Loading...
13 results
Search Results
Now showing 1 - 10 of 13
- Surface modified hydroxyapatites with various functionalized nanostructures: computational studies of the vacancies in HApPublication . Bystrova, V. S.; Paramonova, E. V.; Bystrova, A. V.; Pullar, R. C.; Kopyl, S.; Tobaldi, D. M.; Piccirillo, C.; Avakyan, L. A.; Coutinho, J.Hydroxyapatite (HAp) has structural features that define its basic physical properties, which have an important role at the surface, and it is one of the most used materials in bone implants. In this work, we present a density functional modeling (DFT) study of HAp both as bulk and with special HAp models with various defects, especially oxygen vacancies in HAp surface layers, which can also determine photocatalytic properties, confirmed experimentally. The first-principles calculations of bulk and modified HAp were carried out using local basis (AIMPRO) and plane-wave (VASP) codes. Data obtained are analyzed using both approaches, and compared.
- 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.
- Luminescent calcium phosphate bioceramics doped with europium derived from fish industry byproductsPublication . Piccirillo, Clara; Adamiano, Alessio; Tobaldi, David M.; Montalti, Marco; Manzi, Jeannette; Castro, P. M. Lima; Panseri, Silvia; Montesi, Monica; Sprio, Simone; Tampieri, Anna; Iafisco, MicheleThe recovery of valuable compounds from byproducts is at present a priority topic for social, environmental, and economic reasons. In this work we report for the first time the preparation of luminescent calcium phosphate (CaP) bioceramics from waste codfish bones. Codfish bones were treated in aqueous Eu(NO 3 ) 3 solu- tions of different concentrations, followed by thermal treatment at either 700°Cor 1100°C. The resulting materials consisted of hydroxyapatite (HAp), b-tricalcium phosphate (b-TCP) and a small amount of Eu 2 O 3 . Chemical and structural charac- terization showed that the Eu ions were successfully introduced into the bones and, hence, in the thermally treated CaP phases obtained from them, although mainly in the b-TCP lattice. Photol uminescence investigatio n revealed that all the materials are luminescent, with samples treated at 1100°C having more intense luminescence than those prepared at 700°C. In vitro evaluation of cell-materials interaction indicated that all the samples displayed good cytocompatibility toward osteoblast cells. This work demonstrates that a simple and effective process, employing Eu as a dopant, can convert fish industry byproducts into highly valu- able luminescent CaP bioceramics, having potential applications in biology and medicine for bio-imaging
- 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.
- 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.
- Silver-containing calcium phosphate materials of marine origin with antibacterial activityPublication . Piccirillo, C.; Pullar, R. C.; Tobaldi, D. M.; Castro, Paula M. L.; Estevez Pintado, M. M.Hydroxyapatite (Ca10(PO4)6(OH)2 – HAp) is a common material for bone replacement in artificial implants and prostheses, due to its high biocompatibility. In this work we report about the preparation of HAp-based materials of marine origin with antibacterial properties. Bones from cod fish (Gadhus morua) were treated with a dilute AgNO3 solution, to obtain HAp-containing samples with silver as a minor component. The samples were characterised by XRD, FT-IR spectroscopy and SEM, indicating the presence of HAp, β–TCP and some metallic silver. The determination of unit cell parameters, however, indicated that the majority of silver is substituted in the β-TCP lattice in ionic form. The antibacterial activity of these materials was tested towards both Gram-positive and Gram-negative bacterias; results showed that the material is very effective with Gram-negative strains such as Escherichia coli (inactivation rates of 99.82% and 99.999% after 2 and 5 h, respectively) and had a smaller but still significant effect on Gram-positive MRSA (91% inactivation rate). These results show the potentials of these samples as infection-resistant bone replacement materials.
- Oxygen vacancies, the optical band gap (Eg) and photocatalysis ofhydroxyapatite: Comparing modelling with measured dataPublication . Bystrov, V. S.; Piccirillo, C.; Tobaldi, D. M.; Castro, P. M. L.; Coutinho, J.; Kopyl, S.; Pullar, R.Hydroxyapatite (Ca10(PO4)6(OH)2, HAp) is a calcium phosphate employed both in biomedicine and forenvironmental remediation. It is known that HAp can also be photocatalytic under UV light, probablydue to oxygen deficiencies, but the mechanism is unclear, and reported optical band gap energies varygreatly. For the first time we propose the mechanisms and precise kinds of vacancies which may causethe photocatalytic activity of HAp, and compare these theoretical data with our measured data on bothsamples of marine origin and commercial HAp powders. Density functional theory (DFT) (from firstprinciples calculations and Density of States (DOS) modelling) was used to calculate the optical bandgap energy (Eg) created by various possible oxygen vacancies in the HAp lattice: O from PO4, O fromOH, the loss of an entire OH group, or the simultaneous loss of O from PO4and an entire OH group. Themodelled values match the measured values very closely, suggesting that in non-photocatalytic HAp, ifany vacancies exist, they are O atoms from the OH group, resulting in a band gap of ∼5 eV in the UVCregion (not present in solar light at the Earth’s surface). However, in photocatalytic HAp, reduction fromthe combustion of an organic component at 1000◦C led to oxygen deficiency in the phosphate groups,probably in the O15 position, giving an Egof ∼3.45 eV, in the UVA region (present in sunlight). HeatingHAp with no organic component to 1200◦C also led to vacancies, of both an entire OH group and oxygenfrom PO4groups, which led to an intermediate Egvalue of ∼4 eV, on the boundary of the UVA-UVB regions.Absorption peaks were also predicted in the visible-light region with some types of vacancy.
- A sustainable replacement for TiO2 in photocatalyst construction materials: Hydroxyapatite-based photocatalytic additives, made from the valorisation of food wastes of marine originPublication . Saeli, Manfredi; Piccirillo, Clara; Tobaldi, David M.; Binions, Russell; Castro, Paula M. L.; Pullar, Robert C.The use of waste materials and by-products in building materials is of increasing importance to improve sustainability in construction, as is the incorporation of photocatalytic materials to both combat atmospheric pollution and protect the structures and façades. This work reports the innovative use of photocatalytic hydroxyapatite (HAp) based powders, derived from Atlantic codfish bone wastes, as an additive to natural hydraulic lime mortars. HAp is the main component of bone, and hence is non-toxic and biocompatible. This is the first time that such a calcium phosphate-based photocatalyst, or indeed any fish/marine derived wastes, have been added to building materials. A key factor is that this HApbased photocatalyst contains only 1 wt% TiO2, the material usually used as a photocatalyst in construction materials. As we only add 1e5 wt% of our total HAp-based material to the mortar, this means our photocatalytic mortars only contain 0.01e0.05 wt% titania (100e500 ppm), two orders of magnitude less than the quantities of 2e10 wt% TiO2 which are usually needed. Our photocatalyst is made from a sustainable waste stream by simple solution and thermal processing, and thus with a much smaller impact on the environment. Specimens were made by either traditional intermixing techniques, or by a post-curing coating procedure. All showed gas-phase photocatalytic activity for abatement of NOx pollutants under solar light. With intermixing, NOx abatement of 6.3e8.3% was observed. However, for coated mortars, superior NOx conversion rates were achieved of 7.1% and 23.8%, with 1 and 5 wt% additions, respectively. These results show the potential of this naturally-derived photocatalyst for applications in the construction industry, leading to lower atmospheric pollution and the creation of more durable/lower maintenance building façades, and environmentally sustainable materials for the preservation of cultural heritage.
- Increased UV absorption properties of natural hydroxyapatite-based sunscreen through laser ablation modification in liquidPublication . Piccirillo, Clara; Fernández‐Arias, Mónica; Boutinguiza, Mohamed; Tobaldi, David M.; Del Val, Jesus; Pintado, Maria M.; Pou, JuanSunfilters based on hydroxyapatite (HAp) and iron‐containing compounds (Fe2O3 and calcium iron phosphates) are of increasing interest, as they show UV absorption without generating health endanger free radicals (usually observed when other inorganic sunscreens are used). In this paper, laser ablation of solids in liquids has been applied to improve the UV absorption properties of a HAp based Fe‐containing sunscreen powder derived from cod fish bones. Two different laser wavelengths were explored (532 and 1064 nm, green and infrared, respectively); an improved experimental device was used, to allow a fine control of the volume of the irradiated particles. Results show an increased UV absorbance for the laser‐treated powders in comparison with the untreated ones; this can be explained considering the smaller particle size and increased surface area; the higher iron concentration in the powders may also be determinant. Enhanced absorption was also observed in the near‐infrared range, making the powders even more suitable for sunscreen applications. The green laser was more effective than the infrared one. Overall, laser ablation showed to be a powerful technique to control the size of the sunscreen particles and tailor their optical properties.
- Calcium phosphate-based materials of natural origin showing photocatalytic activityPublication . Piccirillo, Clara; Dunnill, Charles W.; Pullar, Robert C.; Tobaldi, David M.; Labrincha, João A.; Parkin, Ivan P.; Pintado, Manuela M.; Castro, Paula M. L.Calcium phosphate based materials of natural origin with photocatalytic properties were produced. Bones of Atlantic cod fish were treated in appropriate solutions (either Ca- or Ti-containing salts) and successively annealed. Results showed multiphasic materials (hydroxyapatite, beta-tricalcium phosphate and anatase titania) with excellent photocatalytic performance under both UV and visible light, with an anatase concentration of only about 2 mol%. Results with such a low amount of anatase have never been reported before for a calcium phosphate-based material; this is attributed to the presence of anatase being mainly on the surface. Single-phase hydroxyapatite (Ca-10(PO4)(6)(OH)(2) or HAp) also showed some photocatalytic properties and antibacterial activity.