Diffusion-controlled growth of aggregates in layer-by-layer films of poly(o-methoxyaniline)

The adsorption process in layer-by-layer (LBL) films of poly(o-methoxyaniline) alternated with poly(vinyl sulfonic acid) is explained using the Avrami equation. This equation was used due to its mathematical simplicity and adequate description of experimental data in real polymer systems. The Avrami parameters are a convenient means to represent empirical data of crystallization, and if microscopic knowledge is available these parameters can also be associated with adsorption mechanisms. The growth of spherulites in the LBL films was studied as a function of time using atomic force microscopy and the data were used to estimate the number and radii of aggregates, from which the Avrami parameters were determined. We find that the adsorption mechanism may correspond to a tri dimensional, diffusion-controlled growth, with increasing nucleation rate, consistent with results from kinetics of adsorption.

Effect of micelles, microemulsions and other supramolecular aggregates on the hydrolysis of β-lactam antibiotics

A critical revision of the literature was made regarding the stability of β-lactam antibiotics in the presence of surfactants. The factors involved in the drug decomposition were analyzed in the development of the discussion. The analysis has indicated that some organized systems obtained from surfactants can be used to control rates and mechanisms of antibiotic decomposition. These organized systems can also be used to obtain specific information about the drug reactivity in a microenvironment similar to the site of pharmacological effect.

Avaliação da durabilidade de concretos produzidos com agregados graúdos reciclados provenientes de cerâmicas vermelhas com diferentes taxas de pré-saturação

A quantidade de resíduos gerados pelo setor da Construção Civil ultimamente vem chamando atenção devido à dimensão com a qual atua como impacto ambiental utilizando materiais de fontes naturais não renováveis e aumentando as quantidades de lixos produzidos pelo meio urbano. No Brasil, esta estimativa gira em torno de 90.000 toneladas geradas por dia. A proposta de utilizar o agregado proveniente de RCC (resíduo de construção civil) como parte integrante de concretos estruturais torna-se ainda mais interessante a partir do momento em que se busca uma diminuição nos custos para a produção do concreto, carregando consigo a mentalidade ambientalista quando poupa a utilização de recursos naturais os quais alguns já começam a se esgotar. Bancos de areia e fontes de seixo começam a se extinguir devido à larga utilização desses agregados nos concretos produzidos em Belém e cidades interiores do estado do Pará. Assim a necessidade de novas fontes de agregados nos faz buscar nos resíduos da construção civil prováveis fontes de agregados que respondam de forma similar aos naturais. Levando em consideração esta proposta, esta dissertação avaliou a durabilidade de concretos produzidos com o agregado de RCC cerâmico, através de ensaios de absorção de água por capilaridade, carbonatação, penetração de íons cloretos e resistividade elétrica. Para tanto, foi substituído o agregado graúdo natural pelo agregado graúdo cerâmico em 50%, onde esta porcentagem de agregado reciclado foi submetida às taxas de pré-saturação de 60%, 80% e 100%. Nos resultados obtidos pode-se observar que a presença do AGRC (agregado graúdo reciclado cerâmico), independentemente do grau de pré-saturação foi significativa em todos os resultados obtidos, fato que embora deixe os concretos mais suscetíveis à perda de durabilidade, apresentou uma mesma tendência de comportamento em relação às misturas referência. Os resultados mais próximos das misturas convencionais foram alcançados pelos concretos que continham agregados cerâmicos pré-saturados com água à uma taxa de 80%.

Production and evaluation of recycled polymers from açaí fibers

The possibility of recycling and the favorable mechanical properties of the products have encouraged the study and production of thermoplastic composites from natural fibrous waste. Açaí (cabbage palm) fiber, which is removed from the seed, has been slightly investigated, as compared to what is already known about the fruit pulp. In this study, the influence of açaí fiber as an element of reinforcement in recycled everyday usage thermoplastics using simple, low cost methodology was evaluated. Recycled matrixes of high impact polystyrene and polypropylene were molded by hot compression from which the fiber composites were obtained. The FTIR technique showed that the process was efficient in preventing degradation of the açaí fibers. The influence of the fiber on the mechanical behavior of the recycled matrixes was investigated by microscopic images of compression and impact tests. The results showed better impact performance for the fiber combined with the polymeric matrixes.

Easily handling penicillin G acylase magnetic cross-linked enzymes aggregates: Catalytic and morphological studies

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

Physical and mechanical characterization of a recycled polypropylene and wood flour without additives

Recycled polymer matrix composites reinforced with wood flour can be a viable alternative for the replacement of wood and virgin polymers in materials used in floors, door frames, windows and external cladding. The objective of this research was to determine some physical and mechanical parameters of composite made with Pinus taeda and elliottii wood flour (WF) and recycled polypropylene (PP), without the use of compatibilizers or additives. The composites were separated into four traits, namely 100% PP, 90% PP with 10%, WF 80% PP with 20% WF and 70 % PP with 30% WF. The characterization of the composite followed the standards ASTM D-638-10, ASTM D256-00, ASTM D570 -98, ASTM D1238 -10 and ASTM G 155-05, it was also employed the surface analysis by scanning electron microscopy. The dimensional stability tests showed satisfactory results. Even the composite with a higher percentage of wood flour (30%) had a flow index of 10 MFI, considered compatible with that observed for PP (polypropylene) virgin by standard ASTM D 1238-10. The inclusion of wood flour (FM) afforded composites with good mechanical characteristics which can be applied in manufacture of different materials, specifically employed outdoors.

Plasma Treatment to Improve the Surface Properties of Recycled Post-Consumer PVC

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

Albumin-induced circular dichroism in Congo red: applications for studies of amyloid-like fibril aggregates and binding sites

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

Excited-state dynamics of meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates

The excited-state dynamics of free-base meso-tetrakis(sulfonatophenyl) porphyrin J-aggregates obtained by the Z-scan technique in femto- and picosecond time scales, along with UV-Vis spectroscopy and flash photolysis is reported. Besides obtaining the S-1 state lifetime, the discrimination between internal conversion and intersystem crossing nonradiative processes from that state was also possible, and their rates and respective quantum yields were found. The aggregates present reverse saturable absorption at 532 nm for both singlet and triplet excited states. The data shown is important for several applications such as optical limiting, photodynamic therapy and others. (C) 2011 Elsevier B.V. All rights reserved.

Effect of interaction with micelles on the excited-state optical properties of zinc porphyrins and J-aggregates formation

This work reports on the photophysical properties of zinc porphyrins meso-tetrakis methylpyridiniumyl (Zn2+TMPyP) and meso-tetrakis sulfonatophenyl (Zn2+TPPS) in homogeneous aqueous solutions and in the presence of sodium dodecyl sulfate (SDS) and cetyltrimethyl ammonium bromide (CTAB) micelles. The excited-state dynamic was investigated with the Z-scan technique, UV-Vis absorption, and fluorescence spectroscopy. Photophysical parameters were obtained by analyzing the experimental data with a conventional five-energy-level diagram. The interaction of the charged side porphyrin groups with oppositely charged surfactants can reduce the electrostatic repulsion between porphyrin molecules leading to aggregation, which affected the porphyrin characteristics such as absorption cross-sections, lifetimes and quantum yields. The interaction between anionic ZnTPPS with cationic CTAB micelles induced the formation of porphyrin J-aggregates, while this effect was not observed in the interaction of ZnTMPyP with SDS micelles. This difference is, probably, due to the difference in electrostatic repulsion between the porphyrin molecules. The insights obtained by these results are important for the understanding of the photophysical behavior of porphyrins, regarding potential applications in pharmacokinetics as encapsulation of photosensitizer for drug delivery systems and in its interaction with cellular membrane.

Kinematics of fibrous aggregates

This thesis reports on a research into the progressive development of fibrous aggregates, e.g. calcite, quartz and mica crystals in veins and strain fringes. The study is based on microstructural analysis of natural examples and on computer experiments. Investigation of fibrous looking elongate crystals in striped bedding-veins from the Orobic Alps, Italy indicate that these crystals do not track the opening trajectory of the veins but are oriented at an angle of up to 80° to the opening direction. Microstructural analysis of quartz, calcite and chlorite fibres in antitaxial strain fringes indicate that most strain fringes contain complex intergrowth of tracking (displacement-controlled) and non-tracking (face-controlled) fibres. To explain these growth features the computer program

Recycled crustal material in the geochemical record of Pacific ocean island basalts from Pitcairn, Hawaii and Rurutu

Die Isotopenzusammensetzungen des Pitcairn Hotspot (Südpazifik), des Mauna Kea (Hawaii) und der Insel Rurutu (Französisch Polynesien) wurden bestimmt, um Heterogenitäten im Erdmantel zu charakterisieren. Die Bleiisotopenzusammensetzung wurde mit einer Dreiisotopenspiketechnik zur Korrektur der instrumentellen Massenfraktionierung gemessen. An Proben von Pitcairn wurde zusätzlich die Os, Hf, Nd, Sr Isotopenzusammensetzung, sowie die Haupt- und Spurenelementzusammensetzung bestimmt. Die Isotopensignatur des Pitcairn Hotspots kann durch eine Sedimentkomponente in der Magmenquelle erklärt werden. Die Bleiisotopenschwankungen des Mauna Kea in der HSDP-2 Bohrung treten als Oszillationen auf, die sich zu linearen Anordnungen im Bleiisotopenraum zusammensetzen. Das begrenzte zeitliche Auftreten einer linearen Anordnung zeigt, daß die Heterogenitäten mehrere zehner Kilometer Länge im aufsteigenden Mantelmaterial unter dem Vulkan einnehmen. Auch die Bleiisotopenzusammensetzungen der Rurutu-laven zeigen lineare Anordnungen.Diese lineare Anordnungen im Bleiisotopenraum können durch eine vorwiegend binäre Mischung erklärt werden. Ein Bleiisotopenentwicklungsmodell unterstützt, daß die Differenzierung der Ausgangsmaterialien vor weniger als etwa zwei Milliarden Jahren geschah und für Mauna Kea relativ jung sein könnte. Keine der Hotspots weisen identische Mischungsendglieder auf, so daß die Heterogenitäten kleinräumige Merkmale im Erdmantel sind.

NMR studies on supramolecular aggregates in solution and the solid state

The aim of this work presented here is the characterization of structure and dynamics of different types of supramolecular systems by advanced NMR spectroscopy. One of the characteristic features of NMR spectroscopy is based on its high selectivity. Thus, it is desirable to exploit this technique for studying structure and dynamics of large supramolecular systems without isotopic enrichment. The observed resonance frequencies are not only isotope specific but also influenced by local fields, in particular by the distribution of electron density around the investigated nucleus. Barbituric acid are well known for forming strongly hydrogen-bonded complexes with variety of adenine derivatives. The prototropic tautomerism of this material facilitates an adjustment to complementary bases containing a DDA(A = hydrogen bond acceptor site, D = hydrogen bond donor site) or ADA sequences, thereby yielding strongly hydrogen-bonded complexes. In this contribution solid-state structures of the enolizable chromophor "1-n-butyl-5-(4-nitrophenyl)-barbituric acid" that features adjustable hydrogen-bonding properties and the molecular assemblies with three different strength of bases (Proton sponge, adenine mimetic 2,6-diaminopyridine (DAP) and 2,6-diacetamidopyridine (DAC)) are studied. Diffusion NMR spectroscopy gives information over such interactions and has become the method of choice for measuring the diffusion coefficient, thereby reflecting the effective size and shape of a molecular species. In this work the investigation of supramolecular aggregates in solution state by means of DOSY NMR techniques are performed. The underlying principles of DOSY NMR experiment are discussed briefly and more importantly two applications demonstrating the potential of this method are focused on. Calix[n]arenes have gained a rather prominent position, both as host materials and as platforms to design specific receptors. In this respect, several different capsular contents of tetra urea calix[4]arenes (benzene, benzene-d6, 1-fluorobenzene, 1-fluorobenzene-d5, 1,4-difluorobenzene, and cobaltocenium) are studied by solid state NMR spectroscopy. In the solid state, the study of the interaction between tetra urea calix[4]arenes and guest is simplified by the fact that the guests molecule remains complexed and positioned within the cavity, thus allowing a more direct investigation of the host-guest interactions.

Synthesis and characterization of artificial aggregates and their potential applications in road construction

L’obiettivo del progetto è stato quello di realizzare ed analizzare aggregati artificiali creati attraverso geopolimerizzazione e macro-incapsulazione di paraffina in aggregati leggeri espansi, discutendo i loro possibili impieghi nelle pavimentazioni stradali. Dopo un'accurata calibrazione delle miscele geopolimeriche, sono stati realizzati degli aggregati artificiali, in seguito caratterizzati in accordo con la norma UNI EN 10343, con l'intento di sostituire materiali stradali vergini. Contemporaneamente, sono stati prodotti aggregati leggeri impregnati di paraffina (PCM), in grado di cambiare fase una volta raggiunti all'incirca i 3 °C, e successivamente rivestiti da due strati di resina poliestere e polvere di granito, denominati PLA: sfruttandone le proprietà termiche, si è valutato il loro possibile utilizzo come soluzione anti-icing. L’ultima fase della ricerca è stata incentrata nella realizzazione di aggregati geopolimerici espansi e molto porosi che potessero contenere una elevata quantità di PCM, sostituendo l'argilla espansa utilizzata nella produzione degli PLA.