Browsing by Author "Pullar, R. C."
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- Aerosol assisted chemical vapour deposition of hydroxyapatite-embedded titanium dioxide composite thin filmsPublication . Piccirillo, C.; Denis, C. J.; Pullar, R. C.; Binions, R.; Parkin, I. P.; Darr, J. A.; Castro, P. M. L.This work describes the first Aerosol Assisted Chemical Vapour Deposition (AACVD) synthesis of photocatalytic titanium dioxide thin films embedded with synthetic hydroxyapatite, [Ca-10(PO4)(OH)(2)], nanoparticles. The hydroxyapatite nanoparticles were prepared using a low temperature continuous hydrothermal flow synthesis method; analysis of the hydroxyapatite powder showed that it was phase pure and that the as-prepared material was made up of nano-needles. The nanoparticles were then embedded into TiO2 coatings using the AACVD technique by suspending them in a solution of the titania precursor (titanium tetra-isopropoxide). Results showed that the hydroxyapatite, although present in very low concentrations in the coatings (not detectable by XRD or Raman spectroscopy), heavily affected their morphology, depending on their concentration in the precursor solution. Tests of the photocatalytic activity of the composite films showed that the inclusion of the hydroxyapatite led to an increase in methylene blue photodegradation (up to 50% higher) and that the materials were photostable. This study shows that TiO2 coatings embedded with hydroxyapatite nanoparticles have potential as highly efficient photocatalysts.
- Bacteria immobilisation on hydroxyapatite surface for heavy metals removalPublication . Piccirillo, C.; Pereira, S. I. A.; Marques, A. P. G. C.; Pullar, R. C.; Tobaldi, D. M.; Pintado, M. E.; Castro, P. M. L.Selected bacterial strains were immobilised on the surface of hydroxyapatite (Ca-10(PO4)(6)(OH)(2) - HAp) of natural origin (fish bones). The capacity of the material, alone and in combination with the bacterial strains to act as heavy metal removers from aqueous streams was assessed. Pseudomonas fluorescens (S3X), Micro bacterium oxydans (EC29) and Cupriavidus sp. (1C2) were chosen based on their resistance to heavy metals and capacity of adsorbing the metals. These systems were tested using solutions of Zn(II), Cd(II) and in solutions containing both metals. A synergistic effect between the strains and HAp, which is effective in removing the target heavy metals on its own, was observed, as the combination of HAp with the bacterial strains led to higher adsorption capacity for both elements. For the solutions containing only one metal the synergistic effect was greater for higher metal concentrations; 1C2 and EC29 were the most effective strains for Zn(II) and Cd(II) respectively, while S3X was less effective. Overall, an almost four-fold increase was observed for the maximum adsorption capacity for Zn(II) when 10 was employed - 0.433 mmol/g in comparison of 0.121 mmol/g for the unmodified HAP. For Cd(II), on the other hand, an almost three-fold increase was registered with EC29 bacterial strain - 0.090 vs 0.036 mmol/g for the unmodified HAp. When the solutions containing both metals were tested, the effect was more marked for lower concentrations.
- BIONANOSCULP, an ongoing project in biotechnology applications for preventive conservation of outdoor sculpturesPublication . Moreira, P R; Silva, N; Pullar, R. C.; Ben-Arfa, B. A. E.; Abreu, J. G.; Henriques, F.; Pintado, M M E; Vieira, EThe objective of this paper is the presentation of the research strategies adopted and results of the ongoing BIONANOSCULP research project that is aiming to develop solutions in the area of sustainable nanomaterials, which are non-invasive and high-performance in their preventive conservation approach. An integrated methodology was designed as a holistic strategy to the characterisation of the microbiota present on the surface of public outdoor sculptures. Gathering objective data in the characterization of the surface microbiota of public outdoor sculptures is important, in order to design strategies for the preventive conservation of these objects that make use of biotechnology innovative coatings. Such is one of the objectives of the project BIONANOSCULP. Methodologies applied include conservation reports, surface sampling methodologies using gels, 3D modeling, SEM, flow cytometry and metagenomics. The project is already significantly contributing to create a bridge between the experts from different areas: the skills of biotechnologists, microbiologists, materials scientists, art historians and conservators-restorers to assess the state of conservation, biodeterioration and biocontamination of a selected number of sculptures, and to design the appropriate materials to pursue preventive conservation through coatings with anti-microbial activities.
- Biphasic apatite-carbon materials derived from pyrolysed fish bones for effective adsorption of persistent pollutants and heavy metalsPublication . Piccirillo, C.; Moreira, I. S.; Novais, R. M.; Fernandes, A. J. S.; Pullar, R. C.; Castro, P. M. L.Biphasic apatite-carbon biochar-type materials were prepared from pyrolysed cod fish bones and were assessed for the adsorption of persistent organic pollutants (pharmaceuticals diclofenac and fluoxetine), and heavy metals (Pb(II)). The materials, prepared with a simple pyrolysis process at different temperatures (200–1000 °C), were characterised with XRD, FTIR, Raman and SEM. Results showed that the pyrolysis temperature had a significant effect on the features/composition of the materials: up to 800 °C, carbonate apatite Ca10(PO4)6(CO3) was the main component, while for higher temperatures oxyapatite Ca10(PO4)6O was the dominant phase. Graphitic carbon was also detected. The mixed apatite-carbon products (bone char) exhibited high adsorption efficiency. Graphite carbon was the main adsorber for the pharmaceuticals, the best performing material being that pyrolysed at 1000 °C. Xm values of 43.29 and 55.87 mg/g were observed (Langmuir fitting), while KF values of 5.40 and 12.53 (mg/g)(L/mg)nF were obtained with the Freundhlich model (diclofenac and fluoxetine respectively). This is the first time that a biochar-like material has been used for fluoxetine adsorption. For Pb (II), the powder pyrolysed at 600 °C was the most effective, with the apatite playing a key role (Xm = 714.24 mg/g). This work shows that a by-product of the fish industry could be converted into efficient materials for environmental remediation; according to the pyrolysis conditions, powders effective in the removal of either organics or heavy metals can be obtained. Moreover, with pyrolysis at intermediate temperatures, materials capable of adsorbing both kinds of pollutants can be produced, even if less efficient.
- Effect of preparation and processing conditions on UV absorbing properties of hydroxyapatite-Fe2O3 sunscreenPublication . Teixeira, M. A. C.; Piccirillo, C.; Tobaldi, D. M.; Pullar, R. C.; Labrincha, J. A.; Ferreira, M. O.; Castro, Paula M. L.; Pintado, M. M. E.The development of innovative, safe and non-photocatalytic sunscreens is urgently needed, as it is essential to have sunscreen filters offering appropriate UV protection without damaging the environment and/or generating free radicals when in contact with the skin. Hydroxyapatite (Ca-10(PO4)(6)(OH)(2), HAp) when substituted with iron has UV protection properties and is not photocatalytic; HAp was used to make a sunscreen filter by treating cod fish bones in an iron-containing solution, and then calcining them at 700 degrees C. Here we present a systematic and advanced study on this material, to obtain a sunscreen with improved UV absorbing properties, Bones were treated with three different iron salts - Fe(II) chloride, Fe(II) lactate and Fe(III) nitrate - under various pH conditions. Results showed that Fe(II) chloride in basic pH led to the most effective iron inclusion, High energy ball milling or ultrasound were investigated to increase surface area and corresponding UV absorption; high energy ball milling treatment led to the best optical properties. The optimum powders were used to formulate UV protection creams, which showed Sun Protection Factor (SPF) values significantly superior to the control cream (up to 4.1). Moreover the critical wavelength (lambda(crit)) was >370 nm (388-389 nm) and UVA/UVB ratios were very close to 1. With these properties these sunscreens can be classified as broad UV protectors. Results also showed that combining these powders with other sunscreens (i.e. titanium dioxide), a synergic effect between the different components was also observed. This investigation showed that HAp-based sunscreens of marine origin are a valid alternative to commercial products, safe for the health of the customers and, being non-photocatalytic, do not pose a threat to the environment.
- Effects of Cu, Zn and Cu-Zn addition on the microstructure and antibacterial and photocatalytic functional properties of Cu-Zn modified TiO2 nano-heterostructuresPublication . Tobaldi, D. M.; Piccirillo, C.; Rozman, N.; Pullar, R. C.; Seabra, M. P.; Škapin, A. Sever; Castro, Paula M. L.; Labrincha, J. A.Titanium dioxide (TiO2) is well established as one of the most common photocatalysts used for many environmental, anti-pollution and antibacterial applications. However, in this work, novel photocatalytic TiO2 nanopowders were modified with additions of 1 mol% copper, zinc or copper + zinc (with various Cu: Zn ratios). These were prepared via a green sol–gel route and thermally treated at 450 C. For the first time, a direct comparison of the effects of these two modifying agents was performed, both as single and co-substitution. The compounds were thoroughly characterised by means of advanced X-ray diffraction (Whole Powder Pattern Modelling, WPPM) and spectroscopic methods (Raman and UV–vis). For functional properties, the photocatalytic activity in the gas-solid phase (nitrous oxides (NOx) and isopropanol degradation (VOCs)) was tested under UV and visible light, and antibacterial activity against Gram positive and Gram negative bacterial strains was also investigated. Neither copper nor zinc entered into the TiO2 structure, but nucleated as oxides at the surface of titania nanoparticles, thus creating a nano-heterojunction between the semiconductor materials; this also retarded the anatase-to-rutile phase transition. When comparing and contrasting their functional properties, it was found that Zn modification gave greater photocatalytic activity than that with Cu. On the contrary, for antibacterial activity, copper was shown to be a better additive. Co-modification with both metals did not improve the antibacterial behaviour, but did lead to an increase in photocatalytic activity in some cases.
- Extraction and characterisation of apatite- and tricalcium phosphate-based materials from cod fish bonesPublication . Piccirillo, C.; Silva, M. F.; Pullar, R. C.; Braga da Cruz, I.; Jorge, R.; Pintado, M. M. E.; Castro, P. M. L.Apatite- and tricalcium phosphate-based materials were produced from codfish bones, thus converting a waste by-product from the food industry into high added-valued compounds. The bones were annealed at temperatures between 900 and 1200 degrees C, giving a biphasic material of hydroxyapatite and tricalcium phosphate (Ca-10(PO4)(6)(OH)(2) and beta-Ca(PO4)(3)) with a molar proportion of 75:25, a material widely used in biomedical implants. The treatment of the bones in solution prior to their annealing changed the composition of the material. Single phase hydroxyapatite. chlorapatite (Ca-10(PO4)(6)Cl-2) and fluorapatite (Ca-10(PO4)(6)F-2) were obtained using CaCl2 and NaF solutions, respectively. The samples were analysed by several techniques (X-ray diffraction, infrared spectroscopy, scanning electron microscopy and differential thermal/thermogravimetric analysis) and by elemental analyses, to have a more complete understanding of the conversion process. Such compositional modifications have never been performed before for these materials of natural origin to tailor the relative concentrations of elements. This paper shows the great potential for the conversion of this by-product into highly valuable compounds for biomedical applications, using a simple and effective valorisation process.
- Hydroxyapatite and chloroapatite derived from sardine by-productsPublication . Piccirillo, C.; Pullar, R. C.; Tobaldi, D. M.; Castro, Paula M. L.; Pintado, M. E.In this paper, phosphate-based compounds used in biomedicine were extracted from bones and scales of European sardines (Sardina pilchardus); this is the first time that different parts of the same fish are used for the extraction of these kinds of materials. The bones and scales behave very differently with processing, producing different materials when annealed between 600 and 1000 °C. The bones formed a mixture of hydroxyapatite (Ca10(PO4)6(OH)2, HAp) and β-tri-calcium phosphate (β-Ca3(PO4)2, β-TCP), with a higher content of β-TCP obtained with increasing temperature. This bi-phasic material has a high added value, as it is employed as a bioceramic; in fact HAp has good biocompatibility while β-TCP has better resorbability than HAp, despite being less biocompatible. With scales, on the other hand, either a HAp-based material or a chlorine-substitute HAp containing material (chloroapatite (Ca10(PO4)6Cl2, ClAp) were produced. HAp-based material was obtained with a simple annealing process; for ClAp, on the other hand, a combined washing–annealing process was used. ClAp is also used in biomedicine, due to its improved resorption, mechanical properties and bioactivity. This is the first time ClAp of marine origin was produced.
- Hydroxyapatite-based materials of marine origin: a bioactivity and sintering studyPublication . Piccirillo, C.; Pullar, R. C.; Costa, E.; Santos-Silva, A.; Pintado, Manuela; Castro, Paula M. L.Single phase hydroxyapatite (HAp) and biphasic material hydroxyapatite/beta-tricalcium phosphate (HAp/beta-TCP) were obtained from a marine source (Atlantic cod fish bones). Here we report a study on the biological properties of these materials, including cytotoxicity, bioactivity and haemocompatibility. Results showed that the materials are not cytotoxic, neither in their powder nor in pellet form; indeed growth of Saos-2 cells was comparable to that of commercial. The haemolysis rate was lower than 2%; hence the materials can be classified as non-haemolytic. Moreover, when immersed in Simulated Body Fluid (SBF), crystal formation was observed on the surface of both materials. The sintering behaviour of the samples was also studied; both powders showed very high sinterability (density higher than 95% of the theoretical value). Overall, these results confirm the suitability of these materials for biomedical applications.
- A hydroxyapatite–Fe2O3 based material of natural origin as an active sunscreen filterPublication . Piccirillo, C.; Rocha, C.; Tobaldi, D. M.; Pullar, R. C.; Labrincha, J. A.; Ferreira, M. O.; Castro, Paula M. L.; Pintado, M. E.The use of sunscreens as protective barriers against skin damage and cancer, by absorbing harmful UVA and UVB rays, is becoming an increasingly important issue. Such products are usually based on TiO2 or ZnO, although both Fe2O3 and hydroxyapatite (Ca10(PO4)6(OH)2, HAp) doped with metal ions have been reported as being ultraviolet (UV) absorbing materials. HAp is the main component of bone; it is, therefore, highly biocompatible. In the present work, an iron-doped HAp-based material, containing both Fe ions substituted into the HAp structure and iron oxide in hematite (a-Fe2O3) form, was successfully developed from waste cod fish bones. This was achieved through a simple process of treating the bones in a Fe(II) containing solution, followed by heating at 700 C. The material showed good absorption in the whole UV range and did not form radicals when irradiated. The sunscreen cream formulated with this material could be used as a broad sunscreen protector (lcrit > 370 nm), showing high absorption both in the UVA and UVB ranges. Because of its absorption properties it would be classified as 5 star protection according to the Boots UVA star rating system. The cream is also photostable, and does not cause irritation or erythema formation when in contact with the human skin. These results show that a food by-product such as fish bones could be converted into a valuable product, with potential applications in health care and cosmetics. This is the first time a HAp-based sunscreen cream has been developed and validated as a proof of concept.