Symmetric Diblock Copolymers in Thin Films (I): Phase stability in Self-Consistent Field Calculations and Monte Carlo Simulations

We investigate the phase behavior of symmetric AB diblock copolymers confined into a thin film. The film boundaries are parallel, impenetrable and attract the A component of the diblock copolymer. Using a self-consistent field technique [M.W. Matsen, J.Chem.Phys. {\bf 106}, 7781 (1997)], we study the ordered phases as a function of incompatibility $\chi$ and film thickness in the framework of the Gaussian chain model. For large film thickness and small incompatibility, we find first order transitions between phases with different number of lamellae which are parallel oriented to the film boundaries. At high incompatibility or small film thickness, transitions between parallel oriented and perpendicular oriented lamellae occur. We compare the self-consistent field calculations to Monte Carlo simulations of the bond fluctuation model for chain length N=32. In the simulations we quench several systems from $\chi N=0$ to $\chi N=30$ and monitor the morphology into which the diblock copolymers assemble. Three film thicknesses are investigated, corresponding to parallel oriented lamellae with 2 and 4 interfaces and a perpendicular oriented morphology. Good agreement between self-consistent field calculations and Monte Carlo simulations is found.Comment: to appear in J.Chem.Phy

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

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 $\phi_c=1/2$. 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

Transcriptome analysis of highly purified mouse spermatogenic cell populations: gene expression signatures switch from meiotic-to postmeiotic-related processes at pachytene stage

Top five canonical pathways and molecular and cellular functions from pairwise comparisons of the four cell populations in chronological order (LZ relative to 2C; PS relative to LZ; RS relative to PS). (XLSX 10 kb

Sums of magnetic eigenvalues are maximal on rotationally symmetric domains

The sum of the first n energy levels of the planar Laplacian with constant magnetic field of given total flux is shown to be maximal among triangles for the equilateral triangle, under normalization of the ratio (moment of inertia)/(area)^3 on the domain. The result holds for both Dirichlet and Neumann boundary conditions, with an analogue for Robin (or de Gennes) boundary conditions too. The square similarly maximizes the eigenvalue sum among parallelograms, and the disk maximizes among ellipses. More generally, a domain with rotational symmetry will maximize the magnetic eigenvalue sum among all linear images of that domain. These results are new even for the ground state energy (n=1).Comment: 19 pages, 1 figur

A Theory of Expressive International Law

What is the pull of international society and how does it influence the willingness of States to enter into or comply with international law? Since Grotius first identified the concept that States seek esteem from the broader global community, its parameters have proven illusive. Nonetheless, the notion remains central to discussions of why States comply with international agreements. Understanding the reputational mechanism that impels State compliance is especially important to human rights treaties. Unlike other regimes, States that ratify and abide by the terms of these instruments receive neither reciprocal nor immediate benefits. Consequently, the desire for international esteem is the crucible by which compliance with human rights norms is determined. Professor Oona Hathaway has recently raised concerns about the efficacy of the reputational mechanism through an empirical study suggesting that ratification of human rights treaties may lead to increased human rights violations. While these findings have been challenged on both econometric and normative grounds, the need to understand whether Hathaway\u27s findings are simply the result of faulty measurement, improper regime design, or the inability of social forces to compel compliance is crucial to the development and success of the international human rights project. Answers to these questions begin with the development of more detailed models of the way social forces work. Not only will such models enable us to determine if social forces can be harnessed to better ensure compliance with human rights treaties, they also provide a framework that can help us better design human rights instruments

A Theory of Expressive International Law

What is the pull of international society and how does it influence the willingness of States to enter into or comply with international law? Since Grotius first identified the concept that States seek esteem from the broader global community, its parameters have proven illusive. Nonetheless, the notion remains central to discussions of why States comply with international agreements. Understanding the reputational mechanism that impels State compliance is especially important to human rights treaties. Unlike other regimes, States that ratify and abide by the terms of these instruments receive neither reciprocal nor immediate benefits. Consequently, the desire for international esteem is the crucible by which compliance with human rights norms is determined. Professor Oona Hathaway has recently raised concerns about the efficacy of the reputational mechanism through an empirical study suggesting that ratification of human rights treaties may lead to increased human rights violations. While these findings have been challenged on both econometric and normative grounds, the need to understand whether Hathaway\u27s findings are simply the result of faulty measurement, improper regime design, or the inability of social forces to compel compliance is crucial to the development and success of the international human rights project. Answers to these questions begin with the development of more detailed models of the way social forces work. Not only will such models enable us to determine if social forces can be harnessed to better ensure compliance with human rights treaties, they also provide a framework that can help us better design human rights instruments

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

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

Solonamide B Inhibits Quorum Sensing and Reduces Staphylococcus aureus Mediated Killing of Human Neutrophils

Methicillin-resistant Staphylococcus aureus (MRSA) continues to be a serious human pathogen, and particularly the spread of community associated (CA)-MRSA strains such as USA300 is a concern, as these strains can cause severe infections in otherwise healthy adults. Recently, we reported that a cyclodepsipeptide termed Solonamide B isolated from the marine bacterium, Photobacterium halotolerans strongly reduces expression of RNAIII, the effector molecule of the agr quorum sensing system. Here we show that Solonamide B interferes with the binding of S. aureus autoinducing peptides (AIPs) to sensor histidine kinase, AgrC, of the agr two-component system. The hypervirulence of USA300 has been linked to increased expression of central virulence factors like α-hemolysin and the phenol soluble modulins (PSMs). Importantly, in strain USA300 Solonamide B dramatically reduced the activity of α-hemolysin and the transcription of psma encoding PSMs with an 80% reduction in toxicity of supernatants towards human neutrophils and rabbit erythrocytes. To our knowledge this is the first report of a compound produced naturally by a Gram-negative marine bacterium that interferes with agr and affects both RNAIII and AgrA controlled virulence gene expression in S. aureus