Electrochemical and analytical investigation of passive films formed on stainless steels in alkaline media

Passive films were grown in potentiodynamic mode, by cyclic voltammetry on AISI 316 and AISI 304 stainless steels. The composition of these films was investigated by X-ray photoelectron spectroscopy (XPS). The electrochemical behaviour and the chemical composition of the passive films formed by cyclic voltammetry were compared to those of films grown under natural conditions (by immersion at open circuit potential, OCP) in alkaline solutions simulating concrete. The study included the effect of pH of the electrolyte and the effect of the presence of chloride ions. The XPS results revealed important changes in the passive film composition, which becomes enriched in chromium and depleted in magnetite as the pH decreases. On the other hand, the presence of chlorides promotes a more oxidised passive layer. The XPS results also showed relevant differences on the composition of the oxide layers for the films formed under cyclic voltammetry and/or under OCP.

A Obra “Faça-você-mesmo” : Estética da Participação nas Artes Digitais

Doutoramento em Ciências da Comunicação - Especialidade de Comunicação e Artes

A emergência da escrita: produções escritas de crianças no jardim de infância

Relatório da Prática Profissional Supervisionada Mestrado em Educação Pré-Escolar

Estratégias informativas de um jornal híbrido: o caso do “I” nos media portugueses

Dissertação apresentada à Escola Superior de Comunicação Social como parte dos requisitos para obtenção de grau de mestre em Audiovisual e Multimédia.

Destruction of the tar present in syngas by combustion in porous media

The cleaning of syngas is one of the most important challenges in the development of technologies based on gasification of biomass. Tar is an undesired byproduct because, once condensed, it can cause fouling and plugging and damage the downstream equipment. Thermochemical methods for tar destruction, which include catalytic cracking and thermal cracking, are intrinsically attractive because they are energetically efficient and no movable parts are required nor byproducts are produced. The main difficulty with these methods is the tendency for tar to polymerize at high temperatures. An alternative to tar removal is the complete combustion of the syngas in a porous burner directly as it leaves the particle capture system. In this context, the main aim of this study is to evaluate the destruction of the tar present in the syngas from biomass gasification by combustion in porous media. A gas mixture was used to emulate the syngas, which included toluene as a tar surrogate. Initially, CHEMKIN was used to assess the potential of the proposed solution. The calculations revealed the complete destruction of the tar surrogate for a wide range of operating conditions and indicated that the most important reactions in the toluene conversion are C6H5CH3 + OH <-> C6H5CH2 + H2O, C6H5CH3 + OH <-> C6H4CH3 + H2O, and C6H5CH3 + O <-> OC6H4CH3 + H and that the formation of toluene can occur through C6H5CH2 + H <-> C6H5CH3. Subsequently, experimental tests were performed in a porous burner fired with pure methane and syngas for two equivalence ratios and three flow velocities. In these tests, the toluene concentration in the syngas varied from 50 to 200 g/Nm(3). In line with the CHEMKIN calculations, the results revealed that toluene was almost completely destroyed for all tested conditions and that the process did not affect the performance of the porous burner regarding the emissions of CO, hydrocarbons, and NOx.

In Situ Near-Infrared (NIR) Versus High-Throughput Mid- Infrared (MIR) Spectroscopy to Monitor Biopharmaceutical Production

The development of biopharmaceutical manufacturing processes presents critical constraints, with the major constraint being that living cells synthesize these molecules, presenting inherent behavior variability due to their high sensitivity to small fluctuations in the cultivation environment. To speed up the development process and to control this critical manufacturing step, it is relevant to develop high-throughput and in situ monitoring techniques, respectively. Here, high-throughput mid-infrared (MIR) spectral analysis of dehydrated cell pellets and in situ near-infrared (NIR) spectral analysis of the whole culture broth were compared to monitor plasmid production in recombinant Escherichia coil cultures. Good partial least squares (PLS) regression models were built, either based on MIR or NIR spectral data, yielding high coefficients of determination (R-2) and low predictive errors (root mean square error, or RMSE) to estimate host cell growth, plasmid production, carbon source consumption (glucose and glycerol), and by-product acetate production and consumption. The predictive errors for biomass, plasmid, glucose, glycerol, and acetate based on MIR data were 0.7 g/L, 9 mg/L, 0.3 g/L, 0.4 g/L, and 0.4 g/L, respectively, whereas for NIR data the predictive errors obtained were 0.4 g/L, 8 mg/L, 0.3 g/L, 0.2 g/L, and 0.4 g/L, respectively. The models obtained are robust as they are valid for cultivations conducted with different media compositions and with different cultivation strategies (batch and fed-batch). Besides being conducted in situ with a sterilized fiber optic probe, NIR spectroscopy allows building PLS models for estimating plasmid, glucose, and acetate that are as accurate as those obtained from the high-throughput MIR setup, and better models for estimating biomass and glycerol, yielding a decrease in 57 and 50% of the RMSE, respectively, compared to the MIR setup. However, MIR spectroscopy could be a valid alternative in the case of optimization protocols, due to possible space constraints or high costs associated with the use of multi-fiber optic probes for multi-bioreactors. In this case, MIR could be conducted in a high-throughput manner, analyzing hundreds of culture samples in a rapid and automatic mode.

In situ NIR spectroscopy monitoring of plasmid production processes effect of producing strain, medium composition and the cultivation strategy

BACKGROUNDWhile the pharmaceutical industry keeps an eye on plasmid DNA production for new generation gene therapies, real-time monitoring techniques for plasmid bioproduction are as yet unavailable. This work shows the possibility of in situ monitoring of plasmid production in Escherichia coli cultures using a near infrared (NIR) fiber optic probe. RESULTSPartial least squares (PLS) regression models based on the NIR spectra were developed for predicting bioprocess critical variables such as the concentrations of biomass, plasmid, carbon sources (glucose and glycerol) and acetate. In order to achieve robust models able to predict the performance of plasmid production processes, independently of the composition of the cultivation medium, cultivation strategy (batch versus fed-batch) and E. coli strain used, three strategies were adopted, using: (i) E. coliDH5 cultures conducted under different media compositions and culture strategies (batch and fed-batch); (ii) engineered E. coli strains, MG1655endArecApgi and MG1655endArecA, grown on the same medium and culture strategy; (iii) diverse E. coli strains, over batch and fed-batch cultivations and using different media compositions. PLS models showed high accuracy for predicting all variables in the three groups of cultures. CONCLUSIONNIR spectroscopy combined with PLS modeling provides a fast, inexpensive and contamination-free technique to accurately monitoring plasmid bioprocesses in real time, independently of the medium composition, cultivation strategy and the E. coli strain used.