Modification of chitin properties for enzymatic deacetylation

Chitins produced via a conventional chemical route as well as from a new biological process were modified to increase the efficiency of enzymatic deacetylation reactions for the production of novel biological chitosan. These modified chitins were reacted for 24h with extracellular fungal enzymes from Colletotrichum lindemuthianum. The chemical and physical properties of the various substrates were analysed and their properties related to the effectiveness in the deacetylation reaction. Modifications of the chitins affected the degree of deacetylation with varied effects. Without further modification to reduce crystallinity and to open up the solid substrate structure, the chitins were found to be poor substrates for the heterogeneous solid-liquid enzymatic catalysis. It was found that the solvent and drying method used in modifying the chitins had significant impact on the final efficiency of the enzymatic deacetylation reaction. The most successful modifications through freeze drying of a colloidal chitin suspension increased the degree of enzymatic deacetylation by 20 fold. These processes reduce the crystallinity of the chitin making it easier for the enzymes to access their internal structure. X-ray diffraction, scanning electron microscopy, thermogravimetric analysis, and BET isotherm analysis are employed to characterise the modified chitins to ascertain the degree of crystallinity, porous structure, surface area, and morphology.

Acrylic bone cements modified with bioactive and biodegradable fillers

O cimento ósseo acrílico é o único material utilizado para a fixação de próteses em cirurgias ortopédicas, surgindo como uma alternativa às técnicas não cimentadas. Cerca de um milhão de pacientes são anualmente tratados para a substituição total da articulação do quadril e do joelho. Com a maior expectativa de vida da população e o aumento do número de cirurgias realizadas por ano espera-se que o uso do cimento ósseo aumente substancialmente. A fraca ligação do cimento ao osso é um problema comum que pode causar perda asséptica da prótese. Assim, torna-se necessário investir no desenvolvimento de cimentos ósseos alternativos que permitam promover maior estabilidade e melhor desempenho do implante. O principal objetivo desta tese foi desenvolver um cimento ósseo bioativo, capaz de ligar-se ao osso, com propriedades melhoradas relativamente aos sistemas convencionais. A preparação dos materiais foi realizada por dois processos diferentes, a polimerização por via térmica e a polimerização por via química. Inicialmente, utilizando o processo térmico, foram desenvolvidos compósitos de PMMA-co-EHA reforçados com vidro de sílica (CSi) e vidro de boro (CB) e comparados em termos do seu comportamento in vitro em meio acelular e celular. A formação de precipitados de fosfato de cálcio foi observada sobre a superfície de todos os compósitos indicando que estes materiais são potencialmente bioativos. Em relação à avaliação biológica o CSi demonstrou um efeito indutor da proliferação das células. As células apresentaram uma morfologia normal e alta taxa de crescimento quando comparadas com o padrão de cultura. Por outro lado ocorreu inibição da proliferação celular para o CB provavelmente devido à sua elevada taxa de degradação, levando a uma elevada concentraçao de iões de B e de Mg no meio de cultura. O efeito do vidro nos cimentos curados por via química, incorporando um activador de baixa toxicidade, também foi avaliado. Os resultados sugerem que as novas formulações podem diminuir o efeito exotérmico na cura do cimento e melhorar as propriedades mecânicas (flexão e compressão). Outro estudo conduzido neste trabalho explorou a possibilidade de incorporar ibuprofeno (fármaco anti-inflamatório) no cimento, dando origem a um material capaz de ser simultaneamente, bioativo e promotor da libertação controlada de fármacos. Neste contexto foi evidenciado que o desempenho do cimento desenvolvido pode contribuir para minimizar o processo inflamatório associado a uma cirurgia ortopédica. Finalmente, a fase sólida do cimento ósseo bioativo foi modificada por diferentes polímeros biodegradáveis. A adição deste enchimento deu origem a um cimento parcialmente biodegradável que pode permitir a formação de poros e o crescimento ósseo para o interior do cimento, resultando numa melhor fixação da prótese.

Selective N-monomethylation of aniline using Zn1-x CoxFe2O4( x=0, 0.2, 0.5, 0.8 and 1.0)type systems

A series of ferrites having the general formula Zn1-xCoxFe2O4 (x=0, 0.2, 0.5, 0.8 and 1.0)were prepared by soft chemical route. The materials were characterized by adopting various physico-chemical methods. The reaction of aniline with methanol was studied in a fixed-bed reactor system as a potential source for the production of various methyl anilines. It was observed that systems possessing low ‘ x’ values are highly selective and active for N-monoalkylation of aniline leading to N-methylaniline. Reaction parameters were properly varied to optimize the reaction conditions for obtaining N-methylaniline selectively and in better yield. Among the systems Zn0.8Co0.2Fe2O4 is remarkable due to its very high activity and excellent stability. Under the optimized conditions N-methylaniline selectivity exceeded 98%. Even at a methanol to aniline molar ratio of 2, the yield of N-methylaniline was nearly 50%, whereas its yield exceeded 71% at the molar ratio of 5. ZnFe2O4, though executed better conversion than Zn0.8Co0.2Fe2O4 in the initial period of the run, deactivates quickly as the reaction proceeds. The Lewis acidity of the catalysts is mainly responsible for the good performance. Cation distribution in the spinel lattice influences their acido-basic properties and, hence, these factors have been considered as helpful parameters to evaluate the activity of the systems.

Studies on Heat Diffusion in Selected Conducting Polymers using Probe Beam Deflection and Photoacoustic Techniques

In the present study, radio frequency plasma polymerization technique is used to prepare thin films of polyaniline, polypyrrole, poly N-methyl pyrrole and polythiophene. The thermal characterization of these films is carried out using transverse probe beam deflection method. Electrical conductivity and band gaps are also determined. The effect of iodine doping on electrical conductivity and the rate of heat diffusion is explored.Bulk samples of poyaniline and polypyrrole in powder form are synthesized by chemical route. Open photoacoustic cell configuration is employed for the thermal characterization of these samples. The effect of acid doping on heat diffusion in these bulk samples of polyaniline is also investigated. The variation of electrical conductivity of doped polyaniline and polypyrrole with temperature is also studied for drawing conclusion on the nature of conduction in these samples. In order to improve the processability of polyaniline and polypyrrole, these polymers are incorporated into a host matrix of poly vinyl chloride. Measurements of thermal diffusivity and electrical conductivity of these samples are carried out to investigate the variation of these quantities as a function of the content of polyvinyl chloride.

Novel Melt Transurethane Process for Cycloaliphatic Polyurethanes and Their Self-Organization for Nano-Materials

In this introduction part, importance has been given to the elastomeric properties of polyurethanes. Emphasis has been laid to this property based on microphase separation and how this could be modified by modifying the segment lengths, as well as the structure of the segments. Implication was also made on the mechanical and thermal properties of these copolymers based on various analytical methods usually used for characterization of polymers. A brief overview of the challenges faced by the polyurethane chemistry was also done, pointing to the fact that though polyurethane industry is more than 75 years old, still a lot of questions remain unanswered, that too mostly in the synthesis of polyurethanes. A major challenge in this industry is the utilization of more environmental friendly “Green Chemistry Routes” for the synthesis of polyurethanes which are devoid of any isocyanates or harsh solvents.The research work in this thesis was focused to develop non-isocyanate green chemical process for polyurethanes and also self-organize the resultant novel polymers into nano-materials. The thesis was focused on the following three major aspects:(i) Design and development of novel melt transurethane process for polyurethanes under non-isocyanate and solvent free melt condition. (ii) Solvent induced self-organization of the novel cycloaliphatic polyurethanes prepared by the melt transurethane process into microporous templates and nano-sized polymeric hexagons and spheres. (iii) Novel polyurethane-oligophenylenevinylene random block copolymer nano-materials and their photoluminescence properties. The second chapter of the thesis gives an elaborate discussion on the “Novel Melt Transurethane Process ” for the synthesis of polyurethanes under non-isocyanate and solvent free melt condition. The polycondensation reaction was carried out between equimolar amounts of a di-urethane monomer and a diol in the presence of a catalyst under melt condition to produce polyurethanes followed by the removal of low boiling alcohol from equilibrium. The polymers synthesized through this green chemical route were found to be soluble (devoid of any cross links), thermally stable and free from any isocyanate entities. The polymerization reaction was confirmed by various analytical techniques with specific references to the extent of reaction which is the main watchful point for any successful polymerization reaction. The mechanistic aspects of the reaction were another point of consideration for the novel polymerization route which was successfully dealt with by performing various model reactions. Since this route was successful enough in synthesizing polyurethanes with novel structures, they were employed for the solvent induced self-organization which is an important area of research in the polymer world in the present scenario. Chapter three mesmerizes the reader with multitudes of morphologies depending upon the chemical backbone structure of the polyurethane as well as on the nature and amount of various solvents employed for the self-organization tactics. The rationale towards these morphologies-“Hydrogen Bonding ” have been systematically probed by various techniques. These polyurethanes were then tagged with luminescent 0ligo(phenylene vinylene) units and the effects of these OPV blocks on the morphology of the polyurethanes were analyzed in chapter four. These blocks have resulted in the formation of novel “Blue Luminescent Balls” which could find various applications in optoelectronic devices as well as delivery vehicles.

Thermal and structural investigation of Er:YAl(3)(BO(3))(4) nanocrystalline powders

Pure Er:YAB (Er:YAl(3)(BO(3))(4)) nanometer-sized crystalline powder was produced from low cost chemical route, the polymeric precursor method. The initial homogeneous solutions were heat treated from 200 to 700A degrees C under oxygen atmosphere and the unique crystalline phase was synthesized at around 1150A degrees C. The thermal treatments and the initial stoichiometry play a very important role on the Er:YAB preparation. The thermal events of amorphous precursor resins and the crystallization process up to phase formation were investigated.

Synthesis and structural characterization of Eu(III)-doped Zn7Sb2O12

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

Deriving the magnitude of niobium off-center displacement in ferroelectric niobates from infrared spectroscopy

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Heat-treatment effects on the magnetic response of superconducting mesoscopic samples

The use of chemical methods in the synthesis of high-quality and small-size polycrystalline samples has been increased in recent years. In this work, a chemical route based on an aqueous precursor solution of metals followed by the addition of a water-soluble polymer formed by ethylenediaminetetraacetic acid (EDTA) and ethylene glycol (EG) was tested to produce superconducting mesoscopic YBa(2)Cu(3)O(7-gamma) samples. Different conditions of heat treatments and the effects of argon and oxygen atmospheres during the calcination steps were traced using X-ray diffraction (XRD), scanning electron microscopy (SEM) and magnetic measurements. (C) 2008 Elsevier B. V. All rights reserved.

Caracterização de cimento odontológico obtido a partir de um vidro preparado pelo método dos precursores poliméricos

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

Epitaxially grown LiNbO3 thin films by polymeric precursor method

LiNbO3 thin films were grown on (0001) sapphire substrates by a chemical route, using the polymeric precursor method. The overall process consists of preparing a coating solution from the Pechini process, based on metallic citrate polymerization, the precursor films, deposited by dip coating, are then heat treated to eliminate the organic material and to synthesize the phase. In this work, we studied the influence of the heat treatment on the structural and optical properties of single-layered films. Two routes were also investigated to increase the film thickness: increasing the viscosity of the coating solution and/or increasing the number of successively deposited layers. The x-ray diffraction theta -2 theta scans revealed the c-axis orientation of the single- and multilayered films and showed that efficient crystallization can be obtained at temperatures as low as 400 degreesC, the phi-scan diffraction evidenced the epitaxial growth with two in-plane variants, A microstructural study revealed that the films were crack free, homogeneous, and relatively dense. Finally, the investigation of the optical properties (optical transmittance and refractive index) confirmed the good quality of the films. These results indicate that the polymeric precursor method is a promising process to develop lithium niobate waveguides.

Grain boundary electric characterization of Zn7Sb2O12 semiconducting ceramic: A negative temperature coefficient thermistor

The electrical properties of the grain boundary region of electroceramic sensor temperature based on inverse spinel Zn7Sb2O12 were investigated at high temperature. The zinc antimoniate was synthesized by a chemical route based on the modified Pechini method. The electric properties of Zn7Sb2O12 were investigated by impedance spectroscopy in the frequency range from 5 Hz to 13 MHz and from 250 up to 600 degreesC. The grain boundary conductivity follows the Arrhenius law, with two linear branches of different slopes. These branches exhibit activation energies with very similar values; the low-temperature (less than or equal to350 degreesC) and high-temperature (greater than or equal to400 degreesC) regions are equal to 1.15 and 1.16 eV, respectively. Dissimilar behavior is observed on the relaxation time (tau) curve as a function of temperature, where a single slope is identified. The negative temperature coefficient parameters and nature of the polarization phenomenon of the grain boundary are discussed. (C) 2003 American Institute of Physics.

Densification and coarsening of SnO2-based materials containing manganese oxide

The present work presents results on natural sintering of tin dioxide ceramics, prepared by a chemical route or by conventional mixing and containing manganese (X-Mn = Mn/(Mn + Sn)(atomic) with 0 less than or equal to X(Mn)less than or equal to 0.15). This cation, which is practically insoluble in SnO2 network, stays at the grain surface. During thermal treatment (500 degrees C less than or equal to T-s less than or equal to 1400 degrees C), as long as the manganese surface concentration is lower than a critical value, equal to 5.10(-6) mol m(-2), no densification takes place. As soon as this value is reached, densification and grain growth occur simultaneously. The shrinkage kinetics is fast and high rho/rho(t) values can be obtained (for example. rho/rho(t)=0.95 for T-s=1300 degrees C and X-Mn=0.004). The dependence between manganese content, manganese distribution, grain size and sintering behaviour is also discussed. (C) 1998 Published by Elsevier B.V. Limited.

Electroluminescence of zinc oxide thin-films prepared via polymeric precursor and via sol-gel methods

Zinc oxide (ZnO) is an electroluminescent (EL) material that can emit light in different regions of electromagnetic spectrum when electrically excited. Since ZnO is chemically stable, inexpensive and environmentally friendly material, its EL property can be useful to construct solid-state lamps for illumination or as UV emitter. We present here two wet chemical methods to prepare ZnO thin-films: the Pechini method and the sol-gel method, with both methods resulting in crystalline and transparent films with transmittance > 85% at 550 nm. These films were used to make thin-film electroluminescent devices (TFELD) using two different insulator layers: lithium fluoride (LiF) or silica (SiO2). All the devices exhibit at least two wide emission bands in the visible range centered at 420 nm and at 380 nm attributed to the electronic defects in the ZnO optical band gap. Besides these two bands, the device using SiO2 and ZnO film obtained via sol-gel exhibits an additional band in the UV range centered at 350 nm which can be attributed to excitonic emission. These emission bands of ZnO can transfer their energy when a proper dopant is present. For the devices produced the voltage-current characteristics were measured in a specific range of applied voltage. (C) 2007 Elsevier B.V. All rights reserved.

Ferroelectric state analysis in grain boundary of Na0.85Li0.15NbO3 ceramic

The electric and dielectric properties of the grain boundary of Na0.85Li0.15NbO3 lead-free ferroelectric-semiconductor perovskite were investigated. The impedance spectroscopy was carried out as a function of a thermal cycle. The sodium lithium niobate was synthesized by a chemical route based on the evaporation method. Dense ceramic, relative density of 97%, was prepared at 1423 K for 2 h in air atmosphere. ac measurements were carried out in the frequency range of 5 Hz-13 MHz and from 673 to 1023 K. Theoretical adjust of the impedance data was performed to deriving the electric parameters of the grain boundary. The electric conductivity follows the Arrhenius law, with activation energy values equal to 1.55 and 1.54 eV for heating and cooling cycle, respectively. The nonferroelectric state of the grain boundary and its correlation with symmetry are discussed in the temperature domain. (C) 2003 American Institute of Physics.