIII Binds to Two Distant Regions of coa mRNA to Arrest Translation and Promote mRNA Degradation
Staphylococcus aureus RNAIII is the intracellular effector of the quorum sensing system that temporally controls a large number of virulence factors including exoproteins and cell-wall-associated proteins. Staphylocoagulase is one major virulence factor, which promotes clotting of human plasma. Like the major cell surface protein A, the expression of staphylocoagulase is strongly repressed by the quorum sensing system at the post-exponential growth phase. Here we used a combination of approaches in vivo and in vitro to analyze the mechanism used by RNAIII to regulate the expression of staphylocoagulase. Our data show that RNAIII represses the synthesis of the protein through a direct binding with the mRNA. Structure mapping shows that two distant regions of RNAIII interact with coa mRNA and that the mRNA harbors a conserved signature as found in other RNAIII-target mRNAs. The resulting complex is composed of an imperfect duplex masking the Shine-Dalgarno sequence of coa mRNA and of a loop-loop interaction occurring downstream in the coding region. The imperfect duplex is sufficient to prevent the formation of the ribosomal initiation complex and to repress the expression of a reporter gene in vivo. In addition, the double-strand-specific endoribonuclease III cleaves the two regions of the mRNA bound to RNAIII that may contribute to the degradation of the repressed mRNA. This study validates another direct target of RNAIII that plays a role in virulence. It also illustrates the diversity of RNAIII-mRNA topologies and how these multiple RNAIII-mRNA interactions would mediate virulence regulation
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