The key role of polymer grafted nanoparticles in the phase miscibility of an LCST mixture

Blends of bromo-terminated polystyrene (PS-Br) and poly(vinyl methylether) (PVME) exhibit lower critical solution temperatures. In this study, PS-Br was designed by atom transfer radical polymerization and was converted to thiol-capped polystyrene (PS-SH) by reacting with thiourea. The silver nanoparticles (nAg) were then decorated with covalently bound PS-SH macromolecules to improve the phase miscibility in the PS-Br-PVME blends. Thermally induced demixing in this model blend was followed in the presence of polystyrene immobilized silver nanoparticles (PS-g-nAg). The graft density of the PS macromolecules was estimated to be ca. 0.78 chains per nm(2). Although the matrix and the grafted molecular weights were similar, PS-g-nAg particles were expelled from the PS phase and were localized in the PVME phase of the blends. This was addressed with respect to intermediate graft density and favourable PS-PVME contacts from microscopic interactions point of view. Interestingly, blends with 0.5 wt% PS-g-nAg delayed the spinodal decomposition temperature in the blends by ca. 18 degrees C with respect to the control blends. The scale of cooperativity, as determined by differential scanning calorimetry, increased only marginally in the case of PS-g-nAg; however, it increased significantly in the presence of bare nAg particles.

Mapping the intriguing transient morphologies and the demixing behavior in PS/PVME blends in the presence of rod-like nanoparticles

The demixing behavior, transient morphologies and mechanism of phase separation in PS/PVME blends were greatly altered in the presence of a very low concentration of rod-like particles (multiwall carbon nanotubes, MWNTs). This phenomenon is due to the specific interaction of one of the phases (PVME) with the anisotropic MWNTs, which creates a heterogeneous environment in the blend. This specific interaction alters the chain dynamics in the interfacial region as against the bulk. A comprehensive analysis using isochronal temperature sweep was performed to understand the demixing temperature in the blends. The evolution of phase morphology as a function of time and temperature was assessed by polarizing optical microscopy (POM), atomic force microscopy (AFM) and scanning electron microscopy (SEM). The addition of MWNTs increased the rheological demixing temperature and the spinodal temperature in almost all the compositions. The intriguing transient morphologies were mapped, which varied from nucleation and growth to coalescence-induced viscoelastic phase separation (C-VPS) in PVME-rich blends, to spinodal decomposition in the near-critical compositions, to transient gel-induced VPS (T-VPS) in the PS-rich compositions. Mapping of the morphology development displayed two types of fracture mechanisms: ductile fracture for near-critical compositions and brittle fracture for off-critical composition. The change in the phase separation mechanism in the presence of MWNTs was due to the variation in dynamic asymmetry brought about by these anisotropic particles. All these observations were correlated by POM, SEM and AFM studies. The length of the cooperatively rearranging region (CRR), as evaluated using modulated differential scanning calorimetry (MDSC) measurements, was found to be composition-independent. The observed variation of effective glass transition of PVME (low T-g component) on blending with PS (high Tg component) and by the addition of MWNTs accounts for the dynamic heterogeneity introduced by MWNTs in the system.

Selective localisation of multi walled carbon nanotubes in polypropylene/natural rubber blends to reduce the percolation threshold

Polypropylene and natural rubber blends with multiwalled carbon nanotube (PP/NR + MWCNT nanocomposites) were prepared by melt mixing. The melt rheological behaviour of neat PP and PP/NR blends filled with different loadings (1, 3, 5, 7 wt%) of MWCNT was studied. The effect of PP/NR blends (with compositions, 80/20,50/50, 20/80 by wt) on the rheological percolation threshold was investigated. It was found that blending PP with NR (80/20 and 50/50 composition) reduced the rheological percolation threshold from 5 wt% to 3 wt% MWCNT. The melt rheological behaviour of the MWCNT filled PP/NR blends was correlated with the morphology observations from high resolution transmission electron microscopic (HRTEM) images. In predicting the thermodynamically favoured location of MWCNT in PP/NR blend, the specific interaction of phospholipids in NR phase with MWCNTs was considered quantitatively. The MWCNTs were selectively localised in the NR phase. The percolation mechanism in MWCNT filled PP/NR blends was discussed and for each blend composition, the percolation mechanism was found to be different. (C) 2015 Elsevier Ltd. All rights reserved.

Nanoparticle induced miscibility in LCST polymer blends: critically assessing the enthalpic and entropic effects

The use of copolymer and polymer blends widened the possibility of creating materials with multilayered architectures. Hierarchical polymer systems with a wide array of micro and nanostructures are generated by thermally induced phase separation (TIPS) in partially miscible polymer blends. Various parameters like the interaction between the polymers, concentration, solvent/non-solvent ratio, and quenching temperature have to be optimized to obtain these micro/nanophase structures. Alternatively, the addition of nanoparticles is another strategy to design materials with desired hetero-phase structures. The dynamics of the polymer nanocomposite depends on the statistical ordering of polymers around the nanoparticle, which is dependent on the shape of the nanoparticle. The entropic loss due to deformation of polymer chains, like the repulsive interactions due to coiling and the attractive interactions in the case of swelling has been highlighted in this perspective article. The dissipative particle dynamics has been discussed and is correlated with the molecular dynamics simulation in the case of polymer blends. The Cahn Hillard Cook model on variedly shaped immobile fillers has shown difference in the propagation of the composition wave. The nanoparticle shape has a contributing effect on the polymer particle interaction, which can change the miscibility window in the case of these phase separating polymer blends. Quantitative information on the effect of spherical particles on the demixing temperature is well established and further modified to explain the percolation of rod shaped particles in the polymer blends. These models correlate well with the experimental observations in context to the dynamics induced by the nanoparticle in the demixing behavior of the polymer blend. The miscibility of the LCST polymer blend depends on the enthalpic factors like the specific interaction between the components, and the solubility product and the entropic losses occurring due to the formation of any favorable interactions. Hence, it is essential to assess the entropic and enthalpic interactions induced by the nanoparticles independently. The addition of nanoparticles creates heterogeneity in the polymer phase it is localized. This can be observed as an alteration in the relaxation behavior of the polymer. This changes the demixing behavior and the interaction parameter between the polymers. The compositional changes induced due to the incorporation of nanoparticles are also attributed as a reason for the altered demixing temperature. The particle shape anisotropy causes a direction dependent depletion, which changes the phase behavior of the blend. The polymer-grafted nanoparticles with varying grafting density show tremendous variation in the miscibility of the blend. The stretching of the polymer chains grafted on the nanoparticles causes an entropy penalty in the polymer blend. A comparative study on the different shaped particles is not available up to date for understanding these aspects. Hence, we have juxtaposed the various computational studies on nanoparticle dynamics, the shape effect of NPs on homopolymers and also the cases of various polymer blends without nanoparticles to sketch a complete picture on the effect of various particles on the miscibility of LCST blends.

Designer porous antibacterial membranes derived from thermally induced phase separation of PS/PVME blends decorated with an electrospun nanofiber scaffold

We report the development of porous membranes by thermally induced phase separation of a PS/PVME (polystyrene/polyvinylmethyl ether]) blend, which is a typical LCST mixture. The morphology of the membrane after etching out the PVME phase was characterized by scanning electron microscopy. To give the membrane an antibacterial surface, polystyrene (PS) and polyvinyl(methyl ether)]-alt-maleic anhydride (PVME-MAH) with silver nanoparticles (nAg) were electrospun on the membrane surface. Pure water flux was evaluated by using a cross-flow membrane setup. The microgrooved fibers changed the flux across the membrane depending on the surface properties. The antibacterial properties of the membrane were confirmed by the reduction in the colony count of E. coli. The SEM images show the disruption of the bacterial cell membrane and the antibacterial mechanism was discussed.

Differential dynamics of the serotonin(1A) receptor in membrane bilayers of varying cholesterol content revealed by all atom molecular dynamics simulation

The serotonin(1A) receptor belongs to the superfamily of G protein-coupled receptors (GPCRs) and is a potential drug target in neuropsychiatric disorders. The receptor has been shown to require membrane cholesterol for its organization, dynamics and function. Although recent work suggests a close interaction of cholesterol with the receptor, the structural integrity of the serotonin(1A) receptor in the presence of cholesterol has not been explored. In this work, we have carried out all atom molecular dynamics simulations, totaling to 3s, to analyze the effect of cholesterol on the structure and dynamics of the serotonin(1A) receptor. Our results show that the presence of physiologically relevant concentration of membrane cholesterol alters conformational dynamics of the serotonin(1A) receptor and, on an average lowers conformational fluctuations. Our results show that, in general, transmembrane helix VII is most affected by the absence of membrane cholesterol. These results are in overall agreement with experimental data showing enhancement of GPCR stability in the presence of membrane cholesterol. Our results constitute a molecular level understanding of GPCR-cholesterol interaction, and represent an important step in our overall understanding of GPCR function in health and disease.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Nanomechanical Mapping, Hierarchical Polymer Dynamics, and Miscibility in the Presence of Chain-End Grafted Nanoparticles

To improve the spatial distribution of nano particles in a polymeric host and to enhance the interfacial interaction with the host, the use of chain-end grafted nanoparticle has gained popularity in the field of polymeric nanocomposites. Besides changing the material properties of the host, these grafted nanoparticles strongly alter the dynamics of the polymer chain at both local and cooperative length scales (relaxations) by manipulating the enthalpic and entropic interactions. It is difficult to map the distribution of these chain-end grafted nanoparticles in the blend by conventional techniques, and herein, we attempted to characterize it by unique technique(s) like peak force quantitative nanomechanical mapping (PFQNM) through AFM (atomic force microscopy) imaging and dielectric relaxation spectroscopy (DRS). Such techniques, besides shedding light on the spatial distribution of the nanoparticles, also give critical information on the changing elasticity at smaller length scales and hierarchical polymer chain dynamics in the vicinity of the nanoparticles. The effect of one-dimensional rodlike multiwall carbon nanotubes (MWNTs), with the characteristic dimension of the order of the radius of gyration of the polymeric chain, on the phase miscibility and chain dynamics in a classical LCST mixture of polystyrene/ poly(vinyl methyl ether) (PS/PVME) was examined in detail using the above techniques. In order to tune the localization of the nanotubes, different molecular weights of PS (13, 31, and 46 kDa), synthesized using RAFT (reversible addition fragmentation chain transfer) polymerization, was grafted onto MWNTs in situ. The thermodynamic miscibility in the blends was assessed by low-amplitude isochronal temperature sweeps, the spatial distribution of MWNTs in the blends was evaluated by PFQNM, and the hierarchical polymer chain dynamics was studied by DRS. It was observed that the miscibility, concentration fluctuation, and cooperative relaxations of the PS/PVME blends are strongly governed by the spatial distribution of MWNTs in the blends. These findings should help guide theories and simulations of hierarchical chain dynamics in LCST mixtures containing rodlike nanoparticles.

Determinación de la calidad fitosanitaria de la semilla de frijol común en Nicaragua y alternativas de manejo del grano

En Nicaragua el género Phaseolus, representa una fuente importante de nutrientes que la población incluye en su dieta diaria, además provee ingresos a los productores con los que subsanan una parte de sus necesidades, El 95% de la producción de frijol en el país descansa en pequeños y medianos productores que enfrentan problemas como: Falta de asistencia técnica, poca o ninguna disponibilidad de créditos, poseen terrenos no adecuados para este cultivo y el uso constante de semillas remanentes de un ciclo a otro; Esto ha incidido de forma directa en la disminución de los rendimientos y en el aumento de los niveles de inoculo en la semilla. Son muchas las enfermedades que atacan a esta leguminosa y algunas de estas llegan a infestar y/o infectar la semilla logrando así un eficiente mecanismo de dispersión. Con el objetivo de conocer sobre la calidad fitosanitaria de la semilla utilizada por los productores, evaluar algunas técnicas para la preservación de la misma, determinar el nivel de conocimiento de los productores con respecto a las enfermedades y discernir sobre la efectividad de las técnicas de almacenamiento de la semilla utilizadas por los productores, se realizó este trabajo involucrando 75 productores del país, logrando recolectar de sus manos un total de 15 variedades las que corresponden a los nombres de: DOR-364, RAB-310, Honduras-46, Estelí-150, Estelí-90A, Estelí-B, Negro, Blanco, Chiricano, Rojo criollo, DICTA-114, Balin tíco, Revolución-84 y dos variedades del Centro Nacional de Investigación Agropecuaria (CNIA), DOR-805 y DOR-576. El trabajo se dividió en dos fases: una de campo que consistió en la colecta de datos y muestras de semillas en las zonas de estudio en el mes de Marzo y una de laboratorio en la que se determinaron los diferentes tipos de microorganismos presente en las semillas a través de Observación de síntomas, pruebas de laboratorio y identificación de los microorganismos. Se hizo una prueba de almacenaje mediante el uso de botes plásticos con tapadera, los tratamientos utilizados para la preservación fueron• Cal, Ceniza y Ceniza+Cal en dosis de 80gr de producto por libra de semilla, más o menos 25 libras por quintal de grano y un testigo. Los resultados de las encuestas demuestran que los productores reconocen las enfem1edades como tales, pero no pueden diferenciarlas en su totalidad como causadas por hongos, bacterias o virus. Se identificaron los siguientes patógenos: Rhizoctonia sotaní, Thanatephoms cucumeris, Collectotrichum lindemuthianum, Fusarium solani, Fusarium poae, Fusarium tricinctum, l-i1sarium oxyspomm, Penicillium .;pp, Aspergillus ochraceus, Aspergillus ustus, Aspergillus glaucus (Emericella nidulans)(Eim>tium link), Aspergiilus niger, Aspergillus parasitim Aspergillus candidus, Aspergillus terreus, Rhizopus oryzae, Rhizopus stolonifer, Xanthomona;• campestris pv phaseoli, Pseudomonas spp, el virus del mosaico común no se detectó en este trabajo. Los mejores resultados se observaron en los tratamientos de cal y cal+ceniza, siendo cal+ceniza quién presentó alta significancia en la disminución de la infección por hongos, gorgojos (Bruchidae) y bacterias, pudiendo disminuir hasta un 57% las infecciones de hongos, un 68% de las infecciones por bacterias a nivel superficial y un l 00% la población de gorgojos, con respecto a las presentadas por el testigo de laboratorio. El tratamiento de cal+ceniza es más barato, eficaz y menos peligroso que el uso de cualquier químico.

Prolegómenos al análisis de la esfera social en el pensamiento ambiental multimodal

Resumen: En el presente trabajo abordamos la modalidad social en el pensamiento ambiental multimodal. La reflexión requiere primero la descripción del método de acceso, motivo por el cual revisamos la actividad logos en el análisis de la aprehensión primordial. El estudio de la dimensión social requiere repasar la aprehensión de las cosas y luego de los hechos sociales, para finalmente interesarnos por el estudio de la acción. Esto permite mostrar cómo el ambiente y los otros están siempre ya presentes en cada acción propia. Los resultados obtenidos permiten desarrollar una estructura de base para cualquier construcción teórica posterior que dé cuenta de la integración del hombre con la naturaleza y con los otros, mostrando la inseparable relación del ser humano con su ambiente y con su prójimo. Lo anterior sirve como protosociología de la modalidad social.

Zootecnia equina : Apuntes de clases sobre el caballo (Documento de estudio para estudiantes de Ingeniería en Zootecnia)

Estos apuntes de clases han sido preparados para la asignatura de Zootecnia Equina que se imparte en el sexto semestre de la carrera Ingeniería en Zootecnia dictado por el Departamento Sistemas Integrales de Producción Animal (SIPA) de la Facultad de Ciencia Animal. Gran parte del contenido está basado en anotaciones de clases y de algunos artículos técnicos de páginas electrónicas de Internet. Si el lector encuentra en estos apuntes alguna información útil se la debo a las personas experimentadas en la cría caballar y que han escrito e investigado sobre la producción equina, por los errores, que con seguridad existen, asumo total responsabilidad. El contenido de estos apuntes debe cubrir la mayor parte de los temas a tratar en la asignatura, pero en ningún caso reemplazar a un buen texto de estudio. La ganadería equina en Nicaragua se inició desde la época de la conquista española, cuando los colonizadores introdujeron los primeros ejemplares. Las primeras yeguadas traídas en ese entonces correspondían al tipo berberisco español, animales de aptitud cárnica. Estos se abandonaron a la buena de Dios, sobreviviendo los más aptos y los que toleraron las condiciones de nuestro medio, dando lugar así a la formación del caballo criollo o cholenco, animal con muy baja capacidad productiva. La explotación de equinos ofrece para Nicaragua desde el punto de vista económico perspectivas excelentes, en primer lugar por su fácil adaptación en las zonas secas y en segundo lugar porque su alimentación se limita a los pastos de cada región. La población equina de Nicaragua, según la FAO (2006), es de 268.000 cabezas. Para la elaboración de este compendio, hice uso de bibliografía elaborada por varios estudiosos del ganado equino, así como de las observaciones y la experiencia acumulada en los años que llevo de investigar sobre esta especie animal. Los aspectos principales abordados en el presente texto son: Historia, Evolución y Domesticación del Caballo, Importancia y caracterización del exterior del caballo, Clasificación del caballo, Razas explotadas en el mundo y Nicaragua, Sistemas de producción y manejo del caballo, Condiciones ambientales e instalaciones para caballos, Identificación y Registros del Caballo y Enfermedades más comunes, entre otros. Quiero aprovechar este medio para agradecer a reconocidos caballistas del país que desde 1990 nos han brindado su apoyo para reforzar los conocimientos de nuestros estudiantes al permitirnos el ingreso a sus cuadras como son: Sra. Lorena Mántica, Sr. Xavier Aguirre S., Sr. Octavio Lacayo Crespo, Sr. Pepe Matus, Sr. René Bequillard, Sr. José Domingo Bolaños, y a reconocidos entrenadores como el Sr. Julián García T., Sr. Francisco Reyes, Sr. Luís Arróliga, Sr. Arsenio González, Sr. Roy Gaitán y otros conocedores de la cría caballar, que afablemente nos han regalado su valioso tiempo. Por eso, apreciados alumnos y amigos es mi propósito contribuir en la formación de ustedes, con los temas que desarrollo a continuación, y asesorarlos con las correctas técnicas de la Equinotecnia. Aprovechen este texto, estúdienlo, infórmense y aprópiense de él para llevarlo a la práctica.

Sapientia, 2004, Vol. LIX, nº 216 (número completo)

Contenido: Josef Pieper en el centenario de su nacimiento / Héctor J. Delbosco – Misterio filosófico y misterio teológico en Josef Pieper y en Santo Tomás de Aquino / Ignacio Andereggen – El status de la filosofía en la posciencia. Respuestas desde Josef Pieper / Miriam Dolly Arancibía de Calmels – “Miseria y esplendor de la interpretación”. En torno a los límites de la hermenéutica en Pieper y en Ortega / Roberto E. Aras – Si sí : la condicionalidad metafísica de una afirmación absoluta / Santiago Argüello – Una perspectiva del saber y de la fortaleza en el héroe unamuniano a la luz de Josef Pieper / Angélica S. Arza de Bousquet – Manía, mito y conmoción erótica / Luis Baliña ; Juan Torbidoni – Juventud, fiesta y esperanza en la obra de Josef Pieper : una respuesta a la cultura posmoderna / Santiago Bellomo – Pieper y Guardini en Rothenfels : un encuentro fecundo / Alberto Berro – La afirmación real del amor / María José Binetti – Josef Pieper al encuentro de Platón : una relectura de las relaciones entre mito y filosofía / Claudio Calabrese – Orientación y pautas de discernimiento en el ámbito poético-literario : la doctrina de la contemplación terrena enunciada por Josef Pieper e ilustrada en Albert Camus / Inés de Cassagne – La imposibilidad de una filosofía no cristiana según Josef Pieper / Agustín Ignacio Echavarría – Ética y psicoterapia según Josef Pieper / Martín Echavarría – Enseñanzas de un gran maestro : la corruptibilidad de la palabra / María del Carmen Fernández – La inspiración platónica de la filosofía de Josef Pieper / Juan Francisco Franck – Método y lenguaje en el pensamiento de Josef Pieper / Jean Lauand – Josef Pieper y Peter Wust / Juan Andrés Levermann – Aprobación creadora : un aspecto de la dimensión social del bien de la persona / Marisa Mosto – Josef Pieper y la reflexión sobre el mito y la cultura / Héctor Jorge Padrón – Josef Pieper y el tomismo medieval : la controversia sobre la creación / François-Xavier Putallaz – Algunas consideraciones sobre J. Pieper y el tema del mal en la problemática filosófica contemporánea / Juan Pablo Roldán – Josef Pieper y la acedia : la causa afectiva de ciertas deformaciones intelectuales / El hombre de ocio : parásito o transformador del mundo / Bernard N. Schumacher – La templanza en Josef Pieper y Santo Tomás / Zelmira Seligmann – El ideal del trabajo en Josef Pieper / Ludovico Antonio Videla – Valor para la realidad – Valor para la persona : reafirmación cristiana como crítica de la cultura en la obra temprana de Josef Pieper / Berthold Wald – Notas y comentarios -- Bibliografía

[Discurso do Deputado Celso Barros : Sessão Conjunta do Congresso Nacional de 03 de outubro de 1985]

Destaca a peculiaridade da situação de Brasília, tendo em vista a falta de representação política da capital da República. Declara apoio a PEC n. 83/1985, Emenda Paulo Xavier, que dispõe sobre eleições gerais no Distrito Federal.

Planejamento estratégico do Detaq : um histórico e seus primeiros resultados

Aborda o processo de planejamento estratégico do Departamento de Taquigrafia (Detaq), destacando as iniciativas e os eventos relacionados à renovação de práticas administrativas.