Cationic Liposomes as antigenic delivery systems: development of an immunoprotective strategy against Candida albicans

Tese de Doutoramento Biologia Molecular e Ambiental - Especialidade em Biologia Celular e Saúde

Improvign mixing processes with the help of numerical tools

In several industrial applications, highly complex behaviour materials are used together with intricate mixing processes, which difficult the achievement of the desired properties for the produced materials. This is the case of the well-known dispersion of nano-sized fillers in a melt polymer matrix, used to improve the nanocomposite mechanical and/or electrical properties. This mixing is usually performed in twin-screw extruders, that promote complex flow patterns, and, since an in loco analysis of the material evolution and mixing is difficult to perform, numerical tools can be very useful to predict the evolution and behaviour of the material. This work presents a numerical based study to improve the understanding of mixing processes. Initial numerical studies were performed with generalized Newtonian fluids, but, due to the null relaxation time that characterize this type of fluids, the assumption of viscoelastic behavior was required. Therefore, the polymer melt was rheologically characterized, and, a six mode Phan-Thien-Tanner and Giesekus models were used to fit the rheological data. These viscoelastic rheological models were used to model the process. The conclusions obtained in this work provide additional and useful data to correlate the type and intensity of the deformation history promoted to the polymer nanocomposite and the quality of the mixing obtained.

Tailored magnetic and magnetoelectric responses of polymer-based composites

The manipulation of electric ordering with applied magnetic fields has been realized on magnetoelectric (ME) materials, however, their ME switching is often accompanied by significant hysteresis and coercivity that represents, for some applications, a severe weakness. To overcome this obstacle, this work focus on the development of a new type of ME polymer nanocomposites that exhibits tailored ME response at room temperature. The multiferroic nanocomposites are based on three different ferrite nanoparticles, Zn0.2Mn0.8Fe2O4 (ZMFO), CoFe2O4 (CFO) and Fe3O4 (FO), dispersed in a piezoelectric co-polymer poly(vinylindene fluoride-trifluoroethylene), P(VDF-TrFE), matrix. No substantial differences were detected on the time-stable piezoelectric response of the composites (≈ -28 pC.N−1) with distinct ferrite fillers and for the same ferrite content of 10wt.%. Magnetic hysteresis loops from pure ferrite nanopowders showed different magnetic responses. ME results of the nanocomposite films with 10wt.% ferrite content revealed that the ME induced voltage increases with increasing DC magnetic field until a maximum of 6.5 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.26 T, and 0.8 mV∙cm−1∙Oe−1, at an optimum magnetic field of 0.15T, for the CFO/P(VDF-TrFE) and FO/P(VDF-TrFE) composites, respectively. On the contrary, the ME response of the ZMFO/P(VDF-TrFE) exposed no hysteresis and high dependence on the ZMFO filler content. Possible innovative applications such as memories and information storage, signal processing, ME sensors and oscillators have been addressed for such ferrite/PVDF nanocomposites.

Thin films composed of gold nanoparticles dispersed in a dielectric matrix: the influence of the host matrix on the optical and mechanical responses

Gold nanoparticles were dispersed in two different dielectric matrices, TiO2 and Al2O3, using magnetron sputtering and a post-deposition annealing treatment. The main goal of the present work was to study how the two different host dielectric matrices, and the resulting microstructure evolution (including both the nanoparticles and the host matrix itself) promoted by thermal annealing, influenced the physical properties of the films. In particular, the structure and morphology of the nanocomposites were correlated with the optical response of the thin films, namely their localized surface plasmon resonance (LSPR) characteristics. Furthermore, and in order to scan the future application of the two thin film system in different types of sensors (namely biological ones), their functional behaviour (hardness and Young's modulus change) was also evaluated. Despite the similar Au concentrations in both matrices (~ 11 at.%), very different microstructural features were observed, which were found to depend strongly on the annealing temperature. The main structural differences included: (i) the early crystallization of the TiO2 host matrix, while the Al2O3 one remained amorphous up to 800 °C; (ii) different grain size evolution behaviours with the annealing temperature, namely an almost linear increase for the Au:TiO2 system (from 3 to 11 nm), and the approximately constant values observed in the Au:Al2O3 system (4–5 nm). The results from the nanoparticle size distributions were also found to be quite sensitive to the surrounding matrix, suggesting different mechanisms for the nanoparticle growth (particle migration and coalescence dominating in TiO2 and Ostwald ripening in Al2O3). These different clustering behaviours induced different transmittance-LSPR responses and a good mechanical stability, which opens the possibility for future use of these nanocomposite thin film systems in some envisaged applications (e.g. LSPR-biosensors).

Produção e caracterização de filmes finos nanocompósitos de Au-Ag dispersos numa matriz dielétrica, com efeito de ressonância de plasmão de superfície localizado

Dissertação de mestrado em Engenharia de Materiais

Estudos de dispersão de nanografite em polipropileno

Dissertação de mestrado integrado em Engenharia de Materiais

Controlled aggregation of gold nanoparticles in a di-ureasilmatrix. Optical and micro indentation investigation

Nanocomposite materials with an organic-inorganic urea-silicate (di-ureasil) based matrix containing gold nanoparticles (NPs) were synthesized and characterized by optical (UV/Vis) spectroscopy and indentation measurement. The urea silicate gels were obtained by reaction between silicon alkoxyde modified by isocyanate group and polyethylene glycol oligomer with amine terminal groups in presence of catalyst. The latter ensures the successful incorporation of citrate-stabilized gold NPs in the matrix. It is shown that using a convenient destabilizing agent (AgNO3) and governing the preparative conditions, the aggregation degree of gold NPs can be controlled. The developed synthesis procedure significantly simplifies the preparative procedure of gold/urea silicate nanocomposites, compared to the procedure using gold NPs, preliminary covered with silica shells. Mechanical properties of the prepared sample were characterised using depth sensing indentation methods (DSI) and an idea about the type of aggregation structures was suggested.

Desenvolvimento de uma matriz de sensores piezoresistivos baseados em técnicas de impressão

Dissertação de mestrado em Técnicas de Caracterização e Análise Química

Preparação de suspensões aquosas de nanopartículas de carbono para deposição em superfícies

Dissertação de mestrado integrado em Engenharia de Materiais

Rheological characterization of EVA and HDPE polymer modified bitumens under large deformation at 20 º C

Large amplitude oscillatory shear (LAOS) coupled with Fourier transform rheology (FTR) was used for the first time to characterize the large deformation behavior of selected bituminous binders at 20 C. Two polymer modified bitumens (PMB) containing recycled EVA and HDPE and two unmodified bitumens were tested with LAOS-FTR. The LAOS-FTR response of all binders was compared at same frequency, at same Deborah number (by tuning the frequency to the relaxation time of each binder) and at same phase shift angle d (by tuning the frequency to the one corresponding to d = 50 in the SAOS response of each sample). In all the approaches, LAOS-FTR results allowed to differentiate between all the nonlinear mechanical characteristics of the tested binders. All binders show LAOS-FTR patterns reminiscent from colloidal dispersions and emulsions. EVA PMB was less prone to strain-induced microstructural changes when compared to HDPE PMB which showed larger values of nonlinear FTR parameters for the range of shear strains tested in LAOS.

Antibacterial Ag/a-C nanocomposite coatings: The influence of nano-galvanic a-C and Ag couples on Ag ionization rates

Biofilm formation has been pointed as a major concern in different industrial applications, namely on biomedical implants and surgical instruments, which has prompted the development of new strategies for production of efficient antimicrobial surfaces. In this work, nano âgalvanic couples were created to enhance the antibacterial properties of silver, by embedding it into amorphous carbon (a-C) matrix. The developed Ag/a-C nanocomposite coatings, deposited by magnetron sputtering, revealed an outstanding antibacterial activity against S.epidermidis, promoting a total reduction in biofilm formation with no bacteria counts in all dilution. The open circuit potential (OCP) tests in 0.9% NaCl confirmed that a-C shows a positive \OCP\ value, in contrast to Ag coating, thus enhancing the ionization of biocidal Ag+ due to the nano-galvanic couple activation. This result was confirmed by the inductively coupled plasma-optical emission spectroscopy (ICP-OES), which revealed a higher Ag ionization rate in the nanocomposite coating in comparison with the Ag coating. The surface of Ag/a-C and Ag coatings immersed in 0.9% NaCl were monitored by scanning electron microscopy (SEM) over a period of 24 hours, being found that the Ag ionization determined by ICP-OES was accompanied by an Ag nanoparticles coalescence and agglomeration in Ag/a-C coating.