Preparation and Characterization of Polymeric Beads and Membranes for Boron Removal From Water

Boron is an element essential for various biological processes, nevertheless at high concentration it can cause health issues in both plants and animals, thus making boron a pollutant element. Low cost and effective polymeric adsorbents capable of removing boron in aqueous solution at neutral pH were prepared for this purpose. The adsorbent selectivity towards boron was conferred taking advantage of the interaction between boric acid and the alcoholic groups of N-methyl-D-Glucamine, which are able to form specific complexes. Two different kinds of devices were produced and tested: cross-linked chitosan hydrogel beads (CCBMG) and PVA/chitosan membranes, the latter taking advantage of scCO2-assisted phase inversion technique. The capability of the adsorbents to be regenerated and to allow recovery of boric acid from a solution emulating the concentration of boric acid in seawater were evaluated.

Measurement of CP violation with $B^0_{(s)} \to h^+ h^{\prime-}$ decays, $|V_{cb}|$ with $B^0_{s}\to D^{(*)-}_s \mu^+ \nu_\mu$ decays, and simulation and characterisation of the LHCb Upgrade II ECAL

The time-dependent CP asymmetries of the $B^0\to\pi^+\pi^-$ and $B^0_s\toK^+K^-$ decays and the time-integrated CP asymmetries of the $B^0\toK^+\pi^-$ and $B^0_s\to\pi^+K^-$ decays are measured, using the $p-p$ collision data collected with the LHCb detector and corresponding to the full Run2. The results are compatible with previous determinations of these quantities from LHCb, except for the CP-violation parameters of the $B^0_s\to K^+K^-$ decays, that show a discrepancy exceeding 3 standard deviations between different data-taking periods. The investigations being conducted to understand the discrepancy are documented. The measurement of the CKM matrix element $|V_{cb}|$ using $B^0_{s}\to D^{(*)-}_s\mu^+ \nu_\mu$ is also reported, using the $p-p$ collision data collected with the LHCb detector and corresponding to the full Run1. The measurement leads to $|V_{cb}| = (41.4\pm0.6\pm0.9\pm1.2)\times 10^{-3}$, where the first uncertainty is statistical, the second is systematic, and the third is due to external inputs. This measurement is compatible with the world averages and constitutes the first measurement of $|V_{cb}|$ at a hadron collider and the absolute first one with decays of the $B^0_s$ meson. The analysis also provides the very first measurements of the branching ratio and form factors parameters of the signal decay modes. The study of the characteristics ruling the response of an electromagnetic calorimeter (ECAL) to profitably operate in the high luminosity regime foreseen for the Upgrade2 of LHCb is reported in the final part of this Thesis. A fast and flexible simulation framework is developed to this purpose. Physics performance of different configurations of the ECAL are evaluated using samples of fully simulated $B^0\to \pi^+\pi^-\pi^0$ and $B^0\to K^{*0}e^+e^-$ decays. The results are used to guide the development of the future ECAL and are reported in the Framework Technical Design Report of the LHCb Upgrade2 detector.

Vulnerable users' protection with advanced recycling paving materials. Design and characterisation of rubber-based impact-absorbing pavement materials for bike lanes and sidewalks

Our cities are constantly evolving, and the necessity to improve the condition and safety of the urban infrastructures is fundamental. However, on the roads, the specific needs of cyclists and pedestrians are often neglected. The Vulnerable Road Users (VRUs), among whom cyclists and pedestrians are, rarely benefit from the most innovative safety measures. Inspired by playgrounds and aiming to reduce VRUs injuries, the Impact-Absorbing Pavements (IAP) developed as novel sidewalks, and bike lanes surface layers may help decrease injuries, fatalities, and the related societal costs. To achieve this goal, the End-of-Life Tyres (ELTs) crumb rubber (CR) is used as a primary resource, bringing its elastic properties into the surface layer. The thesis is divided into five main chapters. The first concerns the formulation and the definition of a feasible mix. The second explores the mechanical and environmental properties in detail, and the ageing effect is also assessed. The third describes the modelling of the material to simulate accidents and measure the injury reduction, especially on the head. The fourth chapter is reserved for the field trial. The last gives some perspectives on the research and proposes a way to optimize and improve the data and results collected during the doctoral research. It was observed that the specimens made with cold protocol have noticeable performances and reduce the overall carbon footprint impact of this material. The material modelling and the accident simulation proved the performance of the IAP against head injuries, and the field trial confirmed the good results obtained in the laboratory for the cold-made material. Finally, the outcomes of this thesis opened many prospective to the IAP development, such as the use of a plant-based binder or recycled aggregates and gave a positive prospect of an innovative material to the urban road infrastructures.

Biogenic modified silica as a sorbent of cadmium ions: Preparation and characterization

This work describes the preparation and characterization of biogenic modified silica from rice hull ash and its use as a sorbent of cadmium ions. Thus, an agro-industrial residue has been used to produce a new adsorbent product which is able to remove toxic elements. Mesoporous biogenic silica was obtained by alkaline extraction of sodium silicate by hydrolysis with the sol-gel process, and it was modified with salen using 1,2-dichloroethane as a spacer. The surface area of the silica was measured by nitrogen adsorption/desorption analysis. Surface modification was measured by Fourier transform infrared spectroscopy. The degree of functionalization was obtained by elemental analysis. This work showed that biogenic modified silica can be produced in aqueous media from rice hull ash using a simple method, providing an alternative method for adsorbent preparation. Thermogravimetric analysis showed that the salen-modified silica is stable up to 209 C. The modified silica displays appropriate structural characteristics for an adsorbent. The cylindrical pores, open at both ends, allow free diffusion of cadmium ions to the adsorption sites on the silica surface. The surface modification increases cadmium adsorption on the silica surface 100-fold. The salen-modified silica showed specific adsorption for Cd2+ of 44.52 mg/g SiO2 at cadmium concentration of 100 mg/l.

Membrane design and characterisation by incorporation of ionic liquids

Dissertação apresentada para obtenção do Grau de Doutor em Engenharia Química, especialidade de Operações Unitárias e Fenómenos de Transferência, pela Universidade Nova de Lisboa, Faculdade de Ciências e Tecnologia

Evaluation of Magnetic,Dielectric and Mechanical Properties of Rubber Ferrite Composites

In the present study the preparation and characterisation of rubber ferrite composites (RFC) containing barium ferrite (BaF) and strontium ferrite (SrF) have been dealt with. The incorporation of the hard ferrites into natural and nitrile rubber was carried out according to a specific recipe for various loadings of magnetic fillers. For this, the ferrite materials namely barium ferrite and strontium ferrite having the general formula MO6Fe2O3 have been prepared by the conventional ceramic techniques. After characterisation they were incorporated into the natural and nitrile rubber matrix by mechanical method. Carbon black was also incorporated at different loading into the rubber ferrite composites to study its effect on various properties. The cure characteristics, mechanical, dielectric and magnetic properties of these composites were evaluated. The ac electrical conductivity of both the ceramic ferrites and rubber ferrite composites were also calculated using a simple relation. The investigations revealed that the rubber ferrite composites with the required dielectric and magnetic properties can be obtained by the incorporation of ferrite fillers into the rubber matrix, without compromising much on the processability and mechanical properties.

Magnetic, Dielectric and Physicomechanical Properties of Rubber Ferrite Nanocomposites

In the present study the preparation and characterisation of rubber ferrite composites containing nickel ferrite and gamma ferric oxide have been dealt with.Synthetic rubbers viz. ethylene propylene diene rubber and neoprene rubber were used for the incorporation of nickel ferrite and gamma ferric oxide for the synthesis of RFCs. Incorporation of ferrites were carried out according to a specific recipe for various loadings of the magnetic fillers. The ferrites used for the preparation of RFCs were synthesised using sol-gel method and structural characterisation was carried out. Experimental techniques like X-ray diffraction, Transmission electron microscopy and other analytical techniques were used for this. Precharaterised ferrites were then incorporated at different loading into rubber according to conventional mixing methods. The cure characteristics, mechanical, dielectric, magnetic and microwave properties of these composites were evaluated. The effect of carbon black on these properties of RFCs were carried out.

Characterisation and regulation of E2F-6 and E2F-6b in the rat heart: a potential target for myocardial regeneration?

The E2F transcription factors are instrumental in regulating cell cycle progression and growth, including that in cardiomyocytes, which exit the cell cycle shortly after birth. E2F-6 has been demonstrated to act as a transcriptional repressor; however, its potential role in normal cardiomyocyte proliferation and hypertrophy has not previously been investigated. Here we report the isolation and characterisation of E2F-6 and E2F-6b in rat cardiomyocytes and consider its potential as a target for myocardial regeneration following injury. At the mRNA level, both rat E2F-6 and the alternatively spliced variant, E2F-6b, were expressed in E18 myocytes and levels were maintained throughout development into adulthood. Interestingly, E2F-6 protein expression was down-regulated during myocyte development suggesting that it is regulated post-transcriptionally in these cells. During myocyte hypertrophy, the mRNA expressions of E2F-6 and E2F-6b were not regulated whereas E2F-6 protein was up-regulated significantly. Indeed, E2F-6 protein expression levels closely parallel the developmental withdrawal of myocytes from the cell cycle and the subsequent reactivation of their cell cycle machinery during hypertrophic growth. Furthermore, depletion of E2F-6, using anti-sense technology, results in death of cultured neonatal myocytes. Taken together, abrogation of E2F-6 expression in neonatal cardiomyocytes leads to a significant decrease in their viability, consistent with the notion that E2F-6 might be required for maintaining normal myocyte growth.

Purification and functional characterisation of rhiminopeptidase A, a novel aminopeptidase from the venom of Bitis gabonica rhinoceros

This study describes the discovery and characterisation of a novel aminopeptidase A from the venom of B. g. rhinoceros and highlights its potential biological importance. Similar to mammalian aminopeptidases, rhiminopeptidase A might be capable of playing roles in altering the blood pressure and brain function of victims. Furthermore, it could have additional effects on the biological functions of other host proteins by cleaving their N-terminal amino acids. This study points towards the importance of complete analysis of individual components of snake venom in order to develop effective therapies for snake bites.

The synthesis of dicobalt and dinickel complexes of trimethylsilylethynyl-1, 2-dihydrofullerene; characterisation by n.m.r. and structure of the first acyclic metal fullerene derivative: molecular structure of [η2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2(η-C5H5)2]

The synthesis and characterisation of the complexes [η2-{2-H-1-(Me3SiC ≡ C)-C60}Co2(CO)6] (2)} and [η-2-{2-H-1-(Me3SiC ≡ C)-C60}Ni2η-C5H5)2] (3)} is reported, together with a single-crystal molecular structure for (3). This provides the first structural data for an acyclic metal derivative of [60]-fullerene.

The effects of canal preparation and filling on the incidence of dentinal defects

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Tissue engineering of co-cultured skin substitutes using biocomposite membranes based on collagen and polycaprolactone

The preparation and characterisation of collagen: PCL, gelatin: PCL and gelatin/collagen:PCL biocomposites for manufacture of tissue engineered skin substitutes are reported. Films of collagen: PLC, gelatin: PCL (1:4, 1:8 and 1:20 w/w) and gelatin/collagen:PCL (1:8 and 1:20 w/w) biocomposites were prepared by impregnation of lyophilised collagen and/or gelatin mats by PCL solutions followed by solvent evaporation. In vitro assays of total protein release of collagen:PCL and gelatin: PCL biocomposite films revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the biocomposite samples that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. Good compatibility of all biocomposite groups was proven by interaction with 3T3 fibroblasts, normal human epidermal keratinocytes (NHEK), and primary human epidermal keratinocytes (PHEK) and dermal fibroblasts (PHDF) in vitro respectively. The 1:20 collagen: PCL materials exhibiting good cell growth curves and mechanical characteristics were selected for engineering of skin substitutes in this work. The tissue-engineered skin model based on single-donor PHEK and PHDF with differentiated confluent epidermal layer and fibrous porous dermal layer was then developed successfully in vitro proven by SEM and immunohistochemistry assay. The following in vivo animal study on athymic mice revealed early complete wound healing in 10 days and good integration of co-cultured skin substitutes with adjacent mice skin structures. Thus the co-cultured skin substitutes based on 1:20 collagen: PCL biocomposite membranes was proven in principle. The approach to skin modelling reported here may find application in wound treatment, gene therapy and screening of new pharmaceuticals.

Design and development of cationic liposomes as DNA vaccine adjuvants

Cationic liposomes have been extensively explored for their efficacy in delivering nucleic acids, by offering the ability to protect plasmid DNA against degradation, promote gene expression and, in the case of DNA vaccines, induce both humoural and cellular immune responses. DNA vaccines may also offer advantages in terms of safety, but they are less effective and need an adjuvant to enhance their immunogenicity. Therefore, cationic liposomes can be utilised as delivery systems and/or adjuvants for DNA vaccines to stimulate stronger immune responses. To explore the role of liposomal systems within plasmid DNA delivery, parameters such as the effect of lipid composition, method of liposome preparation and presence of electrolytes in the formulation were investigated in characterisation studies, in vitro transfection studies and in vivo biodistribution and immunisation studies. Liposomes composed of 1,2-dioleoyl-sn-glycero 3-phosphoethanolamine (DOPE) in combination with 1,2-dioleoyl-3-trimethylammonium-propane (DOTAP) or 1,2-stearoyl-3- trimethylammonium-propane (DSTAP) were prepared by the lipid hydration method and hydrated in aqueous media with or without presence of electrolytes. Whilst the in vitro transfection efficiency of all liposomes resulted to be higher than Lipofectin, DSTAP-based liposomes showed significantly higher transfection efficiency than DOTAP-based formulations. Furthermore, upon intramuscular injection of liposomal DNA vaccines, DSTAP-based liposomes showed a significantly stronger depot effect at the injection site. This could explain the result of heterologous immunisation studies, which revealed DSTAP-based liposomal vaccines induce stronger immune responses compared to DOTAP-based formulations. Previous studies have shown that having more liposomally associated antigen at the injection site would lead to more drainage of them into the local lymph nodes. Consequently, this would lead to more antigens being presented to antigen presenting cells, which are circulating in lymph nodes, and this would initiate a stronger immune response. Finally, in a comparative study, liposomes composed of dimethyldioctadecylammonium bromide (DDA) in combination with DOPE or immunostimulatory molecule of trehalose 6,6-dibehenate (TDB) were prepared and investigated in vitro and in vivo. Results showed that although DDA:TDB is not able to transfect the cells efficiently in vitro, this formulation induces stronger immunity compared to DDA:DOPE due to the immunostimulatory effects of TDB. This study demonstrated, while the presence of electrolytes did not improve immune responses, small unilamellar vesicle (SUV) liposomes induced stronger humoural immune responses compared to dehydration rehydration vesicle (DRV) liposomes. Moreover, lipid composition was shown to play a key role in in vitro and in vivo behaviour of the formulations, as saturated cationic lipids provided stronger immune responses compared to unsaturated lipids. Finally, heterologous prime/boost immunisation promoted significantly stronger immune responses compared to homologous vaccination of DNA vaccines, however, a single immunisation of subunit vaccine provoked comparable levels of immune response to the heterologous regimen, suggesting more immune efficiency for subunit vaccines compared to DNA vaccines.

Composite cell support membranes based on collagen and polycaprolactone for tissue engineering of skin

The preparation and characterisation of collagen:PCL composites for manufacture of tissue engineered skin substitutes and models are reported. Films having collagen:PCL (w/w) ratios of 1:4, 1:8 and 1:20 were prepared by impregnation of lyophilised collagen mats by PCL solutions followed by solvent evaporation. In vitro assays of collagen release and residual collagen content revealed an expected inverse relationship between the collagen release rate and the content of synthetic polymer in the composite that may be exploited for controlled presentation and release of biopharmaceuticals such as growth factors. DSC analysis revealed the characteristic melting point of PCL at around 60°C and a tendency for the collagen component, at high loading, to impede crystallinity development within the PCL phase. The preparation of fibroblast/composite constructs was investigated using cell culture as a first stage in mimicking the dermal/epidermal structure of skin. Fibroblasts were found to attach and proliferate on all the composites investigated reaching a maximum of 2×105/cm2 on 1:20 collagen:PCL materials at day 8 with cell numbers declining thereafter. Keratinocyte growth rates were similar on all types of collagen:PCL materials investigated reaching a maximum of 6.6×104/cm2 at day 6. The results revealed that composite films of collagen and PCL are favourable substrates for growth of fibroblasts and keratinocytes and may find utility for skin repair. © 2003 Elsevier Ltd. All rights reserved.

Movement-related potentials in Huntington's disease: movement preparation and execution

Movement-related potentials (MRPs) reflect increasing cortical activity related to the preparation and execution of voluntary movement. Execution and preparatory components may be separated by comparing MRPs recorded from actual and imagined movement. Imagined movement initiates preparatory processes, but not motor execution activity. MRPs are maximal over the supplementary motor area (SMA), an area of the cortex involved in the planning and preparation of movement. The SMA receives input from the basal ganglia, which are affected in Huntington's disease (HD), a hyperkinetic movement disorder. In order to further elucidate the effects of the disorder upon the cortical activity relating to movement, MRPs were recorded from ten HD patients, and ten age-matched controls, whilst they performed and imagined performing a sequential button-pressing task. HD patients produced MRPs of significantly reduced size both for performed and imagined movement. The component relating to movement execution was obtained by subtracting the MRP for imagined movement from the MRP for performed movement, and was found to be normal in HD. The movement preparation component was found by subtracting the MRP found for a control condition of watching the visual cues from the MRP for imagined movement. This preparation component in HD was reduced in early slope, peak amplitude, and post-peak slope. This study therefore reported abnormal MRPs in HD. particularly in terms of the components relating to movement preparation, and this finding may further explain the movement deficits reported in the disease.