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- 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.
- Methyl cellulose films containing natural extracts: antibacterial propertiesPublication . Campos, Débora; Piccirillo, Clara; Pullar, Robert C.; Castro, Paula M. L.; Pintado, Manuela E.
- Study of the proximate and mineral composition of different Nigerian yam chips, flakes and floursPublication . Omohimi, C. I.; Piccirillo, C.; Roriz, M.; Ferraro, V.; Vasconcelos, M. W.; Sanni, L. O.; Tomlins, K.; Pintado, M. M.; Abayomi, L. A.Yam (Dioscorea spp) is an essential tuber crop for hundreds of millions of people in many African, Asian and South American countries. Considering in particular Southwest Nigeria, chips, flakes and flours are amongst the most common shelf-stable traditionally-processed yam products. This paper reports a systematic study on the proximate (moisture, protein, carbohydrate, fibre, fat, ash and gross energy) and mineral composition of these three food commodities sold in Nigerian markets. Results showed no significant differences in the moisture, crude protein and fibre content of all samples (10.0–12.3, 2.7–4.3 and 1.3–2.0 wt%, respectively). Gross energy was also comparable for all yam derived food items (between 3300 and 3507 kcal/kg), contradicting the common belief that yam flakes have lower nutritional value than chips and flours. Considering the mineral composition, Ca, Mg, P and K were the predominant macronutrients. Micronutrients such as Zn, Co, Mn and Cu were also detected. Significant differences existed between products, and their various sources (markets). Principal component analysis showed a direct correlation between ash content of the samples and the assessed macronutrients, irrespective of the market, or the seller of the commodities. This study confirmed that yam derived food stuffs have an adequate nutritional composition, irrespective of their form and/or origin.
- Chitosan and codfish hydroxyapatite formulation to be used as coating material to circumvent periprosthetic joint infectionsPublication . Costa-Pinto, Ana R.; Lemos, Ana L.; Piccirillo, Clara; Tavaria, Freni K; Pintado, Manuela E.
- 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.
- Biodegradation of carbamazepine by the bacterial strain labrys portucalensis F11 : metabolism and toxicologic studiesPublication . Bessa, Vânia S.; Moreira, Irina; Murgulo, Sapia; Piccirillo, Clara; Mascolo, Giuseppe; Castro, Paula M. L.Background: Occurrence of pharmaceuticals in the environment is a topic of concern. Most pharmaceuticals are not completely mineralized and are released on the sewage systems through excretion and by improper elimination and disposal. Municipal wastewater treatment plants (WWTPs) are not designed to remove them and they are released into the environment. They are classified as persistent microcontaminants due to their continuous release even if at low concentrations. Carbamazepine (CBZ) is an widely used anticonvulsant and has been suggested as a molecular marker of contamination in surface water and groundwater. Method Biodegradation of CBZ by the bacterial strain Labrys portucalensis F11 was tested as sole carbon and energy source (0.04 mM) and in the presence of acetate as primary carbon source. Transformation products (TPs) were detected and identified by UPLCQTOF/MS/MS. Ecotoxicologiacl effects of CBZ and the TPs resultant from biodegradation were evaluated at different trophic levels, i) zooplanckton (Dapnhia magna) and ii) plants (Lipidium sativum). The 24–48 h immobilization of D. magna bioassays were performed following the Standard Operational Procedures of Daphtoxkit FTM. The toxicity was measured as the immobilization of D. magna according to the procedures OCED Guideline 202. The bioassay with L. sativum evaluated the potential toxicity considering the root elongation according to OECD Guideline 208. Results & Conclusions Strain F11 was able to degrade 95% of initial CBZ concentration during 30 days experiment. Supplementation with acetate increased degradation to 100% in 24 days. A group of 12 TPs formed in the microbial process were identified; CBZ degradation by strain F11 proceeds mainly by oxidation, hydroxilation and cleavage of the aromatic ring. The effect of whole biodegradation products on root elongation of L. sativum was practically neglectable; however the same exhibited toxicity to D. magna. Strain Labrys portucalensis F11 proved to be able to degrade CBZ and may be potentially useful for biotechnological applications.
- Cassava (manihot esculenta crantz) and yam (dioscorea spp.) crops and their derived foodstuffs: safety, security and nutritional valuePublication . Ferraro, Vincenza; Piccirillo, Clara; Tomlins, Keith; Pintado, M. E.Cassava (Manihot esculenta Crantz) and yam (Dioscorea spp.) are tropical crops consumed by ca. 2 billion people and represent the main source of carbohydrate and energy for the approximately 700million people living in the tropical and sub-tropical areas. They are a guarantee of food security for developing countries. The production of these crops and the transformation into food-derived commodities is increasing, it represents a profitable business and farmers generate substantial income from their market. However, there are some important concerns related to the food safety and food security. The high post-harvest losses, mainly for yam, the contamination by endogenous toxic compounds, mainly for cassava, and the contamination by external agents (such as micotoxins, pesticides, and heavy metal) represent a depletion of economic value and income. The loss in the raw crops or the impossibility to market the derived foodstuffs, due to incompliance with food regulations, can seriously limit all yam tubers and the cassava roots processors, from farmers to household, from small-medium to large enterprises. One of the greatest challenges to overcome those concerns is the transformation of traditional or indigenous processing methods into modern industrial operations, from the crop storage to the adequate package of each derived foodstuff.
- 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
- Bioconversion of oleuropein to hydroxytyrosol by lactic acid bacteriaPublication . Santos, M. M.; Piccirillo, C.; Castro, Paula M. L.; Kalogerakis, N.; Pintado, M. E.The aim of this work is to study the conversion of oleuropein—a polyphenol present in olives and olive oil by-products—into hydroxytyrosol, a polyphenol with antioxidant and antibacterial properties. The hydrolysis reaction is performed by lactic acid bacteria. Six bacterial strains (Lactobacillus plantarum 6907, Lactobacillus paracasei 9192, Lactobacillus casei, Bifidobacterium lactis BO, Enterococcus faecium 32, Lactobacillus LAFTI 10) were tested under aerobic and anaerobic conditions. The oleuropein degradation and hydroxytyrosol formation were monitored by HPLC. Results showed that oleuropein could be successfully converted into hydroxytyrosol. The most effective strain was Lactobacillus plantarum 6907, with a reaction yield of hydroxytyrosol of about 30 %. Different reaction mechanisms were observed for different microorganisms; a different yield was observed for Lactobacillus paracasei 9192 under aerobic or anaerobic conditions and an intermediate metabolite (oleuropein aglycone) was detected for Lactobacillus paracasei 9192 and Lactobacillus plantarum 6907 only. This study could have significant applications, as this reaction can be used to increase the value of olive oil by-products and/or to improve the taste of unripe olives.
- 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.