Cetyltrimethylammonium chloride (CTAC) effect on the thermal stability of oxy-HbGp: Dynamic light scattering (DLS) and small angle X-ray scattering (SAXS) studies

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

Characterization of Rhinodrilus alatus hemoglobin (HbRa) and its subunits: Evidence for strong interaction with cationic surfactants DTAB and CTAC

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Influence of the Type of Quaternary Ammonium Salt Used in the Organic Treatment of Montmorillonite on the Properties of Poly(Styrene-co-Butyl Acrylate)/Layered Silicate Nanocomposites Prepared by In Situ Miniemulsion Polymerization

Hybrid latices of poly(styrene-co-butyl acrylate) were synthesized via in situ miniemulsion polymerization in the presence of 3 and 6 wt % organically modified montmorillonite (OMMT). Three different ammonium salts: cetyl trimethyl ammonium chloride (CTAC), alkyl dimethyl benzyl ammonium chloride (Dodigen), and distearyl dimethyl ammonium chloride (Praepagen), were investigated as organic modifiers. Increased affinity for organic liquids was observed after organic modification of the MMT. Stable hybrid latices were obtained even though miniemulsion stability was disturbed to some extent by the presence of the OMMTs during the synthesis. Highly intercalated and exfoliated polymer-MMT nanocomposites films were produced with good MMT dispersion throughout the polymeric matrix. Materials containing MMT modified with the 16 carbons alkyl chain salt (CTAC) resulted in the largest increments of storage modulus, indicating that single chain quaternary salts provide higher increments on mechanical properties. Films presenting exfoliated structure resulted in the largest increments in the onset temperature of decomposition. For the range of OMMT loading studied, the nanocomposite structure influenced more significantly the thermal stability properties of the hybrid material than did the OMMT loading. The film containing 3 wt % MMT modified with the two 18 carbons alkyl chains salt (Praepagen) provided the highest increment of onset temperature of decomposition. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 119: 3658-3669, 2011

Imagem de destinos turísticos: um estudo sobre as publicações brasileiras

Os estudos referentes ao turismo dedicam-se à compreensão de diferentes temas, sendo que um bastante analisado à escala internacional é a questão da imagem de um destino turístico. O interesse por este tema é percebido em diversas áreas do conhecimento, como a sociologia e o marketing. No Brasil, há diversos pesquisadores dedicando-se à imagem dos destinos turísticos. Assim, buscando compreender de que forma este tema tem sido trabalhado no Brasil, este estudo de caráter bibliográfico teve como objetivo analisar e compreender as publicações sobre imagem de destinos turísticos em periódicos brasileiros, nos últimos seis anos (2008-2014). A partir de um levantamento dos artigos publicados neste período, usando como ferramenta de busca o site “Publicações de Turismo”, foram identificados vinte e oito artigos. A análise permitiu verificar que os estudos estão concentrados na compreensão da imagem de um determinado destino. Os artigos analisados são predominantemente estudos empíricos e há um equilíbrio entre os de caráter quantitativo e qualitativo. No que diz respeito à bibliografia, foi possível identificar que os autores brasileiros que têm trabalhado com o tema de imagem de destinos, já buscam bibliografias internacionais para fundamentar os seus estudos. Também nos trabalhos sobre este tema, identificou-se uma maior maturidade dos autores no que diz respeito à utilização das ferramentas estatísticas. Alguns estudos fazem uma análise aprofundada dos estudos internacionais e aplicam estas teorias no Brasil. Conclui-se que este tema tem sido estudado com maior profundidade no país, se comparado com os temas como o da percepção de residentes.

Características químicas de substratos utilizados na produção de mudas de cacaueiros

O objetivo deste trabalho foi realizar monitoramento químico de seis substratos utilizados na produção de mudas de cacaueiros. Os substratos receberam 10 volumes (100mL, cada) de água destilada, e no lixiviado coletado foram determinados o pH, a condutividade elétrica (CE) e os teores de sódio (Na) e potássio (K) em solução. Os valores de pH variaram de 5,0 a 8,0 em Plantmax® e composto do tegumento da amêndoa do cacau (CTAC), respectivamente. Verificou-se que, a partir do primeiro volume lixiviado, a CE de todos os substratos foi reduzida. Foram encontradas correlações positivas para a CE em relação ao K e Na da fibra de coco (FC) (r=0,83 e 0,72 P<0,05) e CTAC (r=0,98 e 0,99 P<0,05). Os resultados indicam que a FC e o CTAC deveriam ser usados após pré-lavagens. Verificou-se que, embora a FC apresente na primeira lixiviação valor de CE superior aos demais substratos, o valor ideal da 2,0 dSm-1 é alcançado na segunda lixiviação. Os teores de K e Na são um indicativo do valor da CE em FC e CTAC.

Determinação de cádmio em amostras de urina e soro humano por espectrometria de absorção atômica em forno de grafite usando irídio como modificador permanente

No presente estudo, foram investigadas diferentes substâncias para atuarem como modificadores químicos na determinação direta de cádmio em soro e urina humanos sem digestão prévia das amostras. A preparação da amostra foi feita diretamente nos copos do amostrador automático por diluição 1+4 de soro e 1+1 de urina com ácido nítrico 1% v/v contendo 0.02% v/v de cloreto de tricetil metil amônio (CTAC). Foram investigadas as melhores condições de determinação por meio de curvas de temperatura de pirólise e atomização na presença da matriz e do analito levando-se em conta a forma do pulso de absorção, baixas temperaturas na atomização, fundo corrigido e sensibilidade. Foram efetuados estudos na ausência de modificador e com a mistura universal em solução de Pd e Mg (10 e 15 µg, respectivamente) e com rutênio (500 µg) e irídio (500 µg) como modificadores permanentes. Para Ir permanente, as massas características foram 0.8 pg para soro e 0.7 pg para urina (recomendado de 2 pg). Na investigação do uso de Ir permanente, foi observado que o pico foi simétrico, retornando à linha de base em 3s e com fundo corrigido completamente com valores ótimos por pirólises e atomização de 300 e 1000°C para soro e 300 e 1100ºC para urina. A calibração foi feita por ajuste de matriz e apresentou coeficiente de correlação de regressão linear típico de 0.999. Análises de soro e urina fortificados mostraram recuperações que variaram entre 99.3 e 103.2 com um desvio padrão relativo (RSD, n=3) menor que 12% para soro e entre 93.1 e 102.2% com um RSD menor que 3% para urina. O limite de detecção (k=3, n=10) foi de 8 e 9 pg para soro e urina, respectivamente.

El profesor frente al trabajo cooperativo : variables que determinan la elección del trabajo cooperativo como método de instrucción.

Estudiar los métodos cooperativos y su relación con la motivación que muestran los alumnos hacia el aprendizaje, profundizando sobre su eficacia y analizando las variables que pueden estar incidiendo en los docentes para no trabajar con ellos. Hipótesis: 1) los profesores no utilizan con la frecuencia precisa los trabajos cooperativos como para que sus efectos hagan mella sobre los alumnos; 2) existen una serie de variables que posiblemente están incidiendo en la escasa utilización de los métodos cooperativos por parte de los profesores. Exhaustiva revisión bibliográfica. Se aplicaron 5 cuestionarios a 248 profesores en ejercicio, de centros públicos, privados y concertados de la Comunidad Autónoma de Madrid, durante el curso 1995-96, de tercero de Primaria a segundo de ESO. La comprobación de la frecuencia de uso de los métodos cooperativos en las aulas constituyó el primer paso dentro del desarrollo experimental. En la segunda parte del trabajo se analizan las variables que pueden estar incidiendo en los docentes para no trabajar con estos métodos de forma sistemática. Variables: variables moduladoras; percepción de los profesores sobre las técnicas cooperativas; valoraciones escuchadas sobre la técnica cooperativa; variables relacionadas con la jerarquía de motivos; valor didáctico general atribuído por los docentes a actividades concretas de tipo cooperativo; variables relacionadas con los conocimientos de los profesores sobre la técnica cooperativa. Cuestionario FTCA.ME; Cuestionario EX-TCA.ME; Test de Percepción Temática de Alonso Tapia, Huertas y Montero; Cuestionario con tres versiones equivalentes (C5-CN.ME, C8-LE.ME y C8-CN.ME); Cuestionario CTAC.MEC. Los métodos de trabajo cooperativo no son usados de forma mayoritaria por los profesores. Existe una serie de variables que no tienen incidencia en las decisiones de los profesores en relación al método elegido por ellos, como son: edad, años de docencia, materia impartida, curso y ratio, experiencia previa como alumnos, y orientación motivacional. Pero sí existen otras variables que pueden estar incidiendo: el grado de acuerdo con la técnica, el tipo de centro, las actitudes hacia el método, y la valoración didáctica. Así, las técnicas cooperativas se usan más en los colegios públicos que en los privados. Los profesores que más usan estas técnicas son aquellos que más las valoran y más acuerdo muestran con sus diversos aspectos. Consideran mejores las actividades grupales que las individuales en relación a su influencia sobre el aprendizaje significativo y la motivación. Valoran más positivamente las actividades abiertas que las cerradas, independientemente del tipo de agrupación. Los profesores no conocen las técnicas cooperativas lo suficiente como para utilizarlas con garantía de éxito en sus aulas. Aparece, sin embargo, una cierta tendencia a usar más los métodos competitivos cuando éstos se conocen. Al menos desde el punto de vista teórico, nos encontramos ante un buen método: coherente, útil de cara a los objetivos escolares, efectivo y factible de ser llevado a la práctica diaria. Utilizado de forma correcta y con la frecuencia precisa, potencia y desarrolla en los alumnos una serie de efectos deseables desde el punto de vista humano. Los métodos cooperativos incrementan, además y de manera importante, la motivación intrínseca de los alumnos hacia el aprendizaje escolar. Pese a ello, diversos autores insisten en su escasa utilización en el ámbito escolar. Sería deseable incrementar el uso de los métodos cooperativos en aquellos casos en los cuales los alumnos pueden obtener un beneficio claro con la utilización sistemática de estas técnicas, para lo cual haría falta tomar en consideración aspectos como: fomentar el trabajo grupal de los propios docentes, resolver los problemas organizativos y de evaluación que aún presentan estos métodos, dar estrategias a los futuros docentes para resolver los problemas que puedan surgirles, formar a los futuros docentes en cuáles son las mejores condiciones de uso de estos métodos para maximizar sus efectos, y formales sobre la forma más adecuada de crear el contexto cooperativo previo, habría que mostrarles la importancia de valorar más los procesos frente a la evaluación de productos, dotarles de los conocimientos necesarios sobre las distintas técnicas y métodos que están a su disposición, mostrando sus ventajas e inconvenientes e indicando cuáles son más adecuadas en función de los grupos, los individuos, la materia y los objetivos a lograr. Además, es importante que los profesores se muestren más flexibles en relación a su propio rol como docentes y que tomen conciencia cierta de que el desarrollo de actitudes como la solidaridad, la aceptación de la diferencia, el respeto a la opinión del otro y la ayuda desinteresada a los demás son objetivos escolares tanto o más importantes que la propia instrucción.

Molecular dynamics simulations of threadlike cetyltrimethylammonium chloride micelles: effects of sodium chloride and sodium salicylate salts

We use atomistic molecular dynamics simulations to probe the effects of added sodium chloride (NaCl) and sodium salicylate (NaSal) salts on the spherical-to-threadlike micelle shape transition in aqueous solutions of cetyltrimethylammonium chloride (CTAC) surfactants. Long threadlike micelles are found to be unstable and break into spherical micelles at low concentrations or NaCl, but remain stable for 20 ns above a threshold value of [NaCl] approximate to 3.0 M, which is about 2.5 times larger than the experimental salt concentration at which the transition between spherical and rodlike micelles occurs. The chloride counterions associate weakly oil the surface of the CTAC micelles with the degree of counterion dissociation decreasing slightly with increasing [NaCl] on spherical micelles, but dropping significantly on the threadlike micelles tit high [NaCl]. This effect indicates that the electrolyte ions drive the micellar shape transition by screening the electrostatic repulsions between the micellar headgroups, The aromatic salicylate counterions, on the other hand, penetrate inside the micelle with their hydrophilic groups staying in the surfactant headgroup region and the hydrophobic groups partially embedded into the hydrophobic core of the micelle. The strong association of the salicylate ions with the surfactant headgroups leads to dense packing of the surfactant molecules, which effectively reduces the surface area per surfactant, and increases intramicellar ordering of the surfactant headgroups, favoring the formation of long threadlike micelles. Simulation predictions of the geometric and electrostatic properties of the spherical and threadlike micelles are in good agreement with experiments.

On the localization of water-soluble porphyrins in micellar systems evaluated by static and time-resolved frequency-domain fluorescence techniques

Fluorescence quenching of meso-tetrakis-4-sulfonatophenyl (TPPS4) and meso-tetrakis-4-N-methylpyridil (TMPyP) porphyrins is studied in aqueous solution and upon addition of micelles of sodium dodecylsulfate (SDS), cetyltrimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and t-octylphenoxypolyethoxyethanol (Triton X-100). Potassium iodide (KI) was used as quencher. Steady-state Stern-Volmer plots were best fitted by a quadratic equation, including dynamic (K-D) and static (K-s) quenching. Ks was significantly smaller than K-D. Frequency-domain fluorescence lifetimes allowed estimating bimolecular quenching constants, k(q). At 25 degrees C, in aqueous solution, TMPyP shows k(q), values a factor of 2-3 higher than the diffusional limit. TPPS4 shows collisional quenching with pH dependent k(q) values. For TMPyP quenching results are consistent with reported binding constants: a significant reduction of quenching takes place for SDS, a moderate reduction is observed for H PS and almost no change is seen for Triton X-100. Similar data were obtained at 50 C. For CTAC-TPPS4 system an enhancement of quenching was observed as compared to pure buffer. This is probably associated to accumulation of iodide at the cationic micellar interface. The attraction between CTAC headgroups and 1(-), and repulsion between SDS and 1(-), enhances and reduces the fluorescence quenching, respectively, of porphyrins located at the micellar interface. The small quenching of TPPS4 in Triton X-100 is consistent with strong binding as reported in the literature. (C) 2008 Elsevier B.V. All rights reserved.

Effects of Micelles and Vesicles on the Oximolysis of p-Nitrophenyl Diphenyl Phosphate: A Model System for Surfactant-Based Skin-defensive Formulations against Organophosphates

The rates of oximolysis of p-nitrophenyl diphenyl phosphate (PNPDPP) by Acetophenoxime; 10-phenyl-10-hydi-oxyiminodecanoic acid; 4-(9-carboxynonanyl)-1-(9-carboxy-1-hydroyiminononanyl) benzene; 1-dodecyl-2-[(hydroxyimino)methyl]-pyridinium chloride (IV) and N-methylpyridinium-2-aldoxime chloride were determined in micelles of N-hexadecyl-N,N,N-trimethylammonium chloride (CTAC), N-hexadecyl-N,N-dimethylammonium propanesulfonate and dioctadecyldimethylammonium chloride (DODAC) vesicles. The effects of CTAC micelles and DODAC vesicles on the rates of oxymolysis of O,O-Diethyl O-(4-nitrophenyl) phosphate (paraoxon) by oxime IV were also determined. Analysis of micellar and vesicular effects on oximolysis of PNPDPP, using pseudophase or pseudophase with explicit consideration of ion exchange models, required the determination of the aggregate`s effects on the pK(a), of oximes and on the rates of PNPDPP hydrolysis. All aggregates increased the rate of oximolysis of PNPDPP and the results were analyzed quantitatively. In particular, DODAC vesicles catalyzed the reaction and increased the rate of oximolysis of PNPDPP by IV several million fold at pH`s compatible with pharmaceutical formulations. The rate increase produced by DODAC vesicles on the rate of oximolysis paraoxon by IV demonstrates the pharmaceutical potential of this system, since the substrate is used as an agricultural defensive agent and the surfactant is extensively employed in cosmetic formulations. (C) 2008 Wiley-Liss, Inc. and the American Pharmacists Association J Pharm Sci 98:1040-1052, 2009

On the interaction of bovine serum albumin with ionic surfactants: Temperature induced EPR changes of a maleimide nitroxide reflect local protein dynamics and probe solvent accessibility

The interaction of bovine serum albumin (BSA) with the ionic surfactants sodium dodecylsulfate (SDS, anionic), cetyltrimethylammonium chloride (CTAC, cationic) and N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS, zwitterionic) was studied by electron paramagnetic resonance (EPR) spectroscopy of spin label covalently bound to the single free thiol group of the protein. EPR spectra simulation allows to monitor the protein dynamics at the labeling site and to estimate the changes in standard Gibbs free energy, enthalpy and entropy for transferring the nitroxide side chain from the more motionally restricted to the less restricted component. Whereas SDS and CTAC showed similar increases in the dynamics of the protein backbone for all measured concentrations. HPS presented a smaller effect at concentrations above 1.5 mM. At 10 mM of surfactants and 0.15 mM BSA, the standard Gibbs free energy change was consistent with protein backbone conformations more expanded and exposed to the solvent as compared to the native protein, but with a less pronounced effect for HPS. In the presence of the surfactants, the enthalpy change, related to the energy required to dissociate the nitroxide side chain from the protein, was greater, suggesting a lower water activity. The nitroxide side chain also detected a higher viscosity environment in the vicinity of the paramagnetic probe induced by the addition of the surfactants. The results suggest that the surfactant-BSA interaction, at higher surfactant concentration, is affected by the affinities of the surfactant to its own micelles and micelle-like aggregates. Complementary DLS data suggests that the temperature induced changes monitored by the nitroxide probe reflects local changes in the vicinity of the single thiol group of Cys-34 BSA residue. (C) 2011 Elsevier B.V. All rights reserved.

Interaction of giant extracellular Glossoscolex paulistus hemoglobin (HbGp) with zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS): Effects of oligomeric dissociation

The present work focuses on the interaction between the zwitterionic surfactant N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and the giant extracellular hemoglobin of Glossoscolex paulistus (HbGp). Electronic optical absorption, fluorescence emission and circular dichroism spectroscopy techniques, together with Gel-filtration chromatography, were used in order to evaluate the oligomeric dissociation as well as the autoxidation of HbGp as a function of the interaction with HPS. A peculiar behavior was observed for the HPS-HbGp interaction: a complex ferric species formation equilibrium was promoted, as a consequence of the autoxidation and oligomeric dissociation processes. At pH 7.0, HPS is more effective up to 1 mM while at pH 9.0 the surfactant effect is more intense above 1 mM. Furthermore, the interaction of HPS with HbGp was clearly less intense than the interaction of this hemoglobin with cationic (CTAC) and anionic (SDS) surfactants. Probably, this lower interaction with HPS is due to two factors: (i) the lower electrostatic attraction between the HPS surfactant and the protein surface ionic sites when compared to the electrostatic interaction between HbGp and cationic and anionic surfactants, and (ii) the low cmc of HPS, which probably reduces the interaction of the surfactant in the monomeric form with the protein. The present work emphasizes the importance of the electrostatic contribution in the interaction between ionic surfactants and HbGp. Furthermore, in the whole HPS concentration range used in this study, no folding and autoxidation decrease induced by this surfactant were observed. This is quite different from the literature data on the interaction between surfactants and tetrameric hemoglobins, that supports the occurrence of this behavior for the intracellular hemoglobins at low surfactant concentration range. Spectroscopic data are discussed and compared with the literature in order to improve the understanding of hemoglobin-surfactant interaction as well as the acid isoelectric point (pI) influence of the giant extracellular hemoglobins on their structure-activity relationship. (c) 2007 Elsevier B.V. All rights reserved.

Interaction of bovine serum albumin (BSA) with ionic surfactants evaluated by electron paramagnetic resonance (EPR) spectroscopy

EPR spectra of 5- and 16-doxyl stearic acid nitroxide probes (5-DSA and 16-DSA, respectively) bound to bovine serum albumin (BSA) revealed that in the presence of ionic surfactants, at least, two label populations coexist in equilibrium. The rotational correlation times (tau) indicated that component I displays a more restricted mobility state, associated to the spin labels bound to the protein; the less immobilized component 2 is due to label localization in the surfactant aggregates. For both probes, the increase of surfactant concentration leads to higher motional levels of component 1 followed by a simultaneous decrease of this fraction of nitroxides and its conversion into component 2. For 10 mM cethyltrimethylammonium chloride (CTAC), the nitroxides are 100% bound to the protein, whereas at 10mM N-hexadecyl-N,N-dimethyl-3-ammonio-1-propanesulfonate (HPS) and sodium dodecyl sulfate (SDS) the fractions of bound nitroxides are reduced to 18% and 86%, respectively. No significant polarity changes were observed in the whole surfactant concentration range for component 1. Moreover, at higher surfactant concentration, component 2 exhibited a similar polarity as in the pure surfactant micelles. For 16-DSA the surfactant effect is different: at 10mM of HPS and CTAC the fractions of bound nitroxides are 76% and 49%, respectively, while at 10 mM SDS they are present exclusively in a micellar environment, consistent with 100% of component 2. Overall, both SDS and HPS are able to effectively displace the nitroxide probes from the protein binding sites. while CTAC seems to affect the nitroxide binding to a significantly smaller extent. (C) 2008 Elsevier B.V. All rights reserved.

Isoelectric Point Determination for Glossoscolex paulistus Extracellular Hemoglobin: Oligomeric Stability in Acidic pH and Relevance to Protein-Surfactant Interactions

The extracellular hemoglobin from Glossoscolex paulistus (HbGp) has a molecular mass of 3.6 M Da, It has a high oligomeric stability at pH 7.0 and low autoxidation rates, as compared to vertebrate hemoglobins. In this work, fluorescence and light scattering experiments were performed with the three oxidation forms of HbGp exposed to acidic pH. Our focus is on the HbGp stability at acidic pH and also on the determination of the isoelectric point (pI) of the protein. Our results show that the protein in the cyanomet form is more stable than in the other two forms, in the whole range. Our zeta-potential data are consistent with light scattering results. Average values apt obtained by different techniques were 5.6 +/- 0.5, 5.4 +/- 0.2 and 5.2 +/- 0.5 for the oxy, met, and cyanomet forms. Dynamic light scattering (DLS) experiments have shown that, at pH 6.0, the aggregation (oligomeric) state of oxy-, met- and cyanomet-HbGp remains the same as that at 7.0. The interaction between the oxy-HbGp and ionic surfactants at pH 5.0 and 6.0 was also monitored in the present study. At pH 5,0, below the protein pI, the effects of sodium dodecyl sulfate (SDS) and cetyltrimethylammonium chloride (CTAC) are inverted when compared to pH 7.0. For CTAC, in acid pH 5.0, no precipitation is observed, while for SDS an intense light scattering appears due to a precipitation process. HbGp interacts strongly with the cationic surfactant at pH 7.0 and with the anionic one at pH 5.0. This effect is due to the predominance, in the protein surface, of residues presenting opposite charges to the surfactant headgroups. This information can be relevant for the development of extracellular hemoglobin-based artificial blood substitutes.