Insights into the biological significance of alternative splicing in Arabidopsis: functional characterization of a dual-targeted E3 ligase and the SCL30a SR protein

Dissertation presented to obtain the Ph.D degree in Molecular Biology

Monitorização e otimização da deposição de filmes de óxidos mistos por RF-sputtering

Dissertação para obtenção do Grau de Mestre em Engenharia Física

Time-of-flight secondary ion mass spectrometry: new application for urinary stones analysis

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Development of ion jelly thin films for electrochemical devices

Dissertação para obtenção do Grau de Doutor em Química Sustentável

The role of electron transfer in DNA building blocks: evaluation of strand breaks and their implications

Dissertação para obtenção do Grau de Doutor em Engenharia Física

Dual track sell-out: Signaling through IPO and Underpricing

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Finance from the NOVA – School of Business and Economics

Characterization of molecular damage induced by UV photons and carbon ions on biomimetic heterostructures

The study of the effect of radiation on living tissues is a rather complex task to address mainly because they are made of a set of complex functional biological structures and interfaces. Particularly if one is looking for where damage is taking place in a first stage and what are the underlying reaction mechanisms. In this work a new approach is addressed to study the effect of radiation by making use of well identified molecular hetero-structures samples which mimic the biological environment. These were obtained by assembling onto a solid support deoxyribonucleic acid (DNA) and phospholipids together with a soft water-containing polyelectrolyte precursor in layered structures and by producing lipid layers at liquid/air interface with DNA as subphase. The effects of both ultraviolet (UV) radiation and carbon ions beams were systematically investigated in these heterostructures, namely damage on DNA by means vacuum ultraviolet (VUV), infrared (IR), X-Ray Photoelectron (XPS) and impedance spectroscopy. Experimental results revealed that UV affects furanose, PO2-, thymines, cytosines and adenines groups. The XPS spectrometry carried out on the samples allowed validate the VUV and IR results and to conclude that ionized phosphate groups, surrounded by the sodium counterions, congregate hydration water molecules which play a role of UV protection. The ac electrical conductivity measurements revealed that the DNA electrical conduction is arising from DNA chain electron hopping between base-pairs and phosphate groups, with the hopping distance equal to the distance between DNA base-pairs and is strongly dependent on UV radiation exposure, due loss of phosphate groups. Characterization of DNA samples exposed to a 4 keV C3+ ions beam revealed also carbon-oxygen bonds break, phosphate groups damage and formation of new species. Results from radiation induced damage carried out on biomimetic heterostructures having different compositions revealed that damage is dependent on sample composition, with respect to functional targeted groups and extent of damage. Conversely, LbL films of 1,2-dipalmitoyl-sn-Glycero-3-[Phospho-rac-(1-glycerol)] (Sodium Salt) (DPPG) liposomes, alternated with poly(allylamine hydrochloride) (PAH) revealed to be unaffected, even by prolonged UV irradiation exposure, in the absence of water molecules. However, DPPG molecules were damaged by the UV radiation in presence of water with cleavage of C-O, C=O and –PO2- bonds. Finally, the study of DNA interaction with the ionic lipids at liquid/air interfaces revealed that electrical charge of the lipid influences the interaction of phospholipid with DNA. In the presence of DNA in the subphase, the effects from UV irrladiation were seen to be smaller, which means that ionic products from biomolecules degradation stabilize the intact DPPG molecules. This mechanism may explain why UV irradiation does not cause immediate cell collapse, thus providing time for the cellular machinery to repair elements damaged by UV.

Ultrastructural study on the morphological changes to male worms of Schistosoma mansoni after in vitro exposure to allicin

INTRODUCTION: Garlic has a wide range of actions, including antibacterial, antiviral, antifungal, antiprotozoal and anthelmintic actions. This antiparasitic activity has been attributed to allicin, which is the main constituent of garlic. The present study aimed to investigate the in vitro activity of allicin on the tegument of adult Schistosoma mansoni worms using scanning electron microscopy. METHODS: Swiss Webster mice were infected with S. mansoni cercariae (100 per mouse) and sacrificed 50 days later to acquire the adult worms. These worms were collected by perfusion and placed in RPMI medium 1,640 at 37°C before transferring to RPMI media containing 0 (control), 5, 10, 15 and 20mg/mL of allicin, where they were incubated for 2h. The worms were fixed in 2.5% glutaraldehyde solution, washed twice, post-fixed in osmium tetroxide, washed twice and then dehydrated with ascending grades of ethanol. The samples were air-dried, mounted on stubs, gold coated in an ion sputtering unit and viewed using a scanning electron microscope. RESULTS: A concentration of 5mg/mL caused wrinkling in the tegument; a concentration of 10mg/mL resulted in changes to tubercles and loss or modification of spines. With 15 and 20mg/mL increasing damage to the tegument could be seen, such as vesicle formation and the presence of ulcers. CONCLUSIONS: These findings demonstrate the effect of allicin on adult S. mansoni worms and indicate that most of the changes occur at concentrations greater than that normally indicated for treatment.

Al-doped ZnO ceramic sputtering targets based on nanocrystalline powders produced by emulsion detonation synthesis – deposition and application as a transparent conductive oxide material

Transparent conducting oxides (TCOs) have been largely used in the optoelectronic industry due to their singular combination of low electrical resistivity and high optical transmittance. They are usually deposited by magnetron sputtering systems being applied in several devices, specifically thin film solar cells (TFSCs). Sputtering targets are crucial components of the sputtering process, with many of the sputtered films properties dependent on the targets characteristics. The present thesis focuses on the development of high quality conductive Al-doped ZnO (AZO) ceramic sputtering targets based on nanostructured powders produced by emulsion detonation synthesis method (EDSM), and their application as a TCO. In this sense, the influence of several processing parameters was investigated from the targets raw-materials synthesis to the application of sputtered films in optoelectronic devices. The optimized manufactured AZO targets present a final density above 99 % with controlled grain size, an homogeneous microstructure with a well dispersed ZnAl2O4 spinel phase, and electrical resistivities of ~4 × 10-4 Ωcm independently on the Al-doping level among 0.5 and 2.0 wt. % Al2O3. Sintering conditions proved to have a great influence on the properties of the targets and their performance as a sputtering target. It was demonstrated that both deposition process and final properties of the films are related with the targets characteristics, which in turn depends on the initial powder properties. In parallel, the influence of several deposition parameters in the film´s properties sputtered from these targets was investigated. The sputtered AZO TCOs showed electrical properties at room temperature that are superior to simple oxides and comparable to a reference TCO – indium tin oxide (ITO), namely low electrical resistivity of 5.45 × 10-4 Ωcm, high carrier mobility (29.4 cm2V-1s-1), and high charge carrier concentration (3.97 × 1020 cm-3), and also average transmittance in the visible region > 80 %. These superior properties allowed their successful application in different optoelectronic devices.

Development of paper transistor with memory effect

This work will discuss the use of different paper membranes as both the substrate and dielectric for field-effect memory transistors. Three different nanofibrillated cellulose membranes (NFC) were used as the dielectric layer of the memory transistors (NFC), one with no additives, one with an added polymer PAE and one with added HCl. Gallium indium zinc oxide (GIZO) was used as the device’s semiconductor and gallium aluminium zinc oxide (GAZO) was used as the gate electrode. Fourier transform infrared spectroscopy (FTIR) was used to access the water content of the paper membranes before and after vacuum. It was found that the devices recovered their water too quickly for a difference to be noticeable in FTIR. The transistor’s electrical performance tests yielded a maximum ION/IOFF ratio of around 3,52x105 and a maximum subthreshold swing of 0,804 V/decade. The retention time of the dielectric charge that grants the transistor its memory capabilities was accessed by the measurement of the drain current periodically during 144 days. During this period the mean drain current did not lower, leaving the retention time of the device indeterminate. These results were compared with similar devices revealing these devices to be at the top tier of the state-of-the-art.

Centrality and rapidity dependence of inclusive jet production in sNN=5.02 TeV proton-lead collisions with the ATLAS detector

Measurements of the centrality and rapidity dependence of inclusive jet production in sNN−−−√=5.02 TeV proton--lead (p+Pb) collisions and the jet cross-section in s√=2.76 TeV proton--proton collisions are presented. These quantities are measured in datasets corresponding to an integrated luminosity of 27.8 nb−1 and 4.0 pb−1, respectively, recorded with the ATLAS detector at the Large Hadron Collider in 2013. The p+Pb collision centrality was characterised using the total transverse energy measured in the pseudorapidity interval −4.9<η<−3.2 in the direction of the lead beam. Results are presented for the double-differential per-collision yields as a function of jet rapidity and transverse momentum (pT) for minimum-bias and centrality-selected p+Pb collisions, and are compared to the jet rate from the geometric expectation. The total jet yield in minimum-bias events is slightly enhanced above the expectation in a pT-dependent manner but is consistent with the expectation within uncertainties. The ratios of jet spectra from different centrality selections show a strong modification of jet production at all pT at forward rapidities and for large pT at mid-rapidity, which manifests as a suppression of the jet yield in central events and an enhancement in peripheral events. These effects imply that the factorisation between hard and soft processes is violated at an unexpected level in proton--nucleus collisions. Furthermore, the modifications at forward rapidities are found to be a function of the total jet energy only, implying that the violations may have a simple dependence on the hard parton--parton kinematics.

Poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) lithium-ion battery separator membranes prepared by phase inversion

Separator membranes based on poly(vinylidene fluoride-co-chlorotrifluoroethylene) (PVDF-CTFE) were prepared by solvent casting technique based on its phase diagram in N,Ndimethylformamide (DMF) solvent. The microstructure of the PVDF-CTFE separator membranes depends on the initial position (temperature and concentration) of the solution in the phase diagram of the PVDF-CTFE/DMF system. A porous microstructure is achieved for PVDF-CTFE membranes with solvent evaporation temperature up to 50 ºC for a polymer/solvent relative concentration of 20 wt%. The ionic conductivity of the separator depends on the degree of porosity and electrolyte uptake, the highest room temperature value being 1.5 mS.cm-1 for the sample with 20 wt% of polymer concentration and solvent evaporation temperature at 25 ºC saturated with 1 mol L-1 lithium bis (trifluoromethanesulfonyl) imide (LiTFSI) in propylene carbonate (PC). This PVDF-CTFE separator membrane in Li/C-LiFePO4 half-cell shows good cyclability and rate capability, showing a discharge value after 50 cycles of 92 mAh.g-1 at 2 C, which is still 55% of the theoretical value. PVDF-CTFE separators are thus excellent candidates for high-power and safety lithium-ion batteries applications.

Effect of the degree of porosity on the performance of poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) blend membranes for lithium-ion battery separators

Porous polymer membranes based on poly(vinylidene fluoride-trifluoroethylene)/poly(ethylene oxide) copolymers, P(VDF-TrFE)/PEO, are prepared through the, from partial to total, elimination of PEO, leading to interconnected micropores in the polymer blends. Electrolyte uptake, thermal and mechanical properties depend on the amount of PEO present in the polymer blend. Further, the degree of crystallinity of PEO and the elastic modulus (E´) of the polymer blend decrease with increasing PEO removal. Electrical properties of the polymer blend membranes are influenced by the porosity and are dominated by diffusion. The temperature dependence of ionic conductivity follows the Arrhenius behavior. It is the highest for the membranes with a volume fraction of pores of 44% (i.e, 90% PEO removal), reaching a value of 0.54 mS.cm-1 at room temperature. Battery performance was determined by assembling Li/C-LiFePO4 swagelok cells. The polymer blends with 90% PEO removal exhibit rate (124 mAhg-1 at C/5 and 47 mAhg-1 at 2C) and cycling capabilities suitable for lithium ion battery applications.

Modeling separator membranes physical characteristics for optimized lithium ion battery performance

The effect of varying separator membrane physical parameters such as degree of porosity, tortuosity and thickness, on battery delivered capacity was studied in order to optimize performance of lithium-ion batteries. This was achieved by a theoretical mathematical model relating the Bruggeman coefficient with the degree of porosity and tortuosity. The inclusion of the separator membrane in the simulation model of the battery system does not affect the delivered capacity of the battery. The ionic conductivity of the separator and consequently the delivered capacity values obtained at different discharge rates depends on the value of the Bruggeman coefficient, which is related with the degree of porosity and tortuosity of the membrane. Independently of scan rate, the optimal value of the degree of porosity is above 50% and the separator thickness should range between 1 μm at 32 μm for improved battery performance.