The increased demand of fossil fuel along with the depletion of economical crude oil resources, environmental challenges such as the accumulation of CO2 and other greenhouse gases in the atmosphere and the reduction of the dependence on imported oil are some of the motivations for the huge interest in biofuels. Biobutanol produced from ABE fermentation has been considered to be a good partial replacement for fossil fuels. However, challenges such as the need for inexpensive feed-stocks, improved fermentation performance to achieve higher final butanol concentration and higher yield, an efficient method for solvent recovery, and water recycle are the main obstacles to make the production of this alcohol economically viable. Pervaporation, a membrane-based process, is considered to be an attractive separation method to remove butanol from ABE fermentation broth. Among the membranes used for butanol separation, PDMS membranes showed reasonable performance such as good permeability, and appropriate selectivity for butanol separation by pervaporation. However, PDMS membranes need to be improved in terms of performance to be applicable in large scale butanol production plants. In this study, activated carbon nanoparticles have been embedded into the matrix of the PDMS membrane to improve its separation performance and, in particular, the permeation flux and butanol selectivity. Result showed that the presence of nanoparticles improves the PDMS membrane performance up to a certain particle loading. Moreover, it was shown that the operating conditions have a major impact on the pervaporation membrane separation process. The best membrane for pervaporation separation of butanol from binary aqueous solutions was obtained for a 6 wt% particle concentration where the total permeation flux and butanol selectivity increased by 42.6% and 51.9%, respectively, compared to neat PDMS membranes. Moreover, the best performance for the separation of butanol from ABE model solutions was achieved for an 8 wt% nanoparticle loading. Both the selectivity for butanol and the total permeation flux more than doubled in comparison to neat PDMS membranes prepared in this study. Moreover, in order to compare the PDMS/AC mixed matrix membrane performance for pervaporation separation of butanol from binary and ABE model solutions with PDMS membranes available on the market, experiments were also performed with a commercial PDMS membrane. Result of butanol separation from ABE model solutions showed that mixed matrix membranes with 8 wt% nanoparticles loading had a higher permeation flux than that of the commercial membranes. It was clearly shown that the presence of activated carbon nanoparticles in the matrix of the PDMS would be beneficial for the pervaporation separation of butanol from ABE fermentation broths. To better comprehend how the presence of activated carbon nanoparticles in the polymeric membranes enhance the performance of the membranes, a series of numerical simulations were performed. A finite difference model was developed to simulate the mass transfer of permeating components through mixed matrix membranes by pervaporation for a wide range of relative permeability, nanoparticle loading, particle shape, particle size and different filler adsorption isotherms. Finally, an investigation has been performed to optimize the butanol pervaporation separation process from ABE fermentation broth at an industrial scale.

Endothelial cells, EC, are the cell type closest to the blood stream in vessel walls. These cells can affect the origin of atherosclerosis, plaques clogging the vessels. The behaviour of EC is affected by neighbouring smooth muscle cells and shear stress from the blood flow. The aim with this thesis was to fabricate a structure for an aorta-on-a-chip that can be used to study these two parameters and their influence on EC and vascular diseases. Previous research using a two-channel system resulted in leakage and low viability of the muscle cells. A three-channel system has therefore been made to include a middle channel with the muscle cells incorporated in a gel. Cell medium is flowed in the outer channels to provide the cells with nutrition. The flow in the channel with EC has been calculated to correspond to the shear stress in an aorta. Membranes of polyethylene terephthalate and polycarbonate were used to divide the channels and both were shown to be compatible with EC. Different bonding procedures were investigated to manufacture leakage-free chips. In the study, adhesive bonding clogged the channels and the parameters for thermal bonding of COC, cyclic olefin copolymer, were not fully optimised. This made chemical bonding with layers of PDMS, polydimethylsiloxane, the best alternative. APTES, (3-Aminopropyl)triethoxysilane, treatment in addition to plasma treatment on the surfaces improved the bonding strength. Polycarbonate membranes got better results in the bonding tests than polyethylene terephthalate. The resulting aorta-on-a-chip was therefore successfully fabricated in PDMS and polycarbonate membranes using plasma and APTES treatment for bonding.

Metabolomics is a post genomic field of research concerned with the study of low molecular weight compounds within a biological system permitting the investigation of the metabolite differences between natural and perturbed systems (such as cells, organs and tissues). Rapid identification and discrimination of biological samples based upon metabolic differences and physiological status in microbiology, mammalian systems (particularly for disease diagnosis), plants and food science is highly desirable. Volatile organic compound (VOC) profiling is a novel area of research where the composition of the VOCs emitted by the biological samples can be correlated to its origin and physiological status. The aim of this project was to investigate the applicability of VOC profiling as a potential complementary tool within metabolomics.In this project the discrimination of bacteria using a novel gas phase separation method was investigated and the development of VOC-based profiling tools for the collections of VOCs emitted from biological samples was also studied. The optimisation and validation of a high throughput method for VOC analysis was achieved and this was used to assess wound healing.VOC metabolite profiling was further extended to the discrimination of S. typhimurium contaminated meat; the study was conducted in parallel with metabolite profiling analysis for the analysis of non-volatile small molecules. Finally, enhanced vibrational spectroscopic techniques were applied to the characterisation and screening of dye molecules in contaminated foodstuffs using Raman spectroscopy. This thesis clearly demonstrates that VOC metabolic profiling is a complementary tool within the metabolomics toolbox, one of its great attractions is that it permits the characterisation of biological samples in a rapid and non-invasive manner. The technique provides detailed chemical information regarding the VOC composition present above the headspace of the sample and can be used to understand its physiological status and biological origin. VOCs metabolite profiling will become a valuable tool for non-invasive analysis of many biological systems. Raman spectroscopy is a sensitive and non-destructive technique which can generate detailed chemical and structural information regarding the analyte under investigation with little or no sample preparation needed. The effect of the weak Raman signal can be significantly amplified by coupling the analyte molecule to surfaces of nanoparticles and demonstrated that it is ideal for analysing aqueous dye solutions in a quantitative manner.

Obtaining new insights into the behavior of free-living marine organisms is fundamental for conservation efforts and anticipating the impact of climate change on marine ecosystems. Despite the recent advances in biotelemetry, collecting physiological and behavioral parameters of underwater free-living animals remains technically challenging. In this thesis, we develop the first magnetic underwater animal monitoring system that utilizes Tunnel magnetoresistance (TMR) sensors, the most sensitive solid-state sensors today, coupled with flexible magnetic composites. The TMR sensors are composed of CoFeB free layers and MgO tunnel barriers, patterned using standard optical lithography and ion milling procedures. The short and long-term stability of the TMR sensors has been studied using statistical and Allan deviation analysis. Instrumentation noise has been reduced using optimized electrical interconnection schemes. We also develop flexible NdFeB-PDMS composite magnets optimized for applications in corrosive marine environments, and which can be attached to marine animals. The magnetic and mechanical properties are studied for different NdFeB powder concentrations and the performance of the magnetic composites for different exposure times to sea water is systematically investigated. Without protective layer, the composite magnets loose more than 50% of their magnetization after 51 days in seawater. The durability of the composite magnets can be considerably improved by using polymer coatings which are protecting the composite magnet, whereby Parylene C is found to be the most effective solution, providing simultaneously corrosion resistance, flexibility, and enhanced biocompatibility. A Parylene C film of 2μm thickness provides the sufficient protection of the magnetic composite in corrosive aqueous environments for more than 70 days. For the high level performance of the system, the theoretically optimal position of the composite magnets with respect to the sensing direction of the sensor has been estimated using finite element modeling software. The magnetic sensing system has been practically implemented for monitoring the belly size of a model fish and for monitoring the behavior of the largest living bivalve, giant clam (Tridacna maxima) in an aquarium. In both of these experiments, the sensing system showed a high performance, indicating its potential for novel marine monitoring applications.

This work deals with fabrication and test of microfluidic chip for separating substances. For separation of substances is used electrophoresis and detection is by integrated electrodes.

The diploma thesis deals with cellular membrane model preparation on microfluidic devices. It summarizes means of microfluidic device fabrication, phospholipid bilayer formation mechanisms, optimization techniques and characterization methods of those systems. It focuses on free-standing planar lipid bilayers which are easily accessible by a number of different characterization methods and at the same time exhibit good stability and variability. The aim of this work is to design and prepare a microfluidic chip on which a planar lipid bilayer can be prepared. It therefore presents microfluidic device prepared by soft lithography of PDMS adapted for model membrane formation by self-assembly of phospholipids at the interface of aqueous and organic phases created by the architecture of the microfluidic device. Formation of the model membrane was visualized by optical microscopy and fluorescence-lifetime imaging microscopy.

Orientador: Marcelo Augusto Assunção Sanches / Resumo: Recentes estudos têm abordado o aprimoramento de sensores de pressão com a finalidade de reproduzir a sensibilidade da pele humana para ser utilizada em robôs. Dentre diversos materiais disponíveis na literatura, destaca-se o material piezoresistivo à base do elastômero Polidimetilsiloxano e Cobre Dendritico (Cu-PDMS), devido à tecnologia empregada na produção destes sensores. Este trabalho trata a síntese e a caracterizações de compósitos piezoresistivo Cu-PDMS para confecção de sensores de pressão, na forma matricial, para aplicações biomédicas, como palmilhas instrumentadas, sensor on/off, dentre outros. Com finalidade de análise do material atuando como sensor de pressão, foram fabricadas e testadas amostras com diferentes composições. Para o estudo das propriedades de cada amostra, foram realizadas caracterizações elétricas (resistência elétrica com pressão variável, condutividade ao longo do tempo e espectroscopia de impedância), mecânicas (caracterização mecânica do material, ensaio de tração e ensaio termogravimétrico) e Microscopia Eletrônica de Varredura (MEV). Os resultados obtidos mostram as faixas possíveis para utilização do material como sensor de pressão, e os fatores que podem influenciar o seu emprego. / Abstract: Recent studies have addressed the improvement of pressure sensors in order to reproduce the sensitivity of human skin to be used in robots. Among the various materials available in the literature, the piezoresistive material based on the polydimethylsiloxane and Dendritic Copper (Cu-PDMS) elastomer stands out, due to the technology used in the production of these sensors. This work deals with the synthesis and characterization of Cu-PDMS piezoresistive composites for making pressure sensors, in matrix form, for biomedical applications such as instrumented insoles, on / off sensor, among others. In order to analyze the material acting as a pressure sensor, samples with different compositions were manufactured and tested. For the study of the properties of each sample, electrical characterizations (electrical resistance with variable pressure, conductivity over time and impedance spectroscopy), mechanical characterizations (mechanical characterization of the material, tensile test and thermogravimetric test) and Scanning Electron Microscopy were performed (ME V). The results obtained show the possible ranges for using the material as a pressure sensor, and the factors that can influence its use. / Mestre

In this study, pervaporation, a membrane-based process was studied for in-situ separation of butanol. This technique has a great potential due to its high selectivity, low energy requirement and high efficiency. The primary objective was to improve the performance of the Polydimethylsiloxane (PDMS) membrane for the pervaporation separation and the recovery of butanol by adding nanoparticles into its matrix to make mixed matrix membrane (MMM). These nanoparticles included zinc-based Metal Organic Frameworks (MOFs) and zinc oxide. Different particle sizes of zeolitic imidazolate framework (ZIF-8) were synthesized. The separation performance of MMMs incorporating different sizes of ZIF-8 nanoparticles was compared to the performance of mixed matrix membranes incorporating zinc oxide as well as pure PDMS membrane. Different characteristics of ZIF-8 and their impact on the performance of the host membrane were discussed. Result showed that the presence of nanoparticles improves the PDMS membrane performance up to a certain particle loading. Moreover, it was shown that the particle size and interfacial bond between polymer and particles have a major impact on the pervaporation membrane separation process. The best membrane for pervaporation separation of butanol from binary aqueous solutions was obtained for the 8 wt% small-size ZIF-8/PDMS MMM where the total permeation flux and butanol selectivity were increased by 350% and 6%, respectively, compared to neat PDMS membranes. In addition to the MOFs, nanotubes are considered emerging nanostructured materials for use in membrane separation applications due to their high molecular diffusivity and unique geometry. Recent progress has also been made on the modification of nanotube surface functionality, and the fabrication of nanotube mixed matrix membranes as well as the ability to align them in MMMs. Since numerous types of nanotubes are available and the process of producing well-aligned nanotube MMMs is very challenging, a theoretical model using finite difference method (FD) was used to gain a deeper understanding on the effect of nanotubes on the separation performance of mixed matrix membranes. A series of numerical simulations were performed and the effects of various structural parameters, including the tubular filler volume fraction, orientation, length-to-diameter aspect ratio, and permeability ratio, were assessed. The results showed that the relative permeability is enhanced by vertically-aligned nanotubes and further increased with an increase of the permeability ratio, filler volume fraction and the length-to-diameter aspect ratio. In addition, comparing the simulation results with existing analytical models for the prediction of the relative permeability acknowledges a need to develop a new correlation that would provide more accurate predictions of the relative permeability of MMMs with embedded nanotube fillers.

Electrospinning is a useful technique that can generate micro- and nano-meter sized fibers from polymer materials. Modification of the electrospinning parameters and apparatus can generate nanofibers for use in diverse applications ranging from tissue engineering to nanocomposite fabrication; however, electrospun fibers are typically collected in a random orientation and over large areas limiting their applications.  Here we present several methods to control the deposition of electrospun nanofibers, such as the use of a single auxiliary electrode ring and a negatively charged collector substrate to control the deposition area and the construction of a parallel electrode collector known as the triple electrode setup to control the uniaxial alignment of nanofibers. The numerous constructed setups were advanced by the use of electric field computations to assess the distribution of the electric field and its effect on the deposition behavior and morphology of the electrospun nanofibers. The electrostatic force imposed by the auxiliary electrodes provides converged electric fields that direct the nanofibers to their desired deposition targets. Here it is shown that the use of the auxiliary electrode ring dramatically decreased the deposition area of nanofibers, the negatively charged substrate yielded more uniform nanofibers and the triple electrode setup is a viable method to achieve uniaxially aligned nanofiber mats.    The electrospinning of copolymers appears as an attractive option for enhancing the overall properties of nanofibers as it offers possibility of an intrinsic control of the polymeric material itself. The poly(methyl methacrylate)-graft-poly(dimethylsiloxane) graft copolymer  (PMMA-g-PDMS) is considered to be an organic-inorganic hybrid material with much potential in its use in nanocomposites, and in this work has been successfully synthesized and electrospun via the various constructed electrospinning setups.   In the final elements of this work, the triple electrode setup is used in combination with a dynamic rotating collector to yield a novel collector and has been successfully used to produce PMMA-g-PDMS nanofiber sheets that were further incorporated in a PDMS matrix to yield nanocomposite sheets. A variant of the triple electrode setup with partially insulated electrodes is devised in combination with a methodology to remove the nanofibers from the collector. The nanofibers once removed and dried were incorporated in a PDMS matrix to yield nanocomposites. The preferential dissolution of the fibers from the matrix rendered the fibers to templates and a final porous material with uniaxial nanochannels could be obtained.   This work is believed to be able to lead to a better understanding of the mechanisms of nanofiber deposition and alignment, and should be of help to the design of more practical collecting structures, hence promoting the applications of the electrospinning technique.

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