Estudo da valorização de um resíduo de ácidos gordos livres

Com o desenvolvimento económico a gestão de recursos é um desafio que a sociedade moderna enfrenta. Um desenvolvimento sustentável, que procure satisfazer as necessidades da geração actual e futuras, é fundamental. É pois necessário encontrar novas fontes de energia e reduzir/valorizar resíduos. O objectivo deste trabalho prende-se com a valorização de um resíduo de ácidos gordos livres como fonte alternativa de energia. Estes ácidos gordos são obtidos na purificação primária da glicerina proveniente da produção de biodiesel por via alcalina, cedida pela empresa SOCIPOLE SA. Inicialmente separaram-se os ácidos gordos livres e ésteres presentes na glicerina, e caracterizou-se o produto obtido. Efectuaram-se dois ensaios, obtendo-se 42,9% e 53,8% em massa de ácidos gordos livres e 41,7% e 34,0% de ésteres no 1º e 2º ensaio respectivamente. Além dos ésteres e ácidos gordos livres, no 1º produto existem 15,4% de matéria não esterificável e no 2º 12,2%. Na primeira parte do trabalho, estudou-se a possibilidade de utilização directa deste produto como combustível. Determinou-se o PCI, obtendo-se 29,8 e 29,4 MJ/kg para o 1º e 2º ensaio respectivamente. Estes valores são superiores aos que se encontram no despacho 17313/2008 de 26 de Junho de 2008, para biogasolina e biodiesel (27,2 MJ/kg), significando que os ácidos gordos livres separados têm forte potencial para serem usados como combustível. Efectuou-se também um estudo de corrosão de aço do corpo e tubos de uma caldeira através de ensaios de polarização, usando um Potenciostato/Galvanostato, e por variação da massa de amostras mergulhadas nos ácidos gordos livres a 105ºC e à temperatura ambiente. Nas condições estudadas, os ácidos gordos não promoveram corrosão nas amostras. Por fim, fez-se a combustão de uma amostra dos ácidos gordos livres num bico de Meeker e verificou-se a formação de depósitos equivalentes a 1,93% da massa inicial. Na segunda parte estudou-se a possibilidade de produzir biodiesel por esterificação, dos ácidos gordos livres. Fez-se um estudo prévio para verificar qual a melhor razão molar de amostra/metanol a utilizar, optando-se por 1:6. Após cinco etapas de esterificação, obteve-se um produto final com 85,6% de ésteres. Não foram então atingidos os 96,5% exigidos pela norma europeia EN 14214, devido à presença de matéria não esterificável na matéria-prima, que não foi possível separar totalmente do produto durante o processo (esterificação, lavagem e secagem). Pela análise de todos os parâmetros, o produto obtido não pode ser considerado biodiesel, não sendo possível ser comercializado como tal. A análise dos resultados aponta para a opção da valorização do resíduo de ácidos gordos na queima directa em geradores e caldeiras que deverá no entanto, ser precedida de um estudo mais detalhado que inclua a análise da constituição da matéria não esterificável, para garantir uma combustão segura.

Analysis of UV spectral bands using multidimensional scaling

This study describes the change of the ultraviolet spectral bands starting from 0.1 to 5.0 nm slit width in the spectral range of 200–400 nm. The analysis of the spectral bands is carried out by using the multidimensional scaling (MDS) approach to reach the latent spectral background. This approach indicates that 0.1 nm slit width gives higher-order noise together with better spectral details. Thus, 5.0 nm slit width possesses the higher peak amplitude and lower-order noise together with poor spectral details. In the above-mentioned conditions, the main problem is to find the relationship between the spectral band properties and the slit width. For this aim, the MDS tool is to used recognize the hidden information of the ultraviolet spectra of sildenafil citrate by using a ShimadzuUV–VIS 2550, which is in theworld the best double monochromator instrument. In this study, the proposed mathematical approach gives the rich findings for the efficient use of the spectrophotometer in the qualitative and quantitative studies.

Analysis of UV spectral bands using multidimensional scaling

This study describes the change of the ultraviolet spectral bands starting from 0.1 to 5.0 nm slit width in the spectral range of 200–400 nm. The analysis of the spectral bands is carried out by using the multidimensional scaling (MDS) approach to reach the latent spectral background. This approach indicates that 0.1 nm slit width gives higher-order noise together with better spectral details. Thus, 5.0 nm slit width possesses the higher peak amplitude and lower-order noise together with poor spectral details. In the above-mentioned conditions, the main problem is to find the relationship between the spectral band properties and the slit width. For this aim, the MDS tool is to used recognize the hidden information of the ultraviolet spectra of sildenafil citrate by using a Shimadzu UV–VIS 2550, which is in the world the best double monochromator instrument. In this study, the proposed mathematical approach gives the rich findings for the efficient use of the spectrophotometer in the qualitative and quantitative studies.

An immunofluorescence test for diagnosis of ophthalmic herpes in a mouse corneal model

Herpes simplex virus type 1 (HSV-1) ophthalmic disease is the most common cause of corneal blindness in humans world-wide. Current culture techniques for HSV take several days and commercially available HSV laboratory based diagnostic techniques vary in sensitivity. Our study was conducted to evaluate the use of a quicker and simpler method to herpes ophthalmic diagnosis. Corneal smears were made by firm imprints of infected mouse eyes to glass slides, after smears were fixated with cold acetone, and an indirect immunofluorescence (IIF) method was performed using monoclonal antibodies in a murine model of ophthalmic herpes. Eye swabs from infected mice were inoculated in Vero cells for virus isolation. Cytology and histology of the eye were also performed, using hematoxylin-eosin routine. Mouse eyes were examined by slit-lamp biomicroscopy for evidence of herpetic disease at various times postinoculation. We made a comparative evaluation of sensitivity, specificity and speed of methods for laboratory detection of HSV. Our results indicate that this IIF method is quick, sensitive, specific and can be useful in the diagnosis of ophthalmic herpes as demonstrated in an animal model.

Otimização do processo de injeção de ZAMAK

A indústria automóvel necessita aumentar a produtividade de forma sistemática, com vista à redução de custos e incremento da competitividade. A otimização dos produtos e processos é uma constante. O presente trabalho foi solicitado pela empresa FicoCables, do Grupo FICOSA, tendo em vista a otimização do processo de injeção de pequenas peças injetadas em ZAMAK, que constituem o bloqueio na extremidade de cada cabo metálico inserido nos automóveis para abertura da mala, portas, travão de mão, reservatório de combustível, capô, etc. A empresa possui cerca de 52 equipamentos de injeção de ZAMAK, cuja temperatura dos bicos era mantida com base numa chama de gás. Os sucessivos problemas de controlo do sistema ditaram uma mudança estratégica no aquecimento desses bicos, passando a ser usadas resistências elétricas anelares. No entanto, esta mudança veio a apresentar problemas inesperados, os quais se vieram inclusivamente a tornar em problemas de segurança, devido ao desgaste interior prematuro dos bicos, os quais apresentaram esmo problema de rotura. Paralelamente, todos os parâmetros relacionados com este processo de fabrico estavam também estudados de forma algo incipiente, pelo que se tornou necessário compreender e dissecar todas as variáveis relacionadas com o processo e implementar sistemas que impedissem o ajuste não controlado dos parâmetros por parte dos operadores. Também os moldes foram alvo de ações de melhoria, com vista a evitar problemas na zona de contacto do bico com o molde. O processo foi analisado em pormenor, permitindo um controlo muito mais apurado do mesmo. Os resultados fizeram sentir-se de forma imediata, graças ao trabalho desenvolvido neste estudo e à abertura demonstrada pela empresa para implementar todas as soluções propostas. O resultado final traduz-se num incremento significativo da segurança para os operadores, num controlo muito mais apurado de todos os parâmetros envolvidos no processo, numa maior garantia da qualidade nos produtos injetados em ZAMAK e em ganhos financeiros significativos para a empresa.

Improved polymeric medical devices for active substances delivery

The work presented in this thesis was developed in collaboration with a Portuguese company, BeyonDevices, devoted to pharmaceutical packaging, medical technology and device industry. Specifically, the composition impact and surface modification of two polymeric medical devices from the company were studied: inhalers and vaginal applicators. The polyethylene-based vaginal applicator was modified using supercritical fluid technology to acquire self-cleaning properties and prevent the transport of bacteria and yeasts to vaginal flora. For that, in-situ polymerization of 2-substituted oxazolines was performed within the polyethylene matrix using supercritical carbon dioxide. The cationic ring-opening polymerization process was followed by end-capping with N,N-dimethyldodecylamine. Furthermore, for the same propose, the polyethylene matrix was impregnated with lavender oil in supercritical medium. The obtained materials were characterized physical and morphologically and the antimicrobial activity against bacteria and yeasts was accessed. Materials modified using 2-substituted oxazolines showed an effective killing ability for all the tested microorganisms, while the materials modified with lavender oil did not show antimicrobial activity. Only materials modified with oligo(2-ethyl-2-oxazoline) maintain the activity during the long term stability. Furthermore, the cytotoxicity of the materials was tested, confirming their biocompatibilty. Regarding the inhaler, its surface was modified in order to improve powder flowability and consequently, to reduce powder retention in the inhaler´s nozzle. New dry powder inhalers (DPIs), with different needle’s diameters, were evaluated in terms of internal resistance and uniformity of the emitted dose. It was observed that they present a mean resistance of 0.06 cmH2O0.5/(L/min) and the maximum emitted dose obtained was 68.9% for the inhaler with higher needle´s diameter (2 mm). Thus, this inhaler was used as a test and modified by the coating with a commonly-used force control agent, magnesium stearate, dried with supercritical carbon dioxide (scCO2) and the uniformity of delivered dose tests were repeated. The modified inhaler showed an increase in emitted dose from 68.9% to 71.3% for lactose and from 30.0% to 33.7% for Foradil.

A continuous solvent- and oil-free method to prepare injectable PEGylated fibrinogen cell-laden microparticles

Injectable biomaterials with in situ cross-linking reactions have been suggested to minimize the invasiveness associated with most implantation procedures. However, problems related with the rapid liquid-to-gel transition reaction can arise because it is difficult to predict the reliability of the reaction and its end products, as well as to mitigate cytotoxicity to the surrounding tissues. An alternative minimally invasive approach to deliver solid implants in vivo is based on injectable microparticles, which can be processed in vitro with high fidelity and reliability, while showing low cytotoxicity. Their delivery to the defect can be performed by injection through a small diameter syringe needle. We present a new methodology for the continuous, solvent- and oil-free production of photopolymerizable microparticles containing encapsulated human dermal fibroblasts. A precursor solution of cells in photo-reactive PEG-fibrinogen (PF) polymer was transported through a transparent injector exposed to light-irradiation before being atomized in a jet-in-air nozzle. Shear rheometry data provided the cross-linking kinetics of each PF/cell solution, which was then used to determine the amount of irradiation required to partially polymerize the mixture prior to atomization. The partially polymerized drops fell into a gelation bath for further polymerization. The system was capable of producing cell-laden microparticles with high cellular viability, with an average diameter of between 88.1 µm to 347.1 µm and a dispersity of between 1.1 and 2.4, depending on the parameters chosen.

In-line rheo-optical characterization during small-scale polymer processing and compounding

As increasingly more sophisticated materials and products are being developed and times-to-market need to be minimized, it is important to make available fast response characterization tools using small amounts of sample, capable of conveying data on the relationships between rheological response, process-induced material structure and product characteristics. For this purpose, a single / twin-screw mini-extrusion system of modular construction, with well-controlled outputs in the range 30-300 g/h, was coupled to a in- house developed rheo-optical slit die able to measure shear viscosity and normal-stress differences, as well as performing rheo-optical experiments, namely small angle light scattering (SALS) and polarized optical microscopy (POM). In addition, the mini-extruder is equipped with ports that allow sample collection, and the extrudate can be further processed into products to be tested later. Here, we present the concept and experimental set-up [1, 2]. As a typical application, we report on the characterization of the processing of a polymer blend and of the properties of extruded sheets. The morphological evolution of a PS/PMMA industrial blend along the extruder, the flow-induced structures developed and the corresponding rheological characteristics are presented, together with the mechanical and structural characteristics of produced sheets. The application of this experimental tool to other material systems will also be discussed.

In-line rheo-optical microstructural characterization of complex polymer systems

Tese de Doutoramento em Ciência e Engenharia de Polímeros e Compósitos.

Analytical and numerical investigation of two-phase flows

Multiphase flows, hyperbolic model, Godunov method, nozzle flow, nonstrictly hyperbolic

Untersuchung des Flüssigkeitseintrages auf die Temperaturverteilung in Gas-/Feststoff-Wirbelschichten

Liquid separation efficiency, liquid penetration, modeling, arrays of temperature, distribution, fluidized bed, two-phase-nozzle

Lymnaea rupestris sp. n. from Southern Brazil (Pulmonata: Lymnaeidae)

A new species of South American lymnaeid snail, Lymnaea rupestris, is described. So far it has been found only in its type-locality, Nova TeuTõnia, a village in the municipality of Seara (27° 07' S, 52° 17' W), state of Santa Catarina, Brazil. It is distinguishable, by characteristics of the shell and internal organs, from the other two lymnaeid species known to occur in the area, Lymnaea columella and L. viatrix. Its shell has 4 markedly shouldered whorls, deep suture, ovoid or rounded aperture occupying about half the length of the shell, and reaches about 6 mm in length in adults; in columella and viatrix the shell has 4-5 rounded whorls, shallow suture, and reaches over 10 mm in adults; the aperture is ovoid, occupying about half the length of the shell in viatrix, about two thirds in columella. Anatomically it is readily separated from L. columella by the shape of the ureter, straight in rupestris, with a double flexure in columella. Comparison with L. viatrix shows the following main differences: distalmost portion of the oviduct with a low, caplike lateral swelling in rupestris, with a well-developed pouch in viatrix; uterus bent abruptly caudalward in rupestris, only slightly curved rightward in viatrix; basal half of the spermathecal duct hidden by the prostate in rupestris, wholly visible or nearly so in viatrix; spermiduct sinuous and uniformly wide in rupestris, straight and gradually narrowing in viatrix; prostate more than half as long and nearly as wide as the nidamental gland, and with a slit-like lumen in cross-section in rupestris, less than half as long as and much narrower than the nidamental gland, and with an inward fold in cross-section in viatrix; penial sheath about as long and as wide as the prepuce in rupesris, shorter and narrower than the prepuce in viatrix. An important ecological characteristic of L. rupestris is its habitat on wet rocks most often outside bodies of water, although in close proximity to them. Specimens were deposited in the following malacological collections: Instituto OswaldoCruz, Rio de Janeiro; Academy of Natural Sciences, Philadelphia; Museum of Zoology, University of Michigan; and British Museum (Natural History).

A corneal dystrophy associated with transforming growth factor beta-induced Gly623Asp mutation an amyloidogenic phenotype.

PURPOSE: To present the light and electron microscopic findings of a unique corneal dystrophy never before described in a German family carrying the Gly623Asp Mutation of the TGFBI gene with late clinical onset. DESIGN: Experimental study. PARTICIPANTS: Four affected and 6 nonaffected family members. METHODS: Slit-lamp examination, photographic documentation, and isolation of genomic DNA from peripheral blood leucocytes obtained from each family member examined. Exons 3, 4, 5, and 11 to 14 of the TGFBI gene were amplified and sequenced in these family members. Five corneal buttons of 3 affected siblings were excised at the time of penetrating keratoplasty. Light and electron microscopic examination were performed including immunohistochemistry with antibodies against keratoepithelin (KE) 2 and 15. MAIN OUTCOME MEASURES: Clinical and histologic characteristics of corneal opacification in affected patients and presence of coding region changes in the TGFBI gene. RESULTS: The specimens showed destructive changes in Bowman's layer and the adjacent stroma. Patchy Congo red-positive amyloid deposits were found within the epithelium in 1 cornea, in Bowman's layer and in the anterior stroma of all specimens also showing KE2, but not KE15, immunostaining. Electron microscopy revealed deposits mainly located in the anterior stroma and Bowman's layer and in small amounts in the basal area of some epithelial cells. The destroyed areas were strongly Alcian blue-positive, the Masson Trichrome stain proved mainly negative for the deposits. All affected but none of the unaffected family members had a heterozygous missense mutation in exon 14 of the TGFBI gene (G-->A transition at nucleotide 1915) replacing glycin by aspartic acid amino acid (Gly623Asp) at position 623 of the KE protein. CONCLUSIONS: In contrast with the patient carrying the Gly623Asp mutation of the TGFBI gene described by Afshari et al, our cases presented with Salzmann's nodular degeneration-like clinical features and their specimens contained KE2-positive amyloid. The reason for this now "meeting the expectation histologic phenotype" is unclear. The histologic findings emphasize that this is a unique corneal dystrophy, which shares no clinical characteristics with Reis-Bücklers' dystrophy and should be treated as a distinct entity. FINANCIAL DISCLOSURE(S): The authors have no proprietary or commercial interest in any materials discussed in this article.

Gundlachia dutrae: n. sp. from northwest Brazil (Mollusca: Basommatophora: Ancylidae)

A new species of Gundlachia, Gundlachia dutrae is described from northwest Brazil. It is distinguishable from other congenerie species by characteristics of the shell, radula and internal organs. Shell relatively high. Aperture near-circular; periostracum dark brown without periostracal hairs. Apex slightly inclined to the right, projected but not hooked, with an apical depression surrounted by a sculpture of well-marked irregular punctations. Shell surface with prominent radial sculpture. No septate specimens were observed. Ratios (n= 59): shell width/shell lenght = 0,66- 0,79 (mean 0,73); shell height/shell length = 0,32- 0,45 ( mean 0,37); shell height/shell width = 0,43- 0,63 (mean 0,51). Body of normal ancylid type; mantle pigmentation dark brown or black, concentrated along the mantle collar. The dorsal surface of the right anterior muscle is elongated and medially constricted. The left anterior and the posterior muscles are almost elliptical. Adhesive area is V-shaped. Pseudobranch unpigmented bearing a very small and thin dorsal lobe. Ovotestis with more than 25 unbranched diverticula. Ovispermiduct with seminal vesicle rather developed. Elongated nidamental gland continous with the glandular wall of the uterus. Nidamental gland appendix ending into a bulbous swelling Spermathecal body almost rounded. Well-developed prostate with five long diverticula. Ejaculatory complex with long glandular flagellum, without a penis or true ultra-penis. "Penis sheath" developed. "Ultra-penis" projected as a tube inside the lumem of prepuce, with a slit between "ultra-penis" and "penis sheath". Rachidian tooth tetracuspid, with two median cusps assymmetrical and aculeated. Lateral teeth tricuspid, with a reduced endocon and a prominent mesocon. A well marked gap occurs between meso and ectocon. Marginal teeth similar to lateral ones. Jaw T-shaped, with about 28 dorsal plates.

Nitrosative stress and corneal transplant endothelial cell death during acute graft rejection.

BACKGROUND: Nitrosative stress takes place in endothelial cells (EC) during corneal acute graft rejection. The purpose of this study was to evaluate the potential role of peroxynitrite on corneal EC death. METHODS: The effect of peroxynitrite was evaluated in vivo. Fifty, 250, and 500 microM in 1.5 microL of the natural or denatured peroxynitrite in 50 microM NaOH, 50 microM NaOH alone, or balanced salt solution were injected into the anterior chamber of rat eyes (n=3/group). Corneal toxic signs after injection were assessed by slit-lamp, in vivo confocal imaging, pachymetry, and EC count. The effect of peroxynitrite was also evaluated on nitrotyrosine and leucocyte elastase inhibitor/LDNase II immunohistochemistry. Human corneas were incubated with peroxynitrite and the effect on EC viability was evaluated. A specific inducible nitric oxide synthase inhibitor (iNOS) was administered systemically in rats undergoing allogeneic corneal graft rejection and the effect on EC was evaluated by EC count. RESULTS: Rat eyes receiving as little as 50 microM peroxynitrite showed a specific dose-dependent toxicity on EC. We observed an intense nitrotyrosine staining of human and rat EC exposed to peroxynitrite associated with leucocyte elastase inhibitor nuclear translocation, a noncaspase dependent apoptosis reaction. Specific inhibition of iNOS generation prevented EC death and enhanced EC survival of the grafted corneas. However, inhibition of iNOS did not have a significant influence on the incidence of graft rejection. CONCLUSION: Nitrosative stress during acute corneal graft rejection in rat eyes induces a noncaspase dependent apoptotic death in EC. Inhibition of nitric oxide production during the corneal graft rejection has protective effects on the corneal EC survival.