On the role of specific interactions in the diffusion of nanoparticles in aqueous polymer solutions

Understanding nanoparticle diffusion within non-Newtonian biological and synthetic fluids is essential in designing novel formulations (e.g., nanomedicines for drug delivery, shampoos, lotions, coatings, paints, etc.), but is presently poorly defined. This study reports the diffusion of thiolated and PEGylated silica nanoparticles, characterized by small-angle neutron scattering, in solutions of various water-soluble polymers such as poly(acrylic acid) (PAA), poly(Nvinylpyrrolidone) (PVP), poly(ethylene oxide) (PEO), and hydroxyethylcellulose (HEC) probed using NanoSight nanoparticle tracking analysis. Results show that the diffusivity of nanoparticles is affected by their dimensions, medium viscosity, and, in particular, the specific interactions between nanoparticles and the macromolecules in solution; strong attractive interactions such as hydrogen bonding hamper diffusion. The water-soluble polymers retarded the diffusion of thiolated particles in the order PEO > PVP > PAA > HEC whereas for PEGylated silica particles retardation followed the order PAA > PVP = HEC > PEO. In the absence of specific interactions with the medium, PEGylated nanoparticles exhibit enhanced mobility compared to their thiolated counterparts despite some increase in their dimensions.

Investigation by Combined Solid-State NMR and SAXS Methods of the Morphology and Domain Size in Polystyrene-b-Polyethylene Oxide-b-Polystyrene Triblock Copolymers

The microphase structure of a series of polystyrene-b-polyethylene oxide-b-polystyrene (SEOS) triblock copolymers with different compositions and molecular weights has been studied by solid-state NMR, DSC, wide and small angle X-ray scattering (WAXS and SAXS). WAXS and DSC measurements were used to detect the presence of crystalline domains of polyethyleneoxide (PEO) blocks at room temperature as a function of the copolymer chemical composition. Furthermore, DSC experiments allowed the determination of the melting temperatures of the crystalline part of the PEO blocks. SAXS measurements, performed above and below the melting temperature of the PEO blocks, revealed the formation of periodic structures, but the absence or the weakness of high order reflections peaks did not allow a clear assessment of the morphological structure of the copolymers. This information was inferred by combining the results obtained by SAXS and (1)H NMR spin diffusion experiments, which also provided an estimation of the size of the dispersed phases of the nanostructured copolymers. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48:55-64,2010

Agar-based films for application as polymer electrolytes

New types of polymer electrolytes based on agar have been prepared and characterized by impedance spectroscopy, X-ray diffraction measurements, UV-vis spectroscopy and scanning electronic microscopy (SEMI). The best ionic conductivity has been obtained for the samples containing a concentration of 50 wt.% of acetic acid. As a function of the temperature the ionic conductivity exhibits an Arrhenius behavior increasing from 1.1 x 10(-4) S/cm at room temperature to 9.6 x 10(-4) S/cm at 80 degrees C. All the samples showed more than 70% of transparency in the visible region of the electromagnetic spectrum, a very homogeneous surface and a predominantly amorphous structure. All these characteristics imply that these polymer electrolytes can be applied in electrochromic devices. (C) 2009 Elsevier Ltd. All rights reserved.

En studie om rehabilitering - en skamgörande process

The purpose of this essay is using theories about labeling and social bonds to study whether a measure of rehabilitation for the psychically disabled contributes to a return to a normal status as not-labeled. Partly we examine whether the activities organized by the regulation-ruled authorities during the work of rehabilitation lead to shame or pride, and partly how these activities are organized regarding the processes that lead to the emotions pride or shame among the participants. Method: qualitative semi-structured face-to-face interviews with professional rehabilitation-actors at the Public Employment Office (PEO), the Social Insurance Office (SIO), the Social Service (SOS), the Psychiatry and the Division of Labour Market (AME).Conclusions: the Psychiatry clients are treated with respect, may participate, and communication is characterized by attunement, therefore strong social bonds can be built. On the contrary, among the other examined activities, we found many elements that arouse shame. Since these are more ruled by regulations, the result is engulfment and demands on conformity, because the compromise-possibilities are almost non-existent. Psychically disabled persons are met by prejudice, ignorance, disrespect and a non-solidarity-language. To get help, the individual has to accept a label in form of a diagnosis, and this labeling leads to a negative self-image. Furthermore the psychically disabled persons are falling between two chairs because of a weak cooperation between the rehabilitation-actors. Bimodal alienation and triangulation contributes to the difficulties in cooperation.Result: the social bonds are not strong enough to achieve a rehabilitation-effect. Even if the treatment from each administrator is important, we find the explanation-level primarily in laws, rules and government, because the structure rules the rehabilitation-measures, with shame as a consequence. Since we found elements of shame institutionalized in the way of working at PEO, SIO, SOS and AME, it means that social bonds can never reach a level good enough for achieving pride and normalization from a deviance or labeled identity.

Um estudo clínico, bioquímico, histoquímico e genético-molecular de pacientes com doenças do DNA mitocondrial

Introdução: As doenças mitocondriais apresentam características heterogêneas devido à própria natureza e função da mitocôndria, que possui o seu próprio DNA (mtDNA). A disfunção mitocondrial pode afetar um único órgão ou ser uma doença multissistêmica, de manifestação na infância ou na vida adulta, podendo ter um padrão de herança materna ou mendeliana. O diagnóstico é complexo e requer uma investigação criteriosa, passo-a-passo, com atenção a história clínica, exames laboratoriais, neuroimagem e, muitas vezes, a biópsia muscular para análise histoquímica, bioquímica e genética. A análise molecular é fundamental na definição do diagnóstico e os protocolos propostos até o momento são, geralmente, direcionados para um grupo de pacientes com características clínicas homogêneas. Objetivos: os objetivos deste trabalho foram: a) propor um protocolo combinando dados clínicos e laboratoriais para indicar a melhor forma de investigação molecular de pacientes com suspeita clínica de doença do DNA mitocondrial, b) Comparar os achados clínicos e laboratoriais nos pacientes com e sem mutação no mtDNA, c) avaliar quais são os fatores clínicos preditivos de mutação no mtDNA que podem ser utilizados como sinalizadores para o médico decidir quando deve ser realizado um procedimento diagnóstico invasivo e de alto custo, c) estimar a proporção de mtDNA mutado, através da técnica PCR em tempo real em um grupo de pacientes com deleção, correlacionando com a idade de início dos sintomas e gravidade de manifestações clínicas, d) relatar achados de RNM com espectroscopia por emissão de prótons em pacientes com deleção no mtDNA. Pacientes, material e métodos: Foram selecionados, no ambulatório de doenças mitocondriais do HCPA, 43 pacientes com suspeita clínica de doença mitocondrial. Esse pacientes foram submetidos à análise, por etapas, de 5 mutações de ponto no mtDNA de leucócitos, de deleção no mtDNA de músculo e ao sequenciamento do tRNAleu e tRNAlys. Os pacientes com resultados positivos e negativos para mutações do mtDNA foram então comparados em relação às suas características clínicas e laboratoriais. Foram selecionados 11 pacientes para a determinação da percentagem relativa de deleção do mtDNA no tecido muscular e 3 pacientes para a descrição da RNM com espectroscopia. Resultados – Foram encontradas mutações no mtDNA em 17 pacientes (39.9%) distribuídas da seguinte forma: 4 pacientes com MELAS (A3243G), 1 paciente com síndrome de Leigh (T8993C) e 12 pacientes com deleções no mtDNA. As características significativamente mais freqüentes no grupo de pacientes com mutação no mtDNA comparados com os demais foram: miopatia (p=0,032), retinopatia pigmentar (p=0,007), oftalmoplegia e ptose (p=0,002), baixa estatura (p=0,04), hipotrofismo (p=0,033) e acidose lática (p=0,006). A quantificação do mtDNA pela técnica de PCR em tempo real foi realizada em 11 amostras de músculo de pacientes com deleção no mtDNA e com diferentes manifestações clínicas. Não houve correlação entre a percentagem relativa de deleção no mtDNA com os fenótipos clínicos (PEO, KSS e encefalomiopatia associado à doença multissistêmica), bem como com a idade de início das manifestações clínicas. A RNM com espectroscopia por emissão de prótons realizada em três pacientes com deleção no mtDNA associada a um quadro clínico não clássico mostrou achados distintos para cada paciente, sendo comum a todos as lesões cerebrais e a presença do pico invertido de lactato. Conclusões - A criteriosa seleção clínica e laboratorial se mostrou apropriada e o protocolo empregado se mostrou eficiente, uma vez que a mutação no mtDNA pode ser detectada em 17 dos 43 pacientes com suspeita de doença mitocondrial. Os pacientes positivos para deleção no mtDNA apresentaram algumas características clínicas preditivas para doença do mtDNA, o que pode ser importante na indicação de um procedimento invasivo (biópsia muscular) e de alto custo. A técnica e PCR em tempo real pode ser utilizado para quantificar a percentagem relativa de mtDNA deletado, porém para o diagnóstico das deleções, essa técnica deve ser realizada de forma complementar à técnica tradicional (Southern blot). O número amostral ainda é pequeno para correlacionar a quantidade relativa de mtDNA deletado com as síndromes mitocondriais clássicas e não clássicas. A RNM com espectroscopia por emissão de prótons, por possibilitar a detecção do lactato cerebral, parece ter utilidade na avaliação clínica de pacientes com suspeita clínica de doença mitocondrial, mesmo quando o quadro não é clássico.

Processos produtivos e trabalho-educação: a incorporação do caboclo catarinense na indústria madeireira

The object theme of the present study is a population of caboclos that absorbed as manual workers in the saw-mills which were mounted in the highland region of Santa Catarina since 1950. The abundance of araucaria (native kind of pine) the opening of markets, and the corroboration of other industrial exploration conditions encouraged a great crowd of small en.- trepreneurs, coming basically from the state of Rio Grande do Sul, to migrate and settle down, building up a lot of saw-mills near rich forests and fields. The saw-mills started aprosperous production of timber sawn in planks. The process of industriali zation was so intensive, the destruction of pine woods soviolent that, in less than three decades, the forests ran out of tree reserves. The caboclos, absorbed as manual workers in production of timber, lived traditionally in an system of subsistense, either from the cultivation of pine the economic their land (planter caboclo) or as labourers in cattle-growing farms (farm hand caboclos). Nevertheless, the 'advantages' that were offered them by the new-comer entrepreneurs (a salary paid in money, a new house in a village, and other favours) helped the great majority of caboclos to abandon their traditional work and enlist as "workmen" in saw-mills. The new job, besides being a novelty, was an opportunity for a change in status. Subsequently, the running out of forests of araucaria and the resultant progressive shut-down of saw-mills caused the crowd of workmen to be out of imployment and to form to form a migratory flood toward the most important town of the region, Lages. The town of Lages, however, having made of the timber i ts main economic support wi thout the implantation of an alternative industry, was unable to offer the migrantssufficient 'work places'. In this way, the 'marginal crowd' began to settle down in the suburbs of the city. This study, in the context of the object theme, analyses two main questions related to the reality 'WOlLQ' and to the economic exploitation forms: ~) the relations of production in the economic regime of subsistence and in the capitalist regime of industrial production with the consequent 'positions' of the workman in the productive processj ~~) the deriving educative effects of the productive process, either in the economic regime of subsistence, or in the capitalist industrial regime. The two questions are theoretically debated andconfro~ ted with the proposed reality, giving origin to conclusions that, in a general formulation, can be summarized as follows: a) the caboclos of the highland region of Santa Catari na, when under an economic regime of subsistence, held in fee the productive processj there was a social division of the work and aclimate of freedom which made possible the development of knowledge from their life and work experience, the production of most of their tools, and the making of necessary manufactures adapted to their own surrounding ditionsi -- - --- other con- ------ b) however, these same caboclos, when absorbed by the capitalist industrial process of production - tipified by the work in saw-mills - lost the control of the productive processj this was caused by the technologic division of the work, since each man began to perform a dull and repeti tive action, directed by the speed of the 'major-saw' j man resigned form his skill and inventive power and surrendered to an executive authority which turned him into a 'collective worker'j the new productive process, besides rnaking each rnan a copy of a pattern, put the caboclos in a situation in which the daily work experiencedidn't add anything in terrns of autogenesis of knowledgei and even the environrnental educative rneans were reduced to new forrns of adaptation to the productive process, relegating rnan's inventive power to inertia.

A concessão de uso especial para fins de moradia na ordem jurídica brasileira: a medida provisória 2.220 a partir de uma análise constitucional

Este trabalho se propõe a analisar a posse dos bens públicos, sob a perspectiva do neoconstitucionalismo, com destaque para o princípio da função social da propriedade. A tese deste estudo se pautou na afirmativa de que a partir do surgimento da concessão de uso especial para fins de moradia, instituída pela Medida Provisória 2.220 para regulamentar o artigo 183, § 1º da Constituição Federal de 1988, a função social da propriedade, antes sobrelevada nos litígios envolvendo a posse dos bens públicos, passou a ser discutida no âmbito dos tribunais. Para a comprovação da referida tese, analisou-se a jurisprudência do Superior Tribunal de Justiça, dos Tribunais Regionais Federais das cinco regiões do país e dos Tribunais de Justiça do Estado do Rio de Janeiro e do Rio Grande do Sul. Feita esta análise, foi possível comprovar a tese defendida. Com o intuito de garantir a máxima eficácia ao princípio da função social da propriedade, defendeu-se a não delimitação temporal imposta pela MP 2.220, tendo por base quatro argumentos de índole constitucional, sendo eles, a observância da força normativa da Constituição, a aplicação dos tratados internacionais de Direitos Humanos, o respeito ao princípio da igualdade e, por fim, o princípio da supremacia da Constituição.

Deficientes visuais nas organizações: a exclusão no processo de inclusão

O presente estudo objetivou identificar como ocorre o processo de inclusão e exclusão do deficiente visual nas organizações, considerando tal deficiência como a mais representativa das deficiências no país. Apesar desse dado, os profissionais cegos são os que possuem menor índice de contratação pelas empresas, que optam por pessoas que possuem as chamadas “deficiências leves” para compor seu quadro de funcionários. Os deficientes visuais sofrem pelo estereótipo de incapacidade que carregam ao longo da história, mesmo com a presença da Lei de Cotas. Para a construção do estudo foi realizada uma pesquisa de campo, que contou com entrevistas semiestruturadas e observação participante. A conclusão a que se chegou sobre o processo de inclusão do deficiente visual, é que este ocorre praticamente no discurso dos representantes de RH das empresas, sendo visível a preferência de contratação de pessoas com deficiências consideradas “leves”, apesar do número de profissionais cegos disponíveis. O estereótipo de incapacidade laborativa aparece ligado a esse processo de exclusão do cego, que demonstra ocorrer por desconhecimento acerca da deficiência visual. Novas construções foram encontradas, como o estereótipo oriundo do próprio cego e também do direcionamento que instituições importantes apresentam para o desenvolvimento de deficientes visuais, que podem afetar de forma significativa a forma como se relacionam com os videntes.

Estudo da permeação em membranas quitosana

This study proposes to do a study on the mathematical modeling of permeation of films based on chitosan. To conduct the study were obtained membranes with various compositions: a virtually pure membrane-based chitosan; one of chitosan associated with poly (ethylene oxide (PEO). The membranes of pure chitosan were treated with plasma in atmospheres of oxygen, argon and methane. The various types of films were characterized as to its permeation regarding sufamerazina sodium. In the process of mathematical modeling were compared the standard method of obtaining the coefficient of permeation recital straight down the slope of the plot obtained by extinction / time with a the integration process of numerical permeability rate will be calculated from the spectroscopy UV

Thermal analysis of chitosan based networks

In this work two kinds of material were studied: chitosan cross-linked with glutaraldehyde and in a blend with PEO. The resulting products as well as chitosan and PEO raw materials, were analyzed by TG/DTG, DSC and DMTA to determinate the in?uence of cross-linking and PEO addition on thermal properties of the resulting materials. It was observed by thermogravimetry that the water-polymer interaction will be different for the cross-linked material compared to the blend, according to the specific site availability. The in?uence of such modifications (cross-linking and PEO addition), on chitosan thermal stability was also studied. The DSC results showed a good agreement with the TG/DTG results, reinforcing the interpretation given for TG/DTG results. DMTA results indicate that glass transition temperature is around 50 degrees C for the polymer under study. (c) 2005 Elsevier Ltd. All rights reserved.

Controlled Drug Release from Ureasil-Polyether Hybrid Materials

Flexible, transparent, and insoluble urea-cross-linked polyether-siloxane hybrids presenting a tunable drug delivery pattern were prepared using the sol-gel method from PEO (poly(ethylene oxide)) and PPO (poly(propylene oxide)) functionalized at both chain ends with triethoxysilane. Different polyether chain lengths were used to control the urea/siloxane (named ureasil) node density, flexibility, and swellability of the hybrid network. We herein demonstrate that the drug release from swellable hydrophilic ureasil-PEO hybrids can be sustained for some days, whereas that from the unswellable ureasil-PPO hybrids can be sustained for some weeks. This outstanding feature conjugated with the biomedically safe formulation of the ureasil cross-linked polyether-siloxane hybrid widens their scope of application to include the domain of soft and implantable drug delivery devices.

Membranas de quitosana micro e macroporosas : preparo, caracterização e estudos de permeabilidade

Two methodologies were proposed to obtain micro and macroporous chitosan membranes, using two different porogenic agents. The methodologies proved to be effective in control the porosity as well as the pore size. Thus, microporous membranes were obtained through the physical blend of chitosan and polyethylene oxide (PEO) on an 80:20 (m/m) ratio, respectively, followed by the partial PEO solubilization in water at 80 ◦C. Macroporous chitosan membranes with asymmetric morphology were obtained using SiO2 as the porogenic agent. In this case, chiotsan-silica ratios used were 1:1, 1:3 and 1:5 (m/m). Membranes characterization were carried out by SEM (scanning electronic microscopy), X-ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Thermal analysis (TG, DTG , DSC and DMTA). Permeability studies were performed using two model drugs: sodium sulfamerazine and sulfametoxipyridazine. By transmission FTIR it was possible to confirm the complete removal of SiO2. The SEM images confirmed the porous formation for both micro and macroporous membranes and also determined their respective sizes. By thermal analysis it was possible to show differences related with water sorption capacity as well as thermal stability for both membranes. DTG and DSC allowed evidencing the PEO presence on microporous membranes. The absorbance x time curves obtained on permeability tests for micro and macroporous membranes showed a linear behavior for both drugs in all range of concentration used. It was also observed, through P versus C curves, an increase in permeability of macroporous membranes according to the increase in porosity and also a decrease on P with increase in drug concentration. The influences of the drug molecular structure, as well as test temperatures were also evaluated

Obtenção e caracterização físico-química de blendas poliméricas, baseadas em POE e PMMA, dopadas com dióxido de titânio

The study of polymer blends has been an alternative method in the search field of new materials for obtaining materials with improved properties. In this work blends of poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) doped with titanium dioxide (TiO2) were studied. The PEO is a polymer semicrystalline structure varying between, 70 and 84% crystallinity, while the PMMA exhibits behavior amorphous in their structure. The use of TiO2 is related to corrosion-resistant of titanium as well as good heat transfer and other characteristics. The study of these polymer blends doped TiO2 gives the properties junction organic (polymer) and inorganic (oxide) which leads to modification of the properties of the resultant material. The blends were doped TiO2 (POE/PMMA/TiO2) in different proportions of the PMMA with the PEO and TiO2 fixed. The ratios were: 90/10/0,1; 85/15/0, 1; 80/20/0,1, 75/25/0,1 and 70/30/0,1. The resulting material was obtained in powder form and being characterized by Fourier Transformed Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Electrochemical Impedance Spectroscopy (EIS). The infrared spectra (IR) for the blends in different ratios showed a band at 1744 cm-1, characteristic of the C=O stretching, which increases in intensity with increasing PMMA composition, while in the spectrum of pure PEO this band is absent. This may suggest that the interaction is occurring between the polymers. In the micrographs of the blends also observed change in their surfaces with variation of the composition of PMMA, contributing to the change of the electrical properties of the material. The EIS data showed that the material exhibited conductivity of the order of 10-6 S.cm-1. The blend in the ratio B2(85/15/0, 1) showed better conductivity, σ = 1.56 x 10-6 S.cm-1. It was observed that the diffusion coefficient for the blends, B5(70/30/0, 1) was the largest, 1.07 x 10-6 m2.s-1. The XRD data showing that, with the variation in the composition of the PMMA blend crystallinity of the material is decreased reaching a minimum B3(80/20/0,1), and then increases again. Thermal analysis suggests that blends made from the material obtained can be applied at room temperature

Interaction between Pluronic F127 and Dioctadecyldimethylammonium Bromide (DODAB) Vesicles Studied by Differential Scanning Calorimetry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Polymer induced condensation of DNA supercoils

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)