Production of Polyhydroxyalkanoates by Pseudomonas mendocina using vegetable oils and their characterisation

Synthesis of Polyhydroxyalkanoates (PHAs) by Pseudomonas mendocina, using different vegetable oils such as, coconut oil, groundnut oil, corn oil and olive oil, as the sole carbon source was investigated for the first time. The PHA yield obtained was compared with that obtained during the production of PHAs using sodium octanoate as the sole carbon source. The fermentation profiles at shaken flask and bioreactor levels revealed that vegetable oils supported the growth of Pseudomonas mendocina and PHA accumulation in this organism. Moreover, when vegetable oil (coconut oil) was used as the sole carbon source, fermentation profiles showed better growth and polymer production as compared to conditions when sodium octanoate was used as the carbon source. In addition, comparison of PHA accumulation at shaken flask and fermenter level confirmed the higher PHA yield at shaken flask level production. The highest cell mass found using sodium octanoate was 1.8 g/L, whereas cell mass as high as 5.1 g/L was observed when coconut oil was used as the feedstock at flask level production. Moreover, the maximum PHA yield of 60.5% dry cell weight (dcw) was achieved at shaken flask level using coconut oil as compared to the PHA yield of 35.1% dcw obtained using sodium octanoate as the sole carbon source. Characterisations of the chemical, physical, mechanical, surface and biocompatibility properties of the polymers produced have been carried out by performing different analyses as described in the second chapter of this study. Chemical analysis using GC and FTIR investigations showed medium chain length (MCL) PHA production in all conditions. GC-MS analysis revealed a unique terpolymer production, containing 3-hydroxyoctanoic acid, 3-hydroxydecanoic acid and 3-hydroxydodecanoic acid when coconut oil, groundnut oil, olive oil, and corn oil were used as the carbon source. Whereas production of the homopolymer containing 3-hydroxyoctanoic acid was observed when sodium octanoate was used as the carbon source. MCL-PHAs produced in this study using sodium octanoate, coconut oil, and olive oil exhibited melting transitions, indicating that each of the PHA was crystalline or semi-crystalline polymer. In contrast, the thermal properties of PHAs produced from groundnut and corn oils showed no melting transition, indicating that they were completely amorphous or semi-crystalline, which was also confirmed by the X-Ray Diffraction (XRD) results obtained in this study. Mechanical analysis of the polymers produced showed higher stiffness of the polymer produced from coconut oil than the polymer from sodium octanoate. Surface characterisation of the polymers using Scanning Electron Microscopy (SEM) revealed a rough surface topography and surface contact angle measurement revealed their hydrophobic nature. Moreover, to investigate the potential applicability of the produced polymers as the scaffold materials for dental pulp regeneration, multipotent human Mesenchymal stem cells (hMSCs) were cultured onto the polymer films. Results indicated that these polymers are not cytotoxic towards the hMSCs and could support their attachment and proliferation. Highest cell growth was observed on the polymer samples produced from corn oil, followed by the polymer produced using coconut oil. In conclusion, this work established, for the first time, that vegetable oils are a good economical source of carbon for production of MCL-PHA copolymers effectively by Pseudomonas mendocina. Moreover, biocompatibility studies suggest that the produced polymers may have potential for dental tissue engineering application.

Novel P(3HB) Composite Films Containing Bioactive Glass Nanoparticles for Wound Healing Applications

Bioactive glass (BG) is considered an ideal material for haemostasis as it releases Ca2+ ions upon hydration, which is required to support thrombosis. In this study the effect of the presence of the BG nanoparticles in P(3HB) microsphere films on the structural properties, thermal properties and biocompatibility of the films were studied. The nanoscaled bioactive glass with a high surface area was also tested for its in vitro haemostatic efficacy and was found to be able to successfully reduce the clot detection time. In an effort to study the effect of the roughness induced by the formation of HA on the cellular functions such as cell adhesion, cell mobility and cell differentiation, the composite films were immersed in SBF for a period of 1, 3 and 7 days. From the SEM images the surface of the P(3HB)/n-BG composite microsphere films appeared fairly uniform and smooth on day 1, however on day 3 and day 7 a rough and uneven surface was observed. The presence of HA on the composite microsphere films on day 3 and day 7 influenced the surface roughness of the films. However, when the P(3HB)/n-BG composite microspheres with enhanced surface roughness were tested for biocompatibility, reduced amount of protein adsorption and cell adhesion were observed. This study thus revealed that there is an optimal surface roughness for the P(3HB) microsphere films for increased cell adhesion, beyond which it could be deleterious for cell adhesion and differentiation.

Strength of the Iberian intraplate lithosphere: Cenozoic deformations and seismicity

Previous studies about the strength of the lithosphere in the Iberia centre fail to resolve the depth of earthquakes because of the rheological uncertainties. Therefore, new contributions are considered (the crustal structure from a density model) and several parameters (tectonic regime, mantle rheology, strain rate) are checked in this paper to properly examine the role of lithospheric strength in the intraplate seismicity and the Cenozoic evolution. The strength distribution with depth, the integrated strength, the effective elastic thickness and the seismogenic thickness have been calculated by a finite element modelling of the lithosphere across the Central System mountain range and the bordering Duero and Madrid sedimentary basins. Only a dry mantle under strike-slip/extension and a strain rate of 10-15 s-1, or under extension and 10-16 s-1, causes a strong lithosphere. The integrated strength and the elastic thickness are lower in the mountain chain than in the basins. These anisotropies have been maintained since the Cenozoic and determine the mountain uplift and the biharmonic folding of the Iberian lithosphere during the Alpine deformations. The seismogenic thickness bounds the seismic activity in the upper–middle crust, and the decreasing crustal strength from the Duero Basin towards the Madrid Basin is related to a parallel increase in Plio–Quaternary deformations and seismicity. However, elasto–plastic modelling shows that current African–Eurasian convergence is resolved elastically or ductilely, which accounts for the low seismicity recorded in this region.

Parametric Analysis of Concrete Solar Collectors

Concrete solar collectors offer a type of solar collector with structural, aesthetic and economic advantages over current populartechnologies. This study examines the influential parameters of concrete solar collectors. In addition to the external conditions,the performance of a concrete solar collector is influenced by the thermal properties of the concrete matrix, piping network andfluid. Geometric and fluid flow parameters also influence the performance of the concrete solar collector. A literature review ofconcrete solar collectors is conducted in order to define the benchmark parameters from which individual parameters are thencompared. The numerical model consists of a 1D pipe flow network coupled with the heat transfer in a 3D concrete domain. Thispaper is concerned with the physical parameters that define the concrete solar collector, thus a constant surface temperature isused as the exposed surface boundary condition with all other surfaces being insulated. Results show that, of the parametersinvestigated, the pipe spacing, ps, concrete conductivity, kc, and the pipe embedment depth, demb, are among those parameterswhich have greatest effect on the collector’s performance. The optimum balance between these parameters is presented withrespect to the thermal performance and discussed with reference to practical development issues.

Composites and foams based on polylactic acid (PLA)

Cette étude est destinée à la production et à la caractérisation des composites d’acide polylactique (PLA) et des fibres naturelles (lin, poudre de bois). Le moussage du PLA et ses composites ont également été étudiés afin d’évaluer les effets des conditions de moulage par injection et du renfort sur les propriétés finales de ces matériaux. Dans la première partie, les composites constitués de PLA et des fibres de lin ont été produits par extrusion suivit par un moulage en injection. L’effet de la variation du taux de charge (15, 25 et 40% en poids) sur les caractéristiques morphologique, mécanique, thermique et rhéologique des composites a été évalué. Dans la deuxième étape, la poudre de bois (WF) a été choisie pour renforcer le PLA. La préparation des composites de PLA et WF a été effectuée comme dans la première partie et une série complète de caractérisations morphologique, mécanique, thermique et l’analyse mécanique dynamique ont été effectués afin d’obtenir une évaluation complète de l’effet du taux de charge (15, 25 et 40% en poids) sur les propriétés du PLA. Finalement, la troisième partie de cette étude porte sur les composites de PLA et de renfort naturel afin de produire des composites moussés. Ces mousses ont été réalisées à l’aide d’un agent moussant exothermique (azodicarbonamide) via le moulage par injection, suite à un mélange du PLA et de fibres naturelles. Dans ce cas, la charge d’injection (quantité de matière injectée dans le moule: 31, 33, 36, 38 et 43% de la capacité de la presse à injection) et la concentration en poudre de bois (15, 25 et 40% en poids) ont été variées. La caractérisation des propriétés mécanique et thermique a été effectuée et les résultats ont démontré que les renforts naturels étudiés (lin et poudre de bois) permettaient d’améliorer les propriétés mécaniques des composites, notamment le module de flexion et la résistance au choc du polymère (PLA). En outre, la formation de la mousse était également efficace pour le PLA vierge et ses composites car les masses volumiques ont été significativement réduites.

Applications for nanomaterials in critical technologies

This thesis is devoted to the development, synthesis, properties, and applications of nano materials for critical technologies, including three areas: (1) Microbial contamination of drinking water is a serious problem of global significance. About 51% of the waterborne disease outbreaks in the United States can be attributed to contaminated ground water. Development of metal oxide nanoparticles, as viricidal materials is of technological and fundamental scientific importance. Nanoparticles with high surface areas and ultra small particle sizes have dramatically enhanced efficiency and capacity of virus inactivation, which cannot be achieved by their bulk counterparts. A series of metal oxide nanoparticles, such as iron oxide nanoparticles, zinc oxide nanoparticles and iron oxide-silver nanoparticles, coated on fiber substrates was developed in this research for evaluation of their viricidal activity. We also carried out XRD, TEM, SEM, XPS, surface area measurements, and zeta potential of these nanoparticles. MS2 virus inactivation experiments showed that these metal oxide nanoparticle coated fibers were extremely powerful viricidal materials. Results from this research suggest that zinc oxide nanoparticles with diameter of 3.5 nm, showing an isoelectric point (IEP) at 9.0, were well dispersed on fiberglass. These fibers offer an increase in capacity by orders of magnitude over all other materials. Compared to iron oxide nanoparticles, zinc oxide nanoparticles didn’t show an improvement in inactivation kinetics but inactivation capacities did increase by two orders of magnitude to 99.99%. Furthermore, zinc oxide nanoparticles have higher affinity to viruses than the iron oxide nanoparticles in presence of competing ions. The advantages of zinc oxide depend on high surface charge density, small nanoparticle sizes and capabilities of generating reactive oxygen species. The research at its present stage of development appears to offer the best avenue to remove viruses from water. Without additional chemicals and energy input, this system can be implemented by both points of use (POU) and large-scale use water treatment technology, which will have a significant impact on the water purification industry. (2) A new family of aliphatic polyester lubricants has been developed for use in micro-electromechanical systems (MEMS), specifically for hard disk drives that operate at high spindle speeds (>15000rpm). Our program was initiated to address current problems with spin-off of the perfluoroether (PFPE) lubricants. The new polyester lubricant appears to alleviate spin-off problems and at the same time improves the chemical and thermal stability. This new system provides a low cost alternative to PFPE along with improved adhesion to the substrates. In addition, it displays a much lower viscosity, which may be of importance to stiction related problems. The synthetic route is readily scalable in case additional interest emerges in other areas including small motors. (3) The demand for increased signal transmission speed and device density for the next generation of multilevel integrated circuits has placed stringent demands on materials performance. Currently, integration of the ultra low-k materials in dual Damascene processing requires chemical mechanical polishing (CMP) to planarize the copper. Unfortunately, none of the commercially proposed dielectric candidates display the desired mechanical and thermal properties for successful CMP. A new polydiacetylene thermosetting polymer (DEB-TEB), which displays a low dielectric constant (low-k) of 2.7, was recently developed. This novel material appears to offer the only avenue for designing an ultra low k dielectric (1.85k), which can still display the desired modulus (7.7Gpa) and hardness (2.0Gpa) sufficient to withstand the process of CMP. We focused on further characterization of the thermal properties of spin-on poly (DEB-TEB) ultra-thin film. These include the coefficient of thermal expansion (CTE), biaxial thermal stress, and thermal conductivity. Thus the CTE is 2.0*10-5K-1 in the perpendicular direction and 8.0*10-6 K-1 in the planar direction. The low CTE provides a better match to the Si substrate which minimizes interfacial stress and greatly enhances the reliability of the microprocessors. Initial experiments with oxygen plasma etching suggest a high probability of success for achieving vertical profiles.

Structure dependencies for multiscale polymer composites using extrusion processes

Multiscale reinforcement, using carbon microfibers and multi-walled carbon nanotubes, of polymer matrix composites manufactured by twin-screw extrusion is investigated for enhanced mechanical and thermal properties with an emphasis on the use of a diverging flow in the die for fluid mechanical fiber manipulation. Using fillers at different length scales (microscale and nanoscale), synergistic combinations have been identified to produce distinct mechanical and thermal behavior. Fiber manipulation has been demonstrated experimentally and computationally, and has been shown to enhance thermal conductivity significantly. Finally, a new physics driven predictive model for thermal conductivity has been developed based on fiber orientation during flow, which is shown to successfully capture composite thermal conductivity.

Síntese, extração e caracterização de biopolímeros de origem microalgal para desenvolvimento de nanofibras

Pesquisas com microalgas estão crescendo devido aos possíveis bioprodutos oriundos de sua biomassa, bem como as suas diferentes aplicabilidades. Microalgas podem ser cultivadas para a produção de biopolímeros com características de biocompatibilidade e biodegradabilidade. Nanofibras produzidas por electrospinning a partir de poli-β-hidroxibutirato (PHB) geram produtos com aplicabilidade na área de alimentos e médica. O objetivo deste trabalho foi selecionar microalgas com maior potencial para síntese de biopolímeros, em diferentes meios de cultivo, bem como purificar poli-β-hidroxibutirato e desenvolver nanofibras. Este trabalho foi dividido em cinco artigos: (1) Seleção de microalgas produtoras de biopolímeros; (2) Produção de biopolímeros pela microalga Spirulina sp. LEB 18 em cultivo com diferentes fontes de carbono e redução de nitrogênio; (3) Síntese de biopolímeros pela microalga Spirulina sp. LEB 18 em cultivos autotróficos e mixotróficos; (4) Purificação de poli-β- hidroxibutirato extraído da microalga Spirulina sp. LEB 18; e (5) Produção de nanofibras a partir de poli-β-hidroxibutirato de origem microalgal. Foram estudadas as microalgas Cyanobium sp., Nostoc ellipsosporum, Spirulina sp. LEB 18 e Synechococcus nidulans. Os biopolímeros foram extraídos nos tempos de 5, 10, 15, 20 e 25 d de cultivo a partir de digestão diferencial. Para os experimentos com diferentes nutrientes, foi utilizado como fonte de carbono, bicarbonato de sódio, acetato de sódio, glicose e glicerina modificando-se as concentrações de nitrogênio e fósforo. Os cultivos foram realizados em fotobiorreatores fechados de 2 L. A concentração inicial de inóculo foi 0,15 g.L-1 e os ensaios foram mantidos em estufa termostatizada a 30 ºC com iluminância de 41,6 µmolfótons.m -2 .s -1 e fotoperíodo 12 h claro/escuro. Para a purificação de PHB, foi utilizada a biomassa da cianobactéria Spirulina sp. LEB 18, cultivada em meio Zarrouk. Após a extração do biopolímero bruto, a amostra foi desengordurada com hexano e purificada com 1,2-carbonato de propileno. Foram determinadas as purezas e as propriedades térmicas no PHB purificado. O biopolímero utilizado para produzir as nanofibras apresentava 70 % de pureza. A técnica para produção de nanofibras foi o electrospinning. As microalgas que apresentaram máxima produtividade foram Nostoc ellipsosporum e Spirulina sp. LEB 18 com rendimento de biopolímero 19,27 e 20,62 % em 10 e 15 d, respectivamente, na fase de máximo crescimento celular. O maior rendimento de biopolímeros (54,48 %) foi obtido quando se utilizou 8,4 g.L-1 de NaHCO3, 0,05 g.L-1 de NaNO3 e 0,1 g.L-1 de K2HPO4. A condição que proporcionou maior pureza do PHB foi a 130 ºC e 5 min de contato entre o solvente (1,2-carbonato de propileno) e o PHB. As análises térmicas para todas as amostras foram semelhantes em relação ao PHB padrão (Sigma-Aldrich). A purificação com 1,2-carbonato de propileno foi eficiente para o PHB extraído de microalga, alcançando pureza acima de 90 %. A condição que apresentou menores diâmetros de nanofibras foi ao utilizar solução contendo 20 % de biopolímero solubilizado em clorofórmio. As condições do electrospinning que apresentou nanofibras com diâmetros de 470 e 537 nm foram, vazão 150 µL.h-1 , diâmetro do capilar 0,45 mm e voltagens entre 24,1 e 29,6 kV, respectivamente. A microalga Spirulina sp. LEB 18 produz PHB ao utilizar menores concentrações de nutrientes no meio de cultivo, que pode ser purificado com 1,2-carbonato de propileno. Este biopolímero possui aplicabilidade para produção de nanofibras.

Numerical analysis of wooden slabs with perforations under fire conditions

Wood is considered an ideal solution for floors and roofs building construction, due the mechanical and thermal properties, associated with acoustic conditions. These constructions have good sound absorption, heat insulation and relevant architectonic characteristics. They are used in many civil applications: concert and conference halls, auditoriums, ceilings, walls… However, the high vulnerability of wooden elements submitted to fire conditions requires the evaluation of its structural behaviour with accuracy. The main objective of this work is to present a numerical model to assess the fire resistance of wooden cellular slabs with different perforations. Also the thermal behaviour of the wooden slabs will be compared considering different material insulation, with different sizes, inside the cavities. A transient thermal analysis with nonlinear material behaviour will be solved using ANSYS© program. This study allows to verify the fire resistance, the temperature evolution and the char-layer, throughout a wooden cellular slab with perforations and considering the insulation effect inside the cavities.

Análise de propriedades térmicas e mecânicas de compósitos de argamassa e resíduo de borracha

Although already to exist alternative technique and economically viable for destination of used tires, quantitative data on properties of constructive elements that use the rubber waste as aggregate still are restricted. In the present work, the waste proceeding from industry of retreading as material for manufacture of composite destined to the production of constructive elements was considered. Mechanical and thermal properties of mortar had been analyzed Portland cement with addition of waste without treatment, in the ratios of 10%, 20% and 30% in mass in relation to the mass of the cement, substituting the aggregate in the trace in mortar 1:5 mass cement and sand. The size of the used residue varied between 0,30mm and 4,8mm (passing in the bolter 4,8mm and being restrained in the one of 0,30mm), being it in the formats fibers and granular. The influences of the size and the percentage of residue added to the mortar (in substitution to the aggregate) in the thermal and mechanical properties had been considered. Assays of body-of-test in thestates had been become fullfilled cool (consistency index) and hardened (absorption of water for capillarity, strength the compression, traction and strength flexural). The work is centralized in the problem of the relation thermal performance /strength mechanics of used constructive systems in regions of low latitudes (Been of the Piauí), characterized for raised indices of solar radiation.

Synthesis of innovative polyelectrolytes using monomers coming from renewable sources

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Desenvolvimento e caracterização de compósitos poli(tereftalato de etileno) reciclado (PET reciclado) com flocos de vidro.

The growing concern with the solid residues management, observed in the last decade, due to its huge amount and impact, has motivated the search for recycling processes, where these residues can be reprocessed to generate new products, enlarging the cycle of materials and energy which are present. Among the polymeric residues, there is poly (ethylene terephthalate) (PET). PET is used in food packaging, preferably in the bottling of carbonated beverages. The reintegration of post-consumer PET in half can be considered a productive action mitigation of environmental impacts caused by these wastes and it is done through the preparation of several different products at the origin, i.e. food packaging, with recycling rates increasing to each year. This work focused on the development and characterization mechanical, thermal, thermo-mechanical, dynamic mechanical thermal and morphology of the pure recycled PET and recycled PET composites with glass flakes in the weight fraction of 5%, 10% and 20% processed in a single screw extruder, using the following analytical techniques: thermogravimetry (TG), differential scanning calorimetry (DSC), tensile, Izod impact, Rockwell hardness, Vicat softening temperature, melt flow rate, burn rate, dynamic mechanical thermal analysis (DMTA) and scanning electron microscopy (SEM). The results of thermal analysis and mechanical properties leading to a positive evaluation, because in the thermograms the addition of glass flakes showed increasing behavior in the initial temperatures of thermal decomposition and melting crystalline, Furthermore was observed growing behavior in the mechanical performance of polymer composites, whose morphological structure was observed by SEM, verifying a good distribution of glass flakes, showing difference orientation in the center and in the surface layer of test body of composites with 10 and 20% of glass flakes. The results of DMTA Tg values of the composites obtained from the peak of tan ä showed little reductions due to poor interfacial adhesion between PET and recycled glass flakes.

Efficient P(3HB) extraction from Burkholderia sacchari cells using non-chlorinated solvents

© 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/

Análise paramétrica do método de injeção alternada de água e CO2(WAG) em reservatórios de petróleo

After the decline of production from natural energy of the reservoir, the methods of enhanced oil recovery, which methods result from the application of special processes such as chemical injection, miscible gases, thermal and others can be applied. The advanced recovery method with alternating - CO2 injection WAG uses the injection of water and gas, normally miscible that will come in contact with the stock oil. In Brazil with the discovery of pre-salt layer that gas gained prominence. The amount of CO2 present in the oil produced in the pre-salt layer, as well as some reservoirs is one of the challenges to be overcome in relation to sustainable production once this gas needs to be processed in some way. Many targets for CO2 are proposed by researchers to describe some alternatives to the use of CO2 gas produced such as enhanced recovery, storage depleted fields, salt caverns storage and marketing of CO2 even in plants. The largest oil discoveries in Brazil have recently been made by Petrobras in the pre -salt layer located between the states of Santa Catarina and Espírito Santo, where he met large volumes of light oil with a density of approximately 28 ° API, low acidity and low sulfur content. This oil that has a large amount of dissolved CO2 and thus a pioneering solution for the fate of this gas comes with an advanced recovery. The objective of this research is to analyze which parameters had the greatest influence on the enhanced recovery process. The simulations were performed using the "GEM" module of the Computer Modelling Group, with the aim of studying the advanced recovery method in question. For this work, semi - synthetic models were used with reservoir and fluid data that can be extrapolated to practical situations in the Brazilian Northeast. The results showed the influence of the alternating injection of water and gas on the recovery factor and flow rate of oil production process, when compared to primary recovery and continuous water injection or continuous gas injection