Organic-inorganic nanostructured multilayers for calcium phosphate biomineralization

The weak fixation of biomaterials within the bone structure is one of the major reasons of implants failures. Calcium phosphate (CaP) coatings are used in bone tissue engineering to improve implant osseointegration by enhancing cellular adhesion, proliferation and differentiation, leading to a tight and stable junction between implant and host bone. It has also been observed that materials compatible with bone tissue either have a CaP coating or develop such a calcified surface upon implantation. Thus, the development of bioactive coatings becomes essential for further improvement of integration with the surrounding tissue. However, most of current applied CaP coatings methods (e.g. physical vapor deposition), cannot be applied to complex shapes and porous implants, provide poor structural control over the coating and prevent incorporation of bioactive organic compounds (e.g. antibiotics, growth factors) because of the used harsh processing conditions. Layer-by-layer (LbL) is a versatile technology that permits the building-up of multilayered polyelectrolyte films in mild conditions based on the alternate adsorption of cationic and anionic elements that can integrate bioactive compounds. As it is recognized in natureâ s biomineralization process the presence of an organic template to induce mineral deposition, this work investigate a ion based biomimetic method where all the process is based on LbL methodology made of weak natural-origin polyelectrolytes. A nanostructured multilayer component, with 5 or 10 bilayers, was produced initially using chitosan and chondroitin sulphate polyelectrolyte biopolymers, which possess similarities with the extracellular matrix and good biocompatibility. The multilayers are then rinsed with a sequential passing of solutions containing Ca2+ and PO43- ions. The formation of CaP over the polyelectrolyte multilayers was confirmed by QCM-D, SEM and EDX. The outcomes show that 10 polyelectrolyte bilayer condition behaved as a  better site for initiating the formation of CaP as the precipitation occur at earlier stages than in 5 polyelectrolyte bilayers one. This denotes that higher number of bilayers could hold the CaP crystals more efficiently. This work achieved uniform coatings that can be applied to any surface with access to the liquid media in a low-temperature method, which potentiates the manufacture of effective bioactive biomaterials with great potential in orthopedic applications.

Biofunctionalization of titanium surfaces for dental implants: osteogenic, anti-microbial and tribocorrosion resistant surfaces

PhD thesis in Biomedical Engineering

Application of near surface mounted (NSM) strengthening technique to traditional timber frame walls

Timber frame buildings are well known as an efficient seismic resistant structure popular all over the world not only due to their seismic performance, but also to their low cost and the strength they offer. These constructions still exist today and it is important to be able to preserve them, so a better knowledge on their behaviour is sought. Furthermore, historic technologies could be used even in modern constructions to build seismic resistant buildings using more natural materials with lesser costs. A great rehabilitation effort is being carried out on this type of buildings, as their neglect has led to decay or their change in use and alterations to the structure has led to the need to retrofit such buildings; only recently studies on their behaviour have become available and only a few of them address the issue of possible strengthening techniques for this kind of walls. In this scope, an innovative retrofitting technique (near surface mounted steel flat bars) is proposed and validated on traditional timber frame walls based on an extensive experimental program. The results of the static cyclic tests on distinct wall typologies retrofitted with the NSM technique are herein presented and discussed in detail. The main features on deformation, lateral stiffness, lateral resistance and seismic performance indexes are analysed

Deploying public surface transit to forward messages in DTN

Delay Tolerant Network (DTN) is a communication architecture enabling connectivity in a topology with unregular end-to-end network connection. DTN enables communication in environments with cross-connectivity, large delays and delivery time variations, and a high error rate. DTN can be used in vehicular networks where public transport get involved. This research aims to analyze the role of public transit as a DTN routing infrastructure. The impact of using public transit as a relay router is investigated by referencing the network performance, defined by its delivery ratio, average delay and overhead. The results show that public transit can be used as a backbone for DTN in an urban scenario using existing protocols. This opens insights for future researches on routing algorithm and protocol design.

Evolution of the surface plasmon resonance of Au:TiO2 nanocomposite thin films with annealing temperature

This paper reports on the changes in the structural and morphological features occurring in a particular type of nanocomposite thin-film system, composed of Au nanoparticles (NPs) dispersed in a host TiO2 dielectric matrix. The structural and morphological changes, promoted by in-vacuum annealing experiments of the as-deposited thin films at different temperatures (ranging from 200 to 800 C), resulted in a well-known localized surface plasmon resonance (LSPR) phenomenon, which gave rise to a set of different optical responses that can be tailored for a wide number of applications, including those for optical-based sensors. The results show that the annealing experiments enabled a gradual increase of the mean grain size of the Au NPs (from 2 to 23 nm), and changes in their distributions and separations within the dielectric matrix. For higher annealing temperatures of the as-deposited films, a broad size distribution of Au NPs was found (sizes up to 100 nm). The structural conditions necessary to produce LSPR activity were found to occur for annealing experiments above 300 C, which corresponded to the crystallization of the gold NPs, with an average size strongly dependent on the annealing temperature itself. The main factor for the promotion of LSPR was the growth of gold NPs and their redistribution throughout the host matrix. On the other hand, the host matrix started to crystallize at an annealing temperature of about 500 C, which is an important parameter to explain the shift of the LSPR peak position to longer wavelengths, i.e. a red-shift.

Bacterial cellulose as a novel substrate for retinal pigment epithelium cells transplantation in age-related macular degeneration

Tese de Doutoramento em Engenharia Química e Biológica.

A cost study of common surface finish systems for steel structures

This paper presents part of a study aimed at finding a suitable, yet cost-effective, surface finish for a steel structure subject to the car washing environment and corrosive chemicals. The initial, life cycle and average equivalent annual (AEAC) costs for surface finishing methods were calculated for a steel structure using the LCCC algorithm developed by American Galvanizers Association (AGA). The cost study consisted of 45 common surface finish systems including: hot-dip galvanization (HDG), metallization, acrylic, alkyd and epoxy as well as duplex coatings such as epoxy zinc and inorganic zinc (IOZ). The results show that initial, life cycle and AEAC costs for hot dip galvanization are the lowest among all the other methods, followed by coal tar epoxy painting. The annual average cost of HDG for this structure was estimated about €0.22/m2, while the other cost-effective alternatives were: IOZ, polyurea, epoxy waterborne and IOZ/epoxy duplex coating.

Surface plasmon resonance-coupled photoluminescence and resistive switching behavior of pulsed laser-deposited Ag:SiC nanocermet thin films

In this study, Ag:SiC nanocermets were prepared via rapid thermal annealing (RTA) of pulsed laser-deposited SiC/Ag/SiC trilayers grown on Si substrate. Atomic force microscope images show that silver nanoparticles (Ag NPs) are formed after RTA, and the size of NPs increases with increasing Ag deposition time (t Ag). Sharp dip observed in the reflectance spectra confirmed the existence of Ag surface plasmons (SPs). The infrared transmission spectra showed an intense and broad absorption band around 780–800 cm−1 that can be assigned to Si-C stretching vibration mode. Influence of t Ag on the spectral characteristics of SP-enhanced photoluminescence (PL) and electrical properties of silicon carbide (SiC) films has been investigated. The maximum PL enhancement by 5.5 times for Ag:SiC nanocermets is achieved when t Ag ≈ 50 s. This enhancement is due to the strong resonant coupling between SiC and the SP oscillations of the Ag NPs. Presence of Ag NPs in SiC also induces a forming-free resistive switching with switching ratio of 2 × 10−2. The analysis of I–V curves demonstrates that the trap-controlled space-charge-limited conduction with filamentary model is the governing mechanism for the resistive switching in nanocerment thin films.

Novel hybrid multifunctional magnetoelectric porous composite films

Novel multifunctional porous films have been developed by the integration of magnetic CoFe2O4 (CFO) nanoparticles into poly(vinylidene fluoride)-Trifuoroethylene (P(VDF-TrFE)), taking advantage of the synergies of the magnetostrictive filler and the piezoelectric polymer. The porous films show a piezoelectric response with an effective d33 coefficient of -22 pC/N-1, a maximum magnetization of 12 emu.g-1 and a maximum magnetoelectric coefficient of 9 mV.cm-1.Oe-1. In this way, a multifunctional membrane has been developed suitable for advanced applications ranging from biomedical to water treatment.

Tailoring microstructure and physical properties of poly(vinylidene fluoride–hexafluoropropylene) porous films

This paper presents a systematic study for the production of poly(vinylidene fluoride-hexafluoropropylene), P(VDF-HFP), porous films using solvent evaporation (SE) and non-solvent induced phase separation (NIPS) techniques. Parameters such as volume fraction of the copolymer solution, film thickness, time exposure to air, non-solvent and temperature of the coagulation bath were investigated on the morphology, crystallization and mechanical properties of the samples. Films with different porous morphologies including homogeneous pore sizes, macrovoids and spherulites were obtained depending on the processing conditions, which in turn affect the wettability and mechanical properties of the material. Knowing that the phase content of the films also depends on the processing conditions, this paper shows that P(VDF-HFP) films with tailored porous morphology, electroactive phase content, hydrophobicity, cristallinity and mechanical properties can be achieved for a specific application using the adequate SE and NIPS techniques conditions.

Poly(vinylidene fluoride-trifluoroethylene) porous films: tailoring microstructure and physical properties by solvent casting strategies

A systematic study for the production of porous poly(vinylidene fluoride-trifluoroethylene), P(VDF-TrFE), films using solvent evaporation and non-solvent induced phase separation techniques is presented. Processing parameters such as copolymer volume fraction, solvent, preset exposure time to air before immersion, and non-solvent and temperature of the coagulation bath were varied and the corresponding sample morphology, hydrophobicity, thermal and mechanical properties were determined. Film morphologies including homogeneous pore distributions, micropores, microvoids, spherulites and non-porous films were obtained. The morphology variations strongly influence sample hydrophobicity and mechanical properties. All samples crystallize in the electroactive β-phase with a degree of crystallinity around 30 %.

Biochemical and physical surface functionalization of polycaprolactone as a key mediator of osteogenic differentiation and vascularized tissue morphogenesis

Tese de Doutoramento em Engenharia de Tecidos, Medicina Regenerativa e Células Estaminais.

Aspergilli and Penicillia related to the surface of ripening italian grana type cheese and its ripening environment

Information available on the mycoflora associated to ripening Italian “grana type” cheese is very poor. Recently, ochratoxin A (OTA) was detected in samples of packed grated cheese [1]; therefore, the need of information to perform a risk management was highlighted. Moreover, sterigmatocystin (STC) has been reported in cheese and it is considered an emerging problem. Despite the fact that both of them are mycotoxins included in group 2B by IARC [2,3], no European regulation exists. So, the main goal of this work is to give for the first time a general overview about Penicillia and Aspergilli growing on the surface of ripening “grana type” cheese, with particular attention on mycotoxigenic species. To perform this, in 2013 and 2014 crust samples were scratched from ripening grana cheese wheels and also Potato Dextrose Agar plates were exposed to monitor ripening house air. Then, 140 fungal isolates were randomly chosen, purified and monosporic colonies were obtained for their identification at specie level. A polyphasic approach is followed, based on morphological characterisation, toxic extrolites profiling and gene sequencing. The identification is still in progress, but the first results based on the morphological approach showed the presence of mycotoxigenic Aspergilli (Aspergillus flavus and A. versicolor) and various Penicillium species; among them Penicillium chrysogenum, P. implicatum and P. solitum were identified. Only P. chrysogenum was reported to produce the mycotoxins cyclopiazonic acid (CPA) and roquefortine-C (ROQ-C) [4]. These results will be presented and discussed. [1] A. Biancardi, R. Piro, G. Galaverna, C. Dall’Asta, "A simple and reliable liquid chromatography–tandem mass spectrometry method for determination of ochratoxin A in hard cheese" International Journal of Food Sciences and Nutrition 64 (5), 2013, 632 – 640. [2] International Agency for Research on Cancer (IARC) “IARC Monographs on the Evaluation of Carcinogenic Risks to Humans” 31, 1983, 191 – 199. [3] International Agency for Research on Cancer (IARC) “IARC Monographs on the Evaluation of carcinogenic Risks to Humans”, suppl. 7, 1987, 72. [4] J. I. Pitt, D. A. Hocking, “Fungi and Food Spoilage” 1997, 291.

Effect of surface plasmon resonance in TiO2/Au thin films on the fluorescence of self-assembled CdTe QDs structure

The exceptional properties of localised surface plasmons (LSPs), such as local field enhancement and confinement effects, resonant behavior, make them ideal candidates to control the emission of luminescent nanoparticles. In the present work, we investigated the LSP effect on the steady-state and time-resolved emission properties of quantum dots (QDs) by organizing the dots into self-assembled dendrite structures deposited on plasmonic nanostructures. Self-assembled structures consisting of water-soluble CdTe mono-size QDs, were developed on the surface of co-sputtered TiO2 thin films doped with Au nanoparticles (NPs) annealed at different temperatures. Their steady-state fluorescence properties were probed by scanning the spatially resolved emission spectra and the energy transfer processes were investigated by the fluorescence lifetime imaging (FLIM) microscopy. Our results indicate that a resonant coupling between excitons confined in QDs and LSPs in Au NPs located beneath the self-assembled structure indeed takes place and results in (i) a shift of the ground state luminescence towards higher energies and onset of emission from excited states in QDs, and (ii) a decrease of the ground state exciton lifetime (fluorescence quenching).

Goblet cell density association with tear function and ocular surface physiology

Purpose: To determine the relationship of goblet cell density (GCD) with tear function and ocular surface physiology. Methods: This was a cross-sectional study conducted in 35 asymptomatic subjects with mean age 23.8±3.6 years. Tear film assessment, conjunctiva and cornea examination were done in each subject. Conjunctival impression cytology was performed by applying Nitrocellulose Millipore MFTM-Membrane filter over the superior bulbar conjunctiva. The filter paper was than fixed with 96% ethanol and stained with Periodic Acid Schiff, Hematoxylin and Eosin. GCD was determined by optical microscopy. Relation between GCD and Schirmer score, tear break-up time (TBUT), bulbar redness, limbal redness and corneal staining was determined. Results: The mean GCD was 151±122 cells/mm2. GCD was found higher in eyes with higher Schirmer score but it was not significant (p = 0.75). There was a significant relationship ofGCDwith TBUT (p = 0.042). GCD was not correlated with bulbar redness (p = 0.126), and limbal redness (p = 0.054) as well as corneal staining (p = 0.079). No relationship of GCD with age and gender of the subjects (p > 0.05) was observed. Conclusion: GCD was found correlated with TBUT but no significant correlation was found with the aqueous portion of the tear, limbal as well as bulbar redness and corneal staining.