Experimentally determined chaotic phase synchronization in a neuronal system

Mathematical analysis of the subthreshold oscillatory properties of inferior olivary neurons in vitro indicates that the oscillation is nonlinear and supports low dimensional chaotic dynamics. This property leads to the generation of complex functional states that can be attained rapidly via phase coherence that conform to the category of “generalized synchronization.” Functionally, this translates into neuronal ensemble properties that can support maximum functional permissiveness and that rapidly can transform into robustly determined multicellular coherence.

Characterization of complex mineral assemblages: Implications for contaminant transport and environmental remediation

Surface reactive phases of soils and aquifers, comprised of phyllosilicate and metal oxohydroxide minerals along with humic substances, play a critical role in the regulation of contaminant fate and transport. Much of our knowledge concerning contaminant-mineral interactions at the molecular level, however, is derived from extensive experimentation on model mineral systems. Although these investigations have provided a foundation for understanding reactive surface functional groups on individual mineral phases, the information cannot be readily extrapolated to complex mineral assemblages in natural systems. Recent studies have elucidated the role of less abundant mineral and organic substrates as important surface chemical modifiers and have demonstrated complex coupling of reactivity between permanent-charge phyllosilicates and variable-charge Fe-oxohydroxide phases. Surface chemical modifiers were observed to control colloid generation and transport processes in surface and subsurface environments as well as the transport of solutes and ionic tracers. The surface charging mechanisms operative in the complex mineral assemblages cannot be predicted based on bulk mineralogy or by considering surface reactivity of less abundant mineral phases based on results from model systems. The fragile nature of mineral assemblages isolated from natural systems requires novel techniques and experimental approaches for investigating their surface chemistry and reactivity free of artifacts. A complete understanding of the surface chemistry of complex mineral assemblages is prerequisite to accurately assessing environmental and human health risks of contaminants or in designing environmentally sound, cost-effective chemical and biological remediation strategies.

Targeting of nitric oxide synthase to endothelial cell caveolae via palmitoylation: implications for nitric oxide signaling.

The membrane association of endothelial nitric oxide synthase (eNOS) plays an important role in the biosynthesis of nitric oxide (NO) in vascular endothelium. Previously, we have shown that in cultured endothelial cells and in intact blood vessels, eNOS is found primarily in the perinuclear region of the cells and in discrete regions of the plasma membrane, suggesting trafficking of the protein from the Golgi to specialized plasma membrane structures. Here, we show that eNOS is found in Triton X-100-insoluble membranes prepared from cultured bovine aortic endothelial cells and colocalizes with caveolin, a coat protein of caveolae, in cultured bovine lung microvascular endothelial cells as determined by confocal microscopy. To examine if eNOS is indeed in caveolae, we purified luminal endothelial cell plasma membranes and their caveolae directly from intact, perfused rat lungs. eNOS is found in the luminal plasma membranes and is markedly enriched in the purified caveolae. Because palmitoylation of eNOS does not significantly influence its membrane association, we next examined whether this modification can affect eNOS targeting to caveolae. Wild-type eNOS, but not the palmitoylation mutant form of the enzyme, colocalizes with caveolin on the cell surface in transfected NIH 3T3 cells, demonstrating that palmitoylation of eNOS is necessary for its targeting into caveolae. These data suggest that the subcellular targeting of eNOS to caveolae can restrict NO signaling to specific targets within a limited microenvironment at the cell surface and may influence signal transduction through caveolae.

Specific and high-affinity binding of inositol phosphates to an isolated pleckstrin homology domain.

Pleckstrin homology (PH) domains are found in many signaling molecules and are thought to be involved in specific intermolecular interactions. Their binding to several proteins and to membranes containing 1-alpha-phosphatidylinositol 4,5-bisphosphate [PtdIns(4,5)P2] has been reported. A region that includes the PH domain has also been implicated in binding of phospholipase C-delta 1 (PLC-delta 1) to both PtdIns(4,5)P2 and D-myo-inositol 1,4,5-trisphosphate [Ins(1,4,5)P3] [Cifuentes, M. E., Delaney, T. & Rebecchi, M. J. (1994) J. Biol. Chem. 269, 1945-1948]. We report herein that the isolated PH domain from PLC-delta 1 binds to both PtdIns(4,5)P2 and Ins(1,4,5)P3 with high affinity and shows the same binding specificity seen by others with whole PLC-delta 1. Thus the PH domain is functionally and structurally modular. These results demonstrate stereo-specific high-affinity binding by an isolated PH domain and further support a functional role for PH domains in the regulation of PLC isoforms. Other PH domains did not bind strongly to the compounds tested, suggesting that inositol phosphates and phospholipids are not likely physiological ligands for all PH domains. Nonetheless, since all PH-domain-containing proteins are associated with membrane surfaces, several PH domains bind to specific sites on membranes, and PH domains appear to be electrostatically polarized, a possible general role for PH domains in membrane association is suggested.

Similar antigenic surfaces, rather than sequence homology, dictate T-cell epitope molecular mimicry.

Molecular mimicry, normally defined by the level of primary-sequence similarities between self and foreign antigens, has been considered a key element in the pathogenesis of autoimmunity. Here we describe an example of molecular mimicry between two overlapping peptides within a single self-antigen, both of which are recognized by the same human self-reactive T-cell clone. Two intervening peptides did not stimulate the T-cell clone, even though they share nine amino acids with the stimulatory peptides. Molecular modeling of major histocompatibility complex class II-peptide complexes suggests that both of the recognized peptides generate similar antigenic surfaces, although these are composed of different sets of amino acids. The molecular modeling of a peptide shifted one residue from the stimulatory peptide, which was recognized in the context of the same HLA molecule by another T-cell clone, generated a completely different antigenic surface. Functional studies using truncated peptides confirmed that the anchor residues of the two "mimicking" epitopes in the HLA groove differ. Our results show, for two natural epitopes, how molecular mimicry can occur and suggest that studies of potential antigenic surfaces, rather than sequence similarity, are necessary for analyzing suspected peptide mimicry.

The electron-furfural scattering dynamics for 63 energetically open electronic states

We report on integral-, momentum transfer-and differential cross sections for elastic and electronically inelastic electron collisions with furfural (C5H4O2). The calculations were performed with two different theoretical methodologies, the Schwinger multichannel method with pseudopotentials (SMCPP) and the independent atom method with screening corrected additivity rule (IAM-SCAR) that now incorporates a further interference (I) term. The SMCPP with N energetically open electronic states (N-open) at either the static-exchange (N-open ch-SE) or the static-exchange-plus-polarisation (N-open ch-SEP) approximation was employed to calculate the scattering amplitudes at impact energies lying between 5 eV and 50 eV, using a channel coupling scheme that ranges from the 1ch-SEP up to the 63ch-SE level of approximation depending on the energy considered. For elastic scattering, we found very good overall agreement at higher energies among our SMCPP cross sections, our IAM-SCAR+I cross sections and the experimental data for furan (a molecule that differs from furfural only by the substitution of a hydrogen atom in furan with an aldehyde functional group). This is a good indication that our elastic cross sections are converged with respect to the multichannel coupling effect for most of the investigated intermediate energies. However, although the present application represents the most sophisticated calculation performed with the SMCPP method thus far, the inelastic cross sections, even for the low lying energy states, are still not completely converged for intermediate and higher energies. We discuss possible reasons leading to this discrepancy and point out what further steps need to be undertaken in order to improve the agreement between the calculated and measured cross sections. (C) 2016 AIP Publishing LLC.

Ligand tethering by ion-exchange for the immobilization of homogeneous catalysts

A Rh phosphine complex, derived from the Wilkinson’s catalyst, has been immobilized by ion-exchange on the ammonium form of a Al-MCM-41 sample. Ammonium ions have been exchanged by cholamine ions, which act as an amine ligand, and then the Wilkinson’s catalyst has been immobilized by substitution of a phosphine ligand by the anchored amine. This is a novel immobilization procedure, as a ligand, instead of the whole complex, is tethered to the support by ion exchange. The obtained hybrid catalyst has been characterized by Elemental Analysis, DRIFTS and XPS. The quantitative exchange of ammonium by cholamine and coordination of Rh to amines has been observed. Most of the anchored Rh is considered to be coordinated to the ligand tethered to the support and a small proportion seems to be interacting with the protonated ligand or with the support surface. The catalyst has been tested in the hydrogenation of cyclohexene and in the hydroformylation of 1-octene. In the first case the catalyst is active and reusable, while a strong Rh leaching takes place in the second one.

Apoyo social formal a un grupo de madres con hijos menores de un año

Objetivo: este trabajo pretende analizar el apoyo social formal a un grupo de madres con hijos menores de un año. Método: estudio cualitativo, descriptivo interpretativo, en el cual participaron diez mujeres en un grupo focal que se reunió en siete ocasiones. Resultados: a partir del análisis de contenido de las dinámicas grupales se detecta que el apoyo formal informativo es el más frecuente y resulta difícil separarlo del emocional. Los profesionales, a través del apoyo informativo, tratan temas relacionados con la promoción de la salud y prevención de la enfermedad y acompañan a las madres en este rol. Conclusión: para las madres el apoyo formal brindado por el personal de enfermería es positivo y percibido como un refuerzo en su vivencia de la maternidad, y debe estar enmarcado en un contexto cultural.

Modifying enzyme activity and selectivity by immobilization

Immobilization of enzymes may produce alterations in their observed activity, specificity or selectivity. Although in many cases an impoverishment of the enzyme properties is observed upon immobilization (caused by the distortion of the enzyme due to the interaction with the support) in some instances such properties may be enhanced by this immobilization. These alterations in enzyme properties are sometimes associated with changes in the enzyme structure. Occasionally, these variations will be positive. For example, they may be related to the stabilization of a hyperactivated form of the enzyme, like in the case of lipases immobilized on hydrophobic supports via interfacial activation. In some other instances, these improvements will be just a consequence of random modifications in the enzyme properties that in some reactions will be positive while in others may be negative. For this reason, the preparation of a library of biocatalysts as broad as possible may be a key turning point to find an immobilized biocatalyst with improved properties when compared to the free enzyme. Immobilized enzymes will be dispersed on the support surface and aggregation will no longer be possible, while the free enzyme may suffer aggregation, which greatly decreases enzyme activity. Moreover, enzyme rigidification may lead to preservation of the enzyme properties under drastic conditions in which the enzyme tends to become distorted thus decreasing its activity. Furthermore, immobilization of enzymes on a support, mainly on a porous support, may in many cases also have a positive impact on the observed enzyme behavior, not really related to structural changes. For example, the promotion of diffusional problems (e.g., pH gradients, substrate or product gradients), partition (towards or away from the enzyme environment, for substrate or products), or the blocking of some areas (e.g., reducing inhibitions) may greatly improve enzyme performance. Thus, in this tutorial review, we will try to list and explain some of the main reasons that may produce an improvement in enzyme activity, specificity or selectivity, either real or apparent, due to immobilization.

Non-covalent immobilization of RhDuphos on carbon nanotubes and carbon xerogels

The immobilization of the chiral complex RhDuphos, by electrostatic or π–π (adsorption) interactions, on carbon nanotubes and carbon xerogels is investigated. To promote such interactions, the supports were either oxidized or heat treated to create carboxylic type surface groups or an apolar surface, respectively. The catalysts were tested in the hydrogenation of methyl 2-acetamidoacrylate. The prepared hybrid catalysts are less active than the homogeneous RhDuphos, but most of them show a high enantioselectivity and the one prepared with the oxidized carbon xerogel is also reusable, being able to give a high substrate conversion, keeping as well a high enantioselectivity. The anchorage by electrostatic interactions is more interesting than the anchorage by π–π interactions, as the π–π adsorption method produces a modification of the metal complex structure leading to an active hybrid catalyst but without enantioselectivity. The creation of carboxylic groups on the support surface has led to some hindering of the complex leaching.

Synthesis of palladium nanoparticles over graphite oxide and carbon nanotubes by reduction in ethylene glycol and their catalytic performance on the chemoselective hydrogenation of para-chloronitrobenzene

Pd nanoparticles have been synthesized over carbon nanotubes (CNT) and graphite oxide (GO) by reduction with ethylene glycol and by conventional impregnation method. The catalysts were tested on the chemoselective hydrogenation of p-chloronitrobenzene and the effect of the synthesis method and surface chemistry on their catalytic performance was evaluated. The catalysts were characterized by N2 adsorption/desorption isotherms at 77 K, TEM, powder X-ray diffraction, thermogravimetry, infrared and X-ray photoelectron spectroscopy and ICP-OES. It was observed that the synthesis of Pd nanoparticles employing ethylene glycol resulted in metallic palladium particles of smaller size compared to those prepared by the impregnation method and similar for both supports. The presence of oxygen groups on the support surface favored the activity and diminished the selectivity. It seems that ethylene glycol reacted with the surface groups of GO, this favoring the selectivity. The activity was higher over the CNT-based catalysts and both catalysts prepared by reduction in ethylene glycol were quite stable upon recycling.

Prática de ensino supervisionada em Educação Pré-escolar e Ensino do 1.º Ciclo do Ensino Básico

O presente relatório foi realizado no âmbito da unidade curricular de Prática de Ensino Supervisionada (PES), integrada no plano de estudos do Mestrado Pré-Escolar e Ensino do 1.º Ciclo do Ensino Básico, descreve e analisa experiências de ensino/aprendizagem realizadas em contexto Pré-Escolar e de 1.º Ciclo do Ensino Básico. Foi nossa intenção promover experiências enriquecedoras que nos permitissem analisar o processo de transição entre estes dois contextos. Procuramos envolver as crianças em novas realidades potenciadoras de múltiplas interações sociais, integradas no contexto escolar, com o objetivo de potenciar as relações educativas entre os diferentes níveis de ensino. Dado que o nosso foco investigativo se centrava na transição entre os dois níveis educativos procuramos delinear uma questão que orientasse o nosso estudo: “Que estratégias se podem desenvolver em contexto de Educação Pré-Escolar e 1.º Ciclo do Ensino Básico que promovam a articulação, numa perspetiva de continuidade educativa, entre estes dois contextos?”. Para dar resposta a esta questão delineamos os seguintes objetivos: desenvolver estratégias integradoras que promovessem a adaptação das crianças a cada etapa formativa, perceber se as estratégias utlizadas foram as adequadas e que reflexos tiveram na transição educativa e perceber se as aprendizagens adquiridas facilitaram a articulação entre os dois níveis educativos, valorizando o desenvolvimento de competências neste domínio. Para orientar metodologicamente a investigação recorremos a uma metodologia qualitativa, cujos dados foram recolhidos através da observação participante, das notas de campo e dos registos fotográficos, respeitando o sigilo inerente à prática de investigação e solicitando autorização prévia para a sua implementação, as dois grupos de crianças, um do Pré-escolar, com idades de 5 e 6 anos e outro do 1.º Ciclo do Ensino Básico com 6 ano de idade. Da análise dos dados, evidencia-se a facilidade de adaptação das crianças, da Educação Pré-escolar para o 1.º CEB, demonstrando saber que as duas realidades são diferentes. Referem-se aos contextos como apresentando caraterísticas distintas e onde se realizam atividades diferentes, diversificadas. Realça-se, ainda, que o relacionamento interpessoal entre e intra grupo que foi de extrema importância para facilitar a transição, tendo-se verificado união, companheirismo, colaboração e apoio constantes dentro do grupo.

Propagation of Behavioral Variations with Delegation Proxies

Scoping behavioral variations to dynamic extents is useful to support non-functional concerns that otherwise result in cross-cutting code. Unfortunately, such forms of scoping are difficult to obtain with traditional reflection or aspects. We propose delegation proxies, a dynamic proxy model that supports behavioral intercession through the interception of various interpretation operations. Delegation proxies permit different behavioral variations to be easily composed together. We show how delegation proxies enable behavioral variations that can propagate to dynamic extents. We demonstrate our approach with examples of behavioral variations scoped to dynamic extents that help simplify code related to safety, reliability, and monitoring.

Final environmental impact statement, general management plan/development concept plan for Natural Bridges National Monument /

"NPS D-18A"--P. [3] of cover.

Predicting the Paths of Peripherals: The Interaction of Identification and Future Possibilities

Two studies investigated how both degree of identification and the individual's position within the group influence aspects of group loyalty. The authors considered ingroup position in terms of both the individual's current position within a group and expectations concerning the likelihood that one's position might change., in the future. Peripheral group members learned that their acceptance by other group members would improve in the future or that they could expect rejection by other group members. Various indices of group loyalty (ingroup homogeneity, motivation to work for the group, and evaluation of a motivated group member) showed that when group members anticipated future rejection, the lower the identification the less loyal they were. In contrast, those who expected future acceptance were more loyal (more motivated to work for the group) the lower their identification. Current group behavior depends on both intragroup future expectations and level of identification.