Search results for: Fernando Eduardo Milioli

Authors: Adriana Garcia G., Alberto A. Escobar P., Amira D. Calvo L., Gabriel Lizama U., Alejandro Zepeda P., Fernando Martínez B., Susana Rincón A.

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Different studies have recently been focused on the use of antioxidants such as polyphenols because of to its anticarcinogenic capacity. However, these compounds are highly sensible to environmental factors such as light and heat, so lose its long-term stability, besides possess an astringent and bitter taste. Nevertheless, the polyphenols can be protected by microcapsule formulation. In this sense, a rich source of polyphenols is sorghum, besides presenting a high starch content. Due to the above, the aim of this work was to obtain modified starches from sorghum by extrusion to encapsulate polyphenols the sorghum by spray drying. Polyphenols were extracted by ethanol solution from sorghum (Pajarero/red) and determined by the method of Folin-Ciocalteu, obtaining GAE at 30 mg/g. Moreover, was extracted starch of sorghum (Sinaloense/white) through wet milling (yield 32 %). The hydrolyzed starch was modified with three treatments: acetic anhydride (2.5g/100g), sodium tripolyphosphate (4g/100g), and sodium tripolyphosphate/ acetic anhydride (2g/1.25g by each 100 g) by extrusion. Processing conditions of extrusion were as follows: barrel temperatures were of 60, 130 and 170 °C at the feeding, transition, and high-pressure extrusion zones, respectively. Analysis of Fourier Transform Infrared spectroscopy (FTIR), showed bands exhibited of acetyl groups (1735 cm-1) and phosphates (1170 cm-1, 910 cm-1 and 525 cm-1), indicating the respective modification of starch. Besides, all modified starches not developed viscosity, which is a characteristic required for use in the encapsulation of polyphenols using the spray drying technique. As result of the modification starch, was obtained a water solubility index (WSI) from 33.8 to 44.8 %, and crystallinity from 8 to 11 %, indicating the destruction of the starch granule. Afterwards, microencapsulation of polyphenols was developed by spray drying, with a blend of 10 g of modified starch, 60 ml polyphenol extract and 30 ml of distilled water. Drying conditions were as follows: inlet air temperature 150 °C ± 1, outlet air temperature 80°C ± 5. As result of the microencapsulation: were obtained yields of 56.8 to 77.4 % and an efficiency of encapsulation from 84.6 to 91.4 %. The FTIR analysis showed evidence of microcapsules loaded with polyphenols in bands 1042 cm-1, 1038 cm-1 and 1148 cm-1. Analysis Differential scanning calorimetry (DSC) showed transition temperatures from 144.1 to 173.9 °C. For the order hand, analysis of Scanning Electron Microscopy (SEM), were observed rounded surfaces with concavities, typical feature of microcapsules produced by spray drying, how result of rapid evaporation of water. Finally, the modified starches were obtained by extrusion with good characteristics for use as cover materials by spray drying, where the phosphorylated starch was the best treatment in this work, according to the encapsulation yield, efficiency, and transition temperature.

Keywords: encapsulation, extrusion, modified starch, polyphenols, spray drying

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Authors: Benjamin Castillo, Luis Pastenes, Fernando Cerdova

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The contamination of food by microbial agents is a common problem in the industry, especially regarding the elaboration of animal source products. Incorrect manipulation of the machinery or on the raw materials can cause a decrease in production or an epidemiological outbreak due to intoxication. In order to improve food product quality, different methods have been used to reduce or, at least, to slow down the growth of the pathogens, especially deteriorated, infectious or toxigenic bacteria. These methods are usually carried out under low temperatures and short processing time (abiotic agents), along with the application of antibacterial substances, such as bacteriocins (biotic agents). This, in a controlled and efficient way that fulfills the purpose of bacterial control without damaging the final product. Therefore, the objective of the present study is to design a secondary mathematical model that allows the prediction of both the biotic and abiotic factor impact associated with animal source food processing. In order to accomplish this objective, the authors propose a three-dimensional differential equation model, whose components are: bacterial growth, release, production and artificial incorporation of bacteriocins and changes in pH levels of the medium. These three dimensions are constantly being influenced by the temperature of the medium. Secondly, this model adapts to an idealized situation of cross-contamination animal source food processing, with the study agents being both the animal product and the contact surface. Thirdly, the stochastic simulations and the parametric sensibility analysis are compared with referential data. The main results obtained from the analysis and simulations of the mathematical model were to discover that, although bacterial growth can be stopped in lower temperatures, even lower ones are needed to eradicate it. However, this can be not only expensive, but counterproductive as well in terms of the quality of the raw materials and, on the other hand, higher temperatures accelerate bacterial growth. In other aspects, the use and efficiency of bacteriocins are an effective alternative in the short and medium terms. Moreover, an indicator of bacterial growth is a low-level pH, since lots of deteriorating bacteria are lactic acids. Lastly, the processing times are a secondary agent of concern when the rest of the aforementioned agents are under control. Our main conclusion is that when acclimating a mathematical model within the context of the industrial process, it can generate new tools that predict bacterial contamination, the impact of bacterial inhibition, and processing method times. In addition, the mathematical modeling proposed logistic input of broad application, which can be replicated on non-meat food products, other pathogens or even on contamination by crossed contact of allergen foods.

Keywords: bacteriocins, cross-contamination, mathematical model, temperature

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Authors: Eduardo Antonio Lozano Hernandez, Nancy Ramirez Alvarez, Lorena Margarita Rios Mendoza, Jose Vinicio Macias Zamora, Felix Augusto Hernandez Guzman, Jose Luis Sanchez Osorio

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Microplastics (MPs) are one of the most numerous reported wastes found in the marine ecosystem, representing one of the greatest risks for organisms that inhabit that environment due to their bioavailability. Such is the case of bivalve mollusks, since they are capable of filtering large volumes of water, which increases the risk of contamination by microplastics through the continuous exposure to these materials. This study aims to determine, quantify and characterize microplastics found in the cultured oyster Crassostrea gigas. We also analyzed if there are spatio-temporal differences in the microplastic concentration of organisms grown in two bays having quite different human population. In addition, we wanted to have an idea of the possible impact on humans via consumption of these organisms. Commercial size organisms (>6cm length; n = 15) were collected by triplicate from eight oyster farming sites in Baja California, Mexico during winter and summer. Two sites are located in Todos Santos Bay (TSB), while the other six are located in San Quintin Bay (SQB). Site selection was based on commercial concessions for oyster farming in each bay. The organisms were chemically digested with 30% KOH (w/v) and 30% H₂O₂ (v/v) to remove the organic matter and subsequently filtered using a GF/D filter. All particles considered as possible MPs were quantified according to their physical characteristics using a stereoscopic microscope. The type of synthetic polymer was determined using a FTIR-ATR microscope and using a user as well as a commercial reference library (Nicolet iN10 Thermo Scientific, Inc.) of IR spectra of plastic polymers (with a certainty ≥70% for polymers pure; ≥50% for composite polymers). Plastic microfibers were found in all the samples analyzed. However, a low incidence of MP fragments was observed in our study (approximately 9%). The synthetic polymers identified were mainly polyester and polyacrylonitrile. In addition, polyethylene, polypropylene, polystyrene, nylon, and T. elastomer. On average, the content of microplastics in organisms were higher in TSB (0.05 ± 0.01 plastic particles (pp)/g of wet weight) than found in SQB (0.02 ± 0.004 pp/g of wet weight) in the winter period. The highest concentration of MPs found in TSB coincides with the rainy season in the region, which increases the runoff from streams and wastewater discharges to the bay, as well as the larger population pressure (> 500,000 inhabitants). Otherwise, SQB is a mainly rural location, where surface runoff from streams is minimal and in addition, does not have a wastewater discharge into the bay. During the summer, no significant differences (Manne-Whitney U test; P=0.484) were observed in the concentration of MPs found in the cultured oysters of TSB and SQB, (average: 0.01 ± 0.003 pp/g and 0.01 ± 0.002 pp/g, respectively). Finally, we concluded that the consumption of oyster does not represent a risk for humans due to the low concentrations of MPs found. The concentration of MPs is influenced by the variables such as temporality, circulations dynamics of the bay and existing demographic pressure.

Keywords: FTIR-ATR, Human risk, Microplastic, Oyster

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Authors: Itze Coronel Salomon

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The rise of organized crime and violence related to drug cartels in Mexico has created serious challenges for the authorities to provide security to those who live within its borders. However, to achieve a significant improvement in security is absolute respect for fundamental human rights by the authorities. Irregular migrants in Mexico are at serious risk of abuse. Research by Amnesty International as well as reports of the NHRC (National Human Rights) in Mexico, have indicated the major humanitarian crisis faced by thousands of migrants traveling in the shadows. However, the true extent of the problem remains invisible to the general population. The fact that federal and state governments leave no proper record of abuse and do not publish reliable data contributes to ignorance and misinformation, often spread by the media that portray migrants as the source of crime rather than their victims. Discrimination and intolerance against irregular migrants can generate greater hostility and exclusion. According to the modus operandi that has been recorded criminal organizations and criminal groups linked to drug trafficking structures deprive migrants of their liberty for forced labor and illegal activities related to drug trafficking, even some have been kidnapped for be trained as murderers . If the victim or their family cannot pay the ransom, the kidnapped person may suffer torture, mutilation and amputation of limbs or death. Migrant women are victims of sexual abuse during her abduction as well. In 2011, at least 177 bodies were identified in the largest mass grave found in Mexico, located in the town of San Fernando, in the border state of Tamaulipas, most of the victims were killed by blunt instruments, and most seemed to be immigrants and travelers passing through the country. With dozens of small graves discovered in northern Mexico, this may suggest a change in tactics between organized crime groups to the different means of obtaining revenue and reduce murder profile methods. Competition and conflict over territorial control drug trafficking can provide strong incentives for organized crime groups send signals of violence to the authorities and rival groups. However, as some Mexican organized crime groups are increasingly looking to take advantage of income and vulnerable groups, such as Central American migrants seem less interested in advertising his work to authorities and others, and more interested in evading detection and confrontation. This paper pretends to analyze the introduction of this new trend of kidnapping migrants for forced labors by drug cartels in Mexico into the forms of contemporary slavery and its implications.

Keywords: international law, migration, transnational organized crime

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Authors: Marlon Gallo, Eduardo Miguel, Laura Oca, Eneko Gonzalez, Unai Iraola

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The heat generation of an energy storage system is an essential topic when designing a battery pack and its cooling system. Heat generation estimation is used together with thermal models to predict battery temperature in operation and adapt the design of the battery pack and the cooling system to these thermal needs guaranteeing its safety and correct operation. In the present work, a comparison between the use of a heat flux sensor (HFS) for indirect measurement of heat losses in a cell and the widely used and simplified version of Bernardi’s equation for estimation is presented. First, a Li-ion cell is thermally characterized with an HFS to measure the thermal parameters that are used in a first-order lumped thermal model. These parameters are the equivalent thermal capacity and the thermal equivalent resistance of a single Li-ion cell. Static (when no current is flowing through the cell) and dynamic (making current flow through the cell) tests are conducted in which HFS is used to measure heat between the cell and the ambient, so thermal capacity and resistances respectively can be calculated. An experimental platform records current, voltage, ambient temperature, surface temperature, and HFS output voltage. Second, an equivalent circuit model is built in a Matlab-Simulink environment. This allows the comparison between the generated heat predicted by Bernardi’s equation and the HFS measurements. Data post-processing is required to extrapolate the heat generation from the HFS measurements, as the sensor records the heat released to the ambient and not the one generated within the cell. Finally, the cell temperature evolution is estimated with the lumped thermal model (using both HFS and Bernardi’s equation total heat generation) and compared towards experimental temperature data (measured with a T-type thermocouple). At the end of this work, a critical review of the results obtained and the possible mismatch reasons are reported. The results show that indirectly measuring the heat generation with HFS gives a more precise estimation than Bernardi’s simplified equation. On the one hand, when using Bernardi’s simplified equation, estimated heat generation differs from cell temperature measurements during charges at high current rates. Additionally, for low capacity cells where a small change in capacity has a great influence on the terminal voltage, the estimated heat generation shows high dependency on the State of Charge (SoC) estimation, and therefore open circuit voltage calculation (as it is SoC dependent). On the other hand, with indirect measuring the heat generation with HFS, the resulting error is a maximum of 0.28ºC in the temperature prediction, in contrast with 1.38ºC with Bernardi’s simplified equation. This illustrates the limitations of Bernardi’s simplified equation for applications where precise heat monitoring is required. For higher current rates, Bernardi’s equation estimates more heat generation and consequently, a higher predicted temperature. Bernardi´s equation accounts for no losses after cutting the charging or discharging current. However, HFS measurement shows that after cutting the current the cell continues generating heat for some time, increasing the error of Bernardi´s equation.

Keywords: lithium-ion battery, heat flux sensor, heat generation, thermal characterization

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Authors: Indika Fernando, Jiangang Fei, Roger Stanely, Hossein Enshaei

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Ever increasing demand for quality fresh produce by the consumers, had increased the gravity on the post-harvest supply chains in multi-fold in the recent years. Mechanical injury to fresh produce was a critical factor for produce wastage, especially with the expansion of supply chains, physically extending to thousands of miles. The impact of vibration damages in transit was identified as a specific area of focus which results in wastage of significant portion of the fresh produce, at times ranging from 10% to 40% in some countries. Several studies were concentrated on quantifying the impact of vibration to fresh produce, and it was a challenge to collect vibration impact data continuously due to the limitations in battery life or the memory capacity in the devices. Therefore, the study samples were limited to a stretch of the transit passage or a limited time of the journey. This may or may not give an accurate understanding of the vibration impacts encountered throughout the transit passage, which limits the accuracy of the results. Consequently, an approach which can extend the capacity and ability of determining vibration signals in the transit passage would contribute to accurately analyze the vibration damage along the post-harvest supply chain. A mechanism was developed to address this challenge, which is capable of measuring the in transit vibration continuously through the transit passage subject to a minimum acceleration threshold (0.1g). A system, consisting six tri-axel vibration transducers installed in different locations inside the cargo (produce) pallets in the truck, transmits vibration signals through LORA (Long Range Radio) technology to a central device installed inside the container. The central device processes and records the vibration signals transmitted by the portable transducers, along with the GPS location. This method enables to utilize power consumption for the portable transducers to maximize the capability of measuring the vibration impacts in the transit passage extending to days in the distribution process. The trial tests conducted using the approach reveals that it is a reliable method to measure and quantify the in transit vibrations along the supply chain. The GPS capability enables to identify the locations in the supply chain where the significant vibration impacts were encountered. This method contributes to determining the causes, susceptibility and intensity of vibration impact damages to fresh produce in the post-harvest supply chain. Extensively, the approach could be used to determine the vibration impacts not limiting to fresh produce, but for products in supply chains, which may extend from few hours to several days in transit.

Keywords: post-harvest, supply chain, wireless transducers, LORA, fresh produce

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Authors: Fernando Cabo Aseguinolaza, Víctor Bouzas Blanco, Alberto Martí Ezpeleta

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Santiago de Compostela became a stable object of literary representation during the period between 1840 and 1915, approximately. This study offers a partial cartographical look at this process, suggesting that a cultural space like Compostela’s becoming an object of literary representation paralleled the first stages of its becoming a tourist destination. We use maps as a method of analysis to show the interaction between a corpus of novels and the emerging tradition of tourist guides on Compostela during the selected period. Often, the novels constitute ways to present a city to the outside, marking it for the gaze of others, as guidebooks do. That leads us to examine the ways of constructing and rendering communicable the local in other contexts. For that matter, we should also acknowledge the fact that a good number of the narratives in the corpus evoke the representation of the city through the figure of one who comes from elsewhere: a traveler, a student or a professor. The guidebooks coincide in this with the emerging fiction, of which the mimesis of a city is a key characteristic. The local cannot define itself except through a process of symbolic negotiation, in which recognition and self-recognition play important roles. Cartography shows some of the forms that these processes of symbolic representation take through the treatment of space. The research uses GIS to find significant models of representation. We used the program ArcGIS for the mapping, defining the databases starting from an adapted version of the methodology applied by Barbara Piatti and Lorenz Hurni’s team at the University of Zurich. First, we designed maps that emphasize the peripheral position of Compostela from a historical and institutional perspective using elements found in the texts of our corpus (novels and tourist guides). Second, other maps delve into the parallels between recurring techniques in the fictional texts and characteristic devices of the guidebooks (sketching itineraries and the selection of zones and indexicalization), like a foreigner’s visit guided by someone who knows the city or the description of one’s first entrance into the city’s premises. Last, we offer a cartography that demonstrates the connection between the best known of the novels in our corpus (Alejandro Pérez Lugín’s 1915 novel La casa de la Troya) and the first attempt to create package tourist tours with Galicia as a destination, in a joint venture of Galician and British business owners, in the years immediately preceding the Great War. Literary cartography becomes a crucial instrument for digging deeply into the methods of cultural production of places. Through maps, the interaction between discursive forms seemingly so far removed from each other as novels and tourist guides becomes obvious and suggests the need to go deeper into a complex process through which a city like Compostela becomes visible on the contemporary cultural horizon.

Keywords: compostela, literary geography, literary cartography, tourism

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Authors: Marcela De Oliveira, Marina P. Da Silva, Fernando C. G. Da Rocha, Jorge M. Santos, Jaime S. Cardoso, Paulo N. Lisboa-Filho

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Multiple Sclerosis (MS) is an immune-mediated disease of the central nervous system characterized by neurodegeneration, inflammation, demyelination, and axonal loss. Magnetic resonance imaging (MRI), due to the richness in the information details provided, is the gold standard exam for diagnosis and follow-up of neurodegenerative diseases, such as MS. Brain atrophy, the gradual loss of brain volume, is quite extensive in multiple sclerosis, nearly 0.5-1.35% per year, far off the limits of normal aging. Thus, the brain volume quantification becomes an essential task for future analysis of the occurrence atrophy. The analysis of MRI has become a tedious and complex task for clinicians, who have to manually extract important information. This manual analysis is prone to errors and is time consuming due to various intra- and inter-operator variability. Nowadays, computerized methods for MRI segmentation have been extensively used to assist doctors in quantitative analyzes for disease diagnosis and monitoring. Thus, the purpose of this work was to evaluate the brain volume in MRI of MS patients. We used MRI scans with 30 slices of the five patients diagnosed with multiple sclerosis according to the McDonald criteria. The computational methods for the analysis of images were carried out in two steps: segmentation of the brain and brain volume quantification. The first image processing step was to perform brain extraction by skull stripping from the original image. In the skull stripper for MRI images of the brain, the algorithm registers a grayscale atlas image to the grayscale patient image. The associated brain mask is propagated using the registration transformation. Then this mask is eroded and used for a refined brain extraction based on level-sets (edge of the brain-skull border with dedicated expansion, curvature, and advection terms). In the second step, the brain volume quantification was performed by counting the voxels belonging to the segmentation mask and converted in cc. We observed an average brain volume of 1469.5 cc. We concluded that the automatic method applied in this work can be used for the brain extraction process and brain volume quantification in MRI. The development and use of computer programs can contribute to assist health professionals in the diagnosis and monitoring of patients with neurodegenerative diseases. In future works, we expect to implement more automated methods for the assessment of cerebral atrophy and brain lesions quantification, including machine-learning approaches. Acknowledgements: This work was supported by a grant from Brazilian agency Fundação de Amparo à Pesquisa do Estado de São Paulo (number 2019/16362-5).

Keywords: brain volume, magnetic resonance imaging, multiple sclerosis, skull stripper

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Authors: Andre Pastori D'Aurea, Lauriston Bertelli Feranades, Luis Eduardo Ferreira, Leandro Dias Pinto, Fabiana Ayumi Shiozaki

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The aim of this study was to improve the production of beef cattle on tropical pasture without harming this environment. On tropical pastures, cattle's live weight gain is lower than feedlot, and forage production is seasonable, changing from season to season. Thus, concerned with sustainable livestock production, the Premix Company has developed strategies to improve the production of beef cattle on tropical pasture to ensure sustainability of welfare and production. There are two important principles in this productivity system: 1) increase individual gains with use of better supplementation and 2) increase the productivity units with better forage quality like corn silage or other forms of forage conservations, actually used only in winter, and adding natural additives in the diet. This production system was applied from June 2017 to May 2018 in the Research Center of Premix Company, Patrocínio Paulista, São Paulo State, Brazil. The area used had 9 hectares of pasture of Brachiaria brizantha. 36 steers Nellore were evaluated for one year. The initial weight was 253 kg. The parameters used were daily average gain and gain per area. This indicated the corrections to be made and helped design future fertilization. In this case, we fertilized the pasture with 30 kg of nitrogen per animal divided into two parts. The diet was pasture and protein-energy supplements (0.4% of live weight). The supplement used was added with natural additive Fator P® – Premix Company). Fator P® is an additive composed by amino acids (lysine, methionine and tyrosine, 16400, 2980 and 3000 mg.kg-1 respectively), minerals, probiotics (Saccharomyces cerevisiae, 7 x 10E8 CFU.kg-1) and essential fatty acids (linoleic and oleic acids, 108.9 and 99g.kg-1 respectively). Due to seasonal changes, in the winter we supplemented the diet by increasing the offer of forage, supplementing with maize silage. It was offered 1% of live weight in silage corn and 0.4% of the live weight in protein-energetic supplements with additive Fator P ®. At the end of the period, the productivity was calculated by summing the individual gains for the area used. The average daily gain of the animals were 693 grams per day and was produced 1.005 kg /hectare/year. This production is about 8 times higher than the average of Brazilian meat national production. To succeed in this project, it is necessary to increase the gains per area, so it is necessary to increase the capacity per area. Pasture management is very important to the project's success because the dietary decisions were taken from the quantity and quality of the forage. We, therefore, recommend the use of animals in the growth phase because the response to supplementation is greater in that phase and we can allocate more animals per area. This system's carbon footprint reduces emissions by 61.2 percent compared to the Brazilian average. This beef cattle production system can be efficient and environmentally friendly to the natural. Another point is that bovines will benefit from their natural environment without competing or having an impact on human food production.

Keywords: cattle production, environment, pasture, sustainability

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Authors: Eduardo Martínez González, Mousumi Dey, Pekka Peljo

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Transitioning to a renewable energy model is inevitable owing to the effects of climate change. These energies are aimed at sustainability and a positive impact on the environment, but they are intermittent energies; their connection to the electrical grid depends on creating long-term, efficient, and low-cost energy storage devices. Redox flow batteries are attractive technologies to address this problem, as they store energy in solution through external tanks known as posolyte (solution to storage positive charge) and negolyte (solution to storage negative charge). During the charging process of the device, the posolyte and negolyte solutions are pumped into an electrochemical cell (which has the anode and cathode separated by an ionic membrane), where they undergo oxidation and reduction reactions at electrodes, respectively. The electrogenerated species should be stable and diffuse into the bulk solution. It has been possible to connect gigantic redox flow batteries to the electrical grid. However, the devices created do not fit with the sustainability criteria since their electroactive material consists of vanadium (material scarce and expensive) solutions dissolved in an acidic medium (e.g., 9 mol L-1 of H₂SO₄) that is highly corrosive; so, work is being done on the design of organic-electroactive electrolytes (posolytes and nogolytes) for their operation at different pH values, including neutral medium. As a main characteristic, negolyte species should have low reduction potential values, while the reverse is true for the oxidation process of posolytes. A wide variety of negolytes that store 1 and up to 2 electrons per molecule (in aqueous medium) have been publised. Gallocyanine compound was recently introduced as an electroactive material for developing alkaline flow battery negolytes. The system can storage two electrons per molecule, but its unexpectedly low water solubility was improved with an amino sulphonic acid additive. The cycling stability of and improved gallocyanine electrolyte was demonstrated by operating a flow battery cell (pairing the system to a posolyte composed of ferri/ferrocyanide solution) outside a glovebox. We also discovered that the additive improves the solubility of gallocyanine, but there is a kinetic price to pay for this advantage. Therefore, in this work, the effect of different amino sulphonic acid derivatives on the kinetics and solubility of gallocyanine compound was studied at alkaline solutions. The additive providing a faster electron transfer rate and high solubility was tested in a flow battery cell. An aqueous organic flow battery electrolyte working outside a glovebox with 15 mAhL-1 will be discussed. Acknowledgments: To Bi3BoostFlowBat Project (2021-2025), funded by the European Research Concil. For support with infrastructure, reagents, and a postdoctoral fellowship to Dr. Martínez-González.

Keywords: alkaline flow battery, gallocyanine electroactive material, amine-sulphonic acid additives, improved solubility

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Authors: Antònio Inês, Davide Silva, Filipa Carvalho, Luís Filipe-Riberiro, Fernando M. Nunes, Luís Abrunhosa, Fernanda Cosme

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The presence of mycotoxins in foodstuff is a matter of concern for food safety. Mycotoxins are toxic secondary metabolites produced by certain molds, being ochratoxin A (OTA) one of the most relevant. Wines can also be contaminated with these toxicants. Several authors have demonstrated the presence of mycotoxins in wine, especially ochratoxin A. Its chemical structure is a dihydro-isocoumarin connected at the 7-carboxy group to a molecule of L-β-phenylalanine via an amide bond. As these toxicants can never be completely removed from the food chain, many countries have defined levels in food in order to attend health concerns. OTA contamination of wines might be a risk to consumer health, thus requiring treatments to achieve acceptable standards for human consumption. The maximum acceptable level of OTA in wines is 2.0 μg/kg according to the Commission regulation No. 1881/2006. Therefore, the aim of this work was to reduce OTA to safer levels using different fining agents, as well as their impact on white wine physicochemical characteristics. To evaluate their efficiency, 11 commercial fining agents (mineral, synthetic, animal and vegetable proteins) were used to get new approaches on OTA removal from white wine. Trials (including a control without addition of a fining agent) were performed in white wine artificially supplemented with OTA (10 µg/L). OTA analyses were performed after wine fining. Wine was centrifuged at 4000 rpm for 10 min and 1 mL of the supernatant was collected and added of an equal volume of acetonitrile/methanol/acetic acid (78:20:2 v/v/v). Also, the solid fractions obtained after fining, were centrifuged (4000 rpm, 15 min), the resulting supernatant discarded, and the pellet extracted with 1 mL of the above solution and 1 mL of H2O. OTA analysis was performed by HPLC with fluorescence detection. The most effective fining agent in removing OTA (80%) from white wine was a commercial formulation that contains gelatin, bentonite and activated carbon. Removals between 10-30% were obtained with potassium caseinate, yeast cell walls and pea protein. With bentonites, carboxymethylcellulose, polyvinylpolypyrrolidone and chitosan no considerable OTA removal was verified. Following, the effectiveness of seven commercial activated carbons was also evaluated and compared with the commercial formulation that contains gelatin, bentonite and activated carbon. The different activated carbons were applied at the concentration recommended by the manufacturer in order to evaluate their efficiency in reducing OTA levels. Trial and OTA analysis were performed as explained previously. The results showed that in white wine all activated carbons except one reduced 100% of OTA. The commercial formulation that contains gelatin, bentonite and activated carbon reduced only 73% of OTA concentration. These results may provide useful information for winemakers, namely for the selection of the most appropriate oenological product for OTA removal, reducing wine toxicity and simultaneously enhancing food safety and wine quality.

Keywords: wine, ota removal, food safety, fining

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Authors: Benjamin Castillo, Luis Pastenes, Fernando Cordova

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The pathogen growth in animal source foods is a common problem in the food industry, causing monetary losses due to the spoiling of products or food intoxication outbreaks in the community. In this sense, the quality of the product is reflected by the population of deteriorating agents present in it, which are mainly bacteria. The factors which are likely associated with freshness in animal source foods are temperature and processing, storage, and transport times. However, the level of deterioration of products depends, in turn, on the characteristics of the bacterial population, causing the decomposition or spoiling, such as pH level and toxins. Knowing the growth dynamics of the agents that are involved in product contamination allows the monitoring for more efficient processing. This means better quality and reasonable costs, along with a better estimation of necessary time and temperature intervals for transport and storage in order to preserve product quality. The objective of this project is to design a secondary model that allows measuring the impact on temperature bacterial growth and the competition for pH adequacy and release of bacteriocins in order to describe such phenomenon and, thus, estimate food product half-life with the least possible risk of deterioration or spoiling. In order to achieve this objective, the authors propose an analysis of a three-dimensional ordinary differential which includes; logistic bacterial growth extended by the inhibitory action of bacteriocins including the effect of the medium pH; change in the medium pH levels through an adaptation of the Luedeking-Piret kinetic model; Bacteriocin concentration modeled similarly to pH levels. These three dimensions are being influenced by the temperature at all times. Then, this differential system is expanded, taking into consideration the variable temperature and the concentration of pulsed bacteriocins, which represent characteristics inherent of the modeling, such as transport and storage, as well as the incorporation of substances that inhibit bacterial growth. The main results lead to the fact that temperature changes in an early stage of transport increased the bacterial population significantly more than if it had increased during the final stage. On the other hand, the incorporation of bacteriocins, as in other investigations, proved to be efficient in the short and medium-term since, although the population of bacteria decreased, once the bacteriocins were depleted or degraded over time, the bacteria eventually returned to their regular growth rate. The efficacy of the bacteriocins at low temperatures decreased slightly, which equates with the fact that their natural degradation rate also decreased. In summary, the implementation of the mathematical model allowed the simulation of a set of possible bacteria present in animal based products, along with their properties, in various transport and storage situations, which led us to state that for inhibiting bacterial growth, the optimum is complementary low constant temperatures and the initial use of bacteriocins.

Keywords: bacterial growth, bacteriocins, mathematical modelling, temperature

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Authors: Tatiane Benvenuti, Fernando Hamerski, Alexandre Giacobbo, Andrea M. Bernardes, Marco A. S. Rodrigues

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Population growth in urban areas has caused damages to the environment, a consequence of the uncontrolled dumping of domestic and industrial wastewater. The capacity of some plants to purify domestic and agricultural wastewater has been demonstrated by several studies. Since natural wetlands have the ability to transform, retain and remove nutrients, constructed wetlands have been used for wastewater treatment. They are widely recognized as an economical, efficient and environmentally acceptable means of treating many different types of wastewater. T. domingensis Pers. species have shown a good performance and low deployment cost to extract, detoxify and sequester pollutants. Constructed Floating Wetlands (CFWs) consist of emergent vegetation established upon a buoyant structure, floating on surface waters. The upper parts of the vegetation grow and remain primarily above the water level, while the roots extend down in the water column, developing an extensive under water-level root system. Thus, the vegetation grows hydroponically, performing direct nutrient uptake from the water column. Biofilm is attached on the roots and rhizomes, and as physical and biochemical processes take place, the system functions as a natural filter. The aim of this study is to diagnose the application of macrophytes in artificial floating in the treatment of domestic sewage in south Brazil. The T. domingensis Pers. plants were placed in a flotation system (polymer structure), in full scale, in a sewage treatment plant. The sewage feed rate was 67.4 m³.d⁻¹ ± 8.0, and the hydraulic retention time was 11.5 d ± 1.3. This CFW treat the sewage generated by 600 inhabitants, which corresponds to 12% of the population served by this municipal treatment plant. During 12 months, samples were collected every two weeks, in order to evaluate parameters as chemical oxygen demand (COD), biochemical oxygen demand in 5 days (BOD5), total Kjeldahl nitrogen (TKN), total phosphorus, total solids, and metals. The average removal of organic matter was around 55% for both COD and BOD5. For nutrients, TKN was reduced in 45.9% what was similar to the total phosphorus removal, while for total solids the reduction was 33%. For metals, aluminum, copper, and cadmium, besides in low concentrations, presented the highest percentage reduction, 82.7, 74.4 and 68.8% respectively. Chromium, iron, and manganese removal achieved values around 40-55%. The use of T. domingensis Pers. in artificial floating for sewage treatment is an effective and innovative alternative in Brazilian sewage treatment systems. The evaluation of additional parameters in the treatment system may give useful information in order to improve the removal efficiency and increase the quality of the water bodies.

Keywords: constructed wetland, floating system, sewage treatment, Typha domingensis Pers.

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Authors: Christine F. Boos, Fernando M. Azevedo

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Electroencephalogram (EEG) is a record of the electrical activity of the brain that has many applications, such as monitoring alertness, coma and brain death; locating damaged areas of the brain after head injury, stroke and tumor; monitoring anesthesia depth; researching physiology and sleep disorders; researching epilepsy and localizing the seizure focus. Epilepsy is a chronic condition, or a group of diseases of high prevalence, still poorly explained by science and whose diagnosis is still predominantly clinical. The EEG recording is considered an important test for epilepsy investigation and its visual analysis is very often applied for clinical confirmation of epilepsy diagnosis. Moreover, this EEG analysis can also be used to help define the types of epileptic syndrome, determine epileptiform zone, assist in the planning of drug treatment and provide additional information about the feasibility of surgical intervention. In the context of diagnosis confirmation the analysis is made using long term EEG recordings with at least 24 hours long and acquired by a minimum of 24 electrodes in which the neurophysiologists perform a thorough visual evaluation of EEG screens in search of specific electrographic patterns called epileptiform discharges. Considering that the EEG screens usually display 10 seconds of the recording, the neurophysiologist has to evaluate 360 screens per hour of EEG or a minimum of 8,640 screens per long term EEG recording. Analyzing thousands of EEG screens in search patterns that have a maximum duration of 200 ms is a very time consuming, complex and exhaustive task. Because of this, over the years several studies have proposed automated methodologies that could facilitate the neurophysiologists’ task of identifying epileptiform discharges and a large number of methodologies used neural networks for the pattern classification. One of the differences between all of these methodologies is the type of input stimuli presented to the networks, i.e., how the EEG signal is introduced in the network. Five types of input stimuli have been commonly found in literature: raw EEG signal, morphological descriptors (i.e. parameters related to the signal’s morphology), Fast Fourier Transform (FFT) spectrum, Short-Time Fourier Transform (STFT) spectrograms and Wavelet Transform features. This study evaluates the application of these five types of input stimuli and compares the classification results of neural networks that were implemented using each of these inputs. The performance of using raw signal varied between 43 and 84% efficiency. The results of FFT spectrum and STFT spectrograms were quite similar with average efficiency being 73 and 77%, respectively. The efficiency of Wavelet Transform features varied between 57 and 81% while the descriptors presented efficiency values between 62 and 93%. After simulations we could observe that the best results were achieved when either morphological descriptors or Wavelet features were used as input stimuli.

Keywords: Artificial neural network, electroencephalogram signal, pattern recognition, signal processing

Procedia PDF Downloads 530

Authors: Sara Camino, Fernando Vega, Mercedes Cano, Benito Navarrete, José A. Camino

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Carbon capture and storage (CCS) technologies should play a relevant role towards low-carbon systems in the European Union by 2030. Partial oxy-combustion emerges as a promising CCS approach to mitigate anthropogenic CO₂ emissions. Its advantages respect to other CCS technologies rely on the production of a higher CO₂ concentrated flue gas than these provided by conventional air-firing processes. The presence of more CO₂ in the flue gas increases the driving force in the separation process and hence it might lead to further reductions of the energy requirements of the overall CO₂ capture process. A higher CO₂ concentrated flue gas should enhance the CO₂ capture by chemical absorption in solvent kinetic and CO₂ cyclic capacity. They have impact on the performance of the overall CO₂ absorption process by reducing the solvent flow-rate required for a specific CO₂ removal efficiency. Lower solvent flow-rates decreases the reboiler duty during the regeneration stage and also reduces the equipment size and pumping costs. Moreover, R&D activities in this field are focused on novel solvents and blends that provide lower CO₂ absorption enthalpies and therefore lower energy penalties associated to the solvent regeneration. In this respect, sterically hindered amines are considered potential solvents for CO₂ capture. They provide a low energy requirement during the regeneration process due to its molecular structure. However, its absorption kinetics are slow and they must be promoted by blending with faster solvents such as monoethanolamine (MEA) and piperazine (PZ). In this work, the kinetic behavior of two sterically hindered amines were studied under partial oxy-combustion conditions and compared with MEA. A lab-scale semi-batch reactor was used. The CO₂ composition of the synthetic flue gas varied from 15%v/v – conventional coal combustion – to 60%v/v – maximum CO₂ concentration allowable for an optimal partial oxy-combustion operation. Firstly, 2-amino-2-methyl-1-propanol (AMP) showed a hybrid behavior with fast kinetics and a low enthalpy of CO₂ absorption. The second solvent was Isophrondiamine (IF), which has a steric hindrance in one of the amino groups. Its free amino group increases its cyclic capacity. In general, the presence of higher CO₂ concentration in the flue gas accelerated the CO₂ absorption phenomena, producing higher CO₂ absorption rates. In addition, the evolution of the CO2 loading also exhibited higher values in the experiments using higher CO₂ concentrated flue gas. The steric hindrance causes a hybrid behavior in this solvent, between both fast and slow kinetic solvents. The kinetics rates observed in all the experiments carried out using AMP were higher than MEA, but lower than the IF. The kinetic enhancement experienced by AMP at a high CO2 concentration is slightly over 60%, instead of 70% – 80% for IF. AMP also improved its CO₂ absorption capacity by 24.7%, from 15%v/v to 60%v/v, almost double the improvements achieved by MEA. In IF experiments, the CO₂ loading increased around 10% from 15%v/v to 60%v/v CO₂ and it changed from 1.10 to 1.34 mole CO₂ per mole solvent, more than 20% of increase. This hybrid kinetic behavior makes AMP and IF promising solvents for partial oxy–combustion applications.

Keywords: absorption, carbon capture, partial oxy-combustion, solvent

Procedia PDF Downloads 191

Authors: Margarida Soares, Zlatina Genisheva, Lucas Nascimento, André Ribeiro, Tiago Miranda, Eduardo Pereira, Joana Carvalho

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In the current global context, we face a significant challenge: the rapid population increase combined with the pressing need for sustainable management of agro-industrial waste. Beyond understanding how population growth impacts waste generation, it is essential to first identify the primary types of waste produced and the countries responsible to guide targeted actions. This study presents key statistical data on waste production from the agriculture, forestry, and fishing sectors across the European Union, alongside information on the agricultural areas dedicated to crop production in each European Union country. These insights will form the basis for future research into waste production by crop type and country to improve waste management practices and promote recovery methods that are vital for environmental sustainability. The agricultural sector must stay at the forefront of scientific and technological advancements to meet climate change challenges, protect the environment, and ensure food and health security. The study's findings indicate that population growth significantly increases pressure on natural resources, leading to a rise in agro-industrial waste production. EUROSTAT data shows that, in 2020, the agriculture, forestry, and fishing sectors produced over 21 million tons of waste. Spain emerged as the largest producer, contributing nearly 30% of the EU's total waste in these sectors. Furthermore, five countries—Spain, the Netherlands, France, Sweden, and Germany—were responsible for producing more than two-thirds of the waste from these sectors. Regarding agricultural land use, the data for 2020 revealed that around two-thirds of the total agricultural area was concentrated in six countries: France, Spain, Germany, Poland, Romania, and Italy. Regarding waste production per capita, the Netherlands had the highest figures in the EU for 2020. The data presented in this study highlights the urgent need for action in managing agricultural waste in the EU. As population growth continues to drive up demand for agricultural products, waste generation will inevitably rise unless significant changes are made in managing of agro-industrial waste. The countries must lead the way in adopting technological waste management strategies that focus on reducing, reusing, and recycling waste to benefit both the environment and society. Equally important is the need to promote collaborative efforts between governments, industries, and research institutions to develop and implement technologies that transform waste into valuable resources. The insights from this study are critical for informing future strategies to improve the management and valorization of waste from the agro-industrial sector. One of the most promising approaches is adopting circular economy principles to create closed-loop systems that minimize environmental impacts. By rethinking waste as a valuable resource rather than a by-product, agricultural industries can contribute to more sustainable practices that support both environmental health and economic growth.

Keywords: agricultural area, agricultural waste, circular economy, environmental challenges, population growth

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Authors: Fernando Vega, Esmeralda Portillo, Sara Camino, Benito Navarrete, Elena Montavez

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The European Union aims at strongly reducing their CO₂ emissions from energy and industrial sector by 2030. The energy sector contributes with more than two-thirds of the CO₂ emission share derived from anthropogenic activities. Although efforts are mainly focused on the use of renewables by energy production sector, carbon capture and storage (CCS) remains as a frontline option to reduce CO₂ emissions from industrial process, particularly from fossil-fuel power plants and cement production. Among the most feasible and near-to-market CCS technologies, namely post-combustion and oxy-combustion, partial oxy-combustion is a novel concept that can potentially reduce the overall energy requirements of the CO₂ capture process. This technology consists in the use of higher oxygen content in the oxidizer that should increase the CO₂ concentration of the flue gas once the fuel is burnt. The CO₂ is then separated from the flue gas downstream by means of a conventional CO₂ chemical absorption process. The production of a higher CO₂ concentrated flue gas should enhance the CO₂ absorption into the solvent, leading to further reductions of the CO₂ separation performance in terms of solvent flow-rate, equipment size, and energy penalty related to the solvent regeneration. This work evaluates a portfolio of CCS technologies applied to fossil-fuel power plants. For this purpose, an economic evaluation methodology was developed in detail to determine the main economical parameters for CO₂ emission removal such as the levelized cost of electricity (LCOE) and the CO₂ captured and avoided costs. ASPEN Plus™ software was used to simulate the main units of power plant and solve the energy and mass balance. Capital and investment costs were determined from the purchased cost of equipment, also engineering costs and project and process contingencies. The annual capital cost and operating and maintenance costs were later obtained. A complete energy balance was performed to determine the net power produced in each case. The baseline case consists of a supercritical 500 MWe coal-fired power plant using anthracite as a fuel without any CO₂ capture system. Four cases were proposed: conventional post-combustion capture, oxy-combustion and partial oxy-combustion using two levels of oxygen-enriched air (40%v/v and 75%v/v). CO₂ chemical absorption process using monoethanolamine (MEA) was used as a CO₂ separation process whereas the O₂ requirement was achieved using a conventional air separation unit (ASU) based on Linde's cryogenic process. Results showed a reduction of 15% of the total investment cost of the CO₂ separation process when partial oxy-combustion was used. Oxygen-enriched air production also reduced almost half the investment costs required for ASU in comparison with oxy-combustion cases. Partial oxy-combustion has a significant impact on the performance of both CO₂ separation and O₂ production technologies, and it can lead to further energy reductions using new developments on both CO₂ and O₂ separation processes.

Keywords: carbon capture, cost methodology, economic evaluation, partial oxy-combustion

Procedia PDF Downloads 149

Authors: Benjamin Glasner, Carlos Henriquez, Fernando Alfaro, Nicole Trefault, Santiago Andrade, Rodrigo De La Iglesia

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A central question in ecology refers to the relative importance that local-scale variables have over community composition, when compared with regional-scale variables. In coastal environments, strong seasonal abiotic influence dominates these systems, weakening the impact of other parameters like micronutrients. After the industrial revolution, micronutrients like trace metals have increased in ocean as pollutants, with strong effects upon biotic entities and biological processes in coastal regions. Coastal picoplankton communities had been characterized as a cyanobacterial dominated fraction, but in recent years the eukaryotic component of this size fraction has gained relevance due to their high influence in carbon cycle, although, diversity patterns and responses to disturbances are poorly understood. South Pacific upwelling coastal environments represent an excellent model to study seasonal changes due to a strong influence in the availability of macro- and micronutrients between seasons. In addition, some well constrained coastal bays of this region have been subjected to strong disturbances due to trace metal inputs. In this study, we aim to compare the influence of seasonality and trace metals concentrations, on the community structure of planktonic picoeukaryotes. To describe seasonal patterns in the study area, satellite data in a 6 years time series and in-situ measurements with a traditional oceanographic approach such as CTDO equipment were performed. In addition, trace metal concentrations were analyzed trough ICP-MS analysis, for the same region. For biological data collection, field campaigns were performed in 2011-2012 and the picoplankton community was described by flow cytometry and taxonomical characterization with next-generation sequencing of ribosomal genes. The relation between the abiotic and biotic components was finally determined by multivariate statistical analysis. Our data show strong seasonal fluctuations in abiotic parameters such as photosynthetic active radiation and superficial sea temperature, with a clear differentiation of seasons. However, trace metal analysis allows identifying strong differentiation within the study area, dividing it into two zones based on trace metals concentration. Biological data indicate that there are no major changes in diversity but a significant fluctuation in evenness and community structure. These changes are related mainly with regional parameters, like temperature, but by analyzing the metal influence in picoplankton community structure, we identify a differential response of some plankton taxa to metal pollution. We propose that some picoeukaryotic plankton groups respond differentially to metal inputs, by changing their nutritional status and/or requirements under disturbances as a derived outcome of toxic effects and tolerance.

Keywords: Picoeukaryotes, plankton communities, trace metals, seasonal patterns

Procedia PDF Downloads 174

Authors: Ricardo Alberto Chiong Zevallos, Eduardo Moraes Rego Reis

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Pancreatic adenocarcinoma (PDAC) patients have a less than 10% 5-year survival rate. PDAC has no defined diagnostic and prognostic biomarkers. Gemcitabine is the first-line drug in PDAC and several other cancers. Long non-coding RNAs (lncRNAs) contribute to the tumorigenesis and are potential biomarkers for PDAC. Although lncRNAs aren’t translated into proteins, they have important functions. LncRNAs can decoy or recruit proteins from the epigenetic machinery, act as microRNA sponges, participate in protein translocation through different cellular compartments, and even promote chemoresistance. The chromatin remodeling enzyme EZH2 is a histone methyltransferase that catalyzes the methylation of histone 3 at lysine 27, silencing local expression. EZH2 is ambivalent, it can also activate gene expression independently of its histone methyltransferase activity. EZH2 is overexpressed in several cancers and interacts with lncRNAs, being recruited to a specific locus. EZH2 can be recruited to activate an oncogene or silence a tumor suppressor. The lncRNAs misregulation in cancer can result in the differential recruitment of EZH2 and in a distinct epigenetic landscape, promoting chemoresistance. The relevance of the EZH2-lncRNAs interaction to chemoresistant PDAC was assessed by Real Time quantitative PCR (RT-qPCR) and RNA Immunoprecipitation (RIP) experiments with naïve and gemcitabine-resistant PDAC cells. The expression of several lncRNAs and EZH2 gene targets was evaluated contrasting naïve and resistant cells. Selection of candidate genes was made by bioinformatic analysis and literature curation. Indeed, the resistant cell line showed higher expression of chemoresistant-associated lncRNAs and protein coding genes. RIP detected lncRNAs interacting with EZH2 with varying intensity levels in the cell lines. During RIP, the nuclear fraction of the cells was incubated with an antibody for EZH2 and with magnetic beads. The RNA precipitated with the beads-antibody-EZH2 complex was isolated and reverse transcribed. The presence of candidate lncRNAs was detected by RT-qPCR, and the enrichment was calculated relative to INPUT (total lysate control sample collected before RIP). The enrichment levels varied across the several lncRNAs and cell lines. The EZH2-lncRNA interaction might be responsible for the regulation of chemoresistance-associated genes in multiple cancers. The relevance of the lncRNA-EZH2 interaction to PDAC was assessed by siRNA knockdown of a lncRNA, followed by the analysis of the EZH2 target expression by RT-qPCR. The chromatin immunoprecipitation (ChIP) of EZH2 and H3K27me3 followed by RT-qPCR with primers for EZH2 targets also assess the specificity of the EZH2 recruitment by the lncRNA. This is the first report of the interaction of EZH2 and lncRNAs HOTTIP and PVT1 in chemoresistant PDAC. HOTTIP and PVT1 were described as promoting chemoresistance in several cancers, but the role of EZH2 is not clarified. For the first time, the lncRNA LINC01133 was detected in a chemoresistant cancer. The interaction of EZH2 with LINC02577, LINC00920, LINC00941, and LINC01559 have never been reported in any context. The novel lncRNAs-EZH2 interactions regulate chemoresistant-associated genes in PDAC and might be relevant to other cancers. Therapies targeting EZH2 alone weren’t successful, and a combinatorial approach also targeting the lncRNAs interacting with it might be key to overcome chemoresistance in several cancers.

Keywords: epigenetics, chemoresistance, long non-coding RNAs, pancreatic cancer, histone modification

Procedia PDF Downloads 96

Authors: Andrés Quiroz, Emilio Hormazábal, Ana Mutis, Fernando Ortega, Loreto Méndez, Leonardo Parra

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Red clover root borer, Hylastinus obscurus Marsham (Coleoptera: Curculionidae), is the main insect pest associated to red clover, Trifolium pratense L. An average of 1.5 H. obscurus per plant can cause 5.5% reduction in forage yield in pastures of two to three years old. Moreover, insect attack can reach 70% to 100% of the plants. To our knowledge, there is no a chemical strategy for controlling this pest. Therefore alternative strategies for controlling H. obscurus are a high priority for red clover producers. One of this alternative is related to the study of secondary metabolites involved in intrinsic chemical defenses developed by plants, such as isoflavonoids. The isoflavonoids formononetin and daidzein have elicited an antifeedant and phagostimult effect on H. obscurus respectively. However, we do not know how is the dynamic variation of these isoflavonoids under field conditions. The main objective of this work was to evaluate the variation of the antifeedant isoflavonoids formononetin, the phagostimulant isoflavonoids daidzein, and their respective glycosides over time in different ecotypes of red clover. Fourteen red clover ecotypes (8 cultivars and 6 experimental lines), were collected at INIA-Carillanca (La Araucanía, Chile). These plants were established in October 2015 under irrigated conditions. The cultivars were distributed in a randomized complete block with three replicates. The whole plants were sampled in four times: 15th October 2016, 12th December 2016, 27th January 2017 and 16th March 2017 with sufficient amount of soil to avoid root damage. A polar fraction of isoflavonoid was obtained from 20 mg of lyophilized root tissue extracted with 2 mL of 80% MeOH for 16 h using an orbital shaker in the dark at room temperature. After, an aliquot of 1.4 mL of the supernatant was evaporated, and the residue was resuspended in 300 µL of 45% MeOH. The identification and quantification of isoflavonoid root extracts were performed by the injection of 20 µL into a Shimadzu HPLC equipped with a C-18 column. The sample was eluted with a mobile phase composed of AcOH: H₂O (1:9 v/v) as solvent A and CH₃CN as solvent B. The detection was performed at 260 nm. The results showed that the amount of aglycones was higher than the respective glycosides. This result is according to the biosynthetic pathway of flavonoids, where the formation of glycoside is further to the glycosides biosynthesis. The amount of formononetin was higher than daidzein. In roots, where H. obscurus spent the most part of its live cycle, the highest content of formononetin was found in G 27, Pawera, Sabtoron High, Redqueli-INIA and Superqueli-INIA cvs. (2.1, 1.8, 1.8, 1.6 and 1.0 mg g⁻¹ respectively); and the lowest amount of daidzein were found Superqueli-INIA (0.32 mg g⁻¹) and in the experimental line Sel Syn Int4 (0.24 mg g⁻¹). This ecotype showed a high content of formononetin (0.9 mg g⁻¹). This information, associated with cultural practices, could help farmers and breeders to reduce H. obscurus in grassland, selecting ecotypes with high content of formononetin and low amount of daidzein in the roots of red clover plants. Acknowledgements: FONDECYT 1141245 and 11130715.

Keywords: daidzein, formononetin, isoflavonoid glycosides, trifolium pratense

Procedia PDF Downloads 219

Authors: Sandra Cardoso, Gaspar Pais, Judite Neves, Sandra Cavaca, Fernando Araújo

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In 2021, Portugal has 63 emergency department (ED) visits per 100 people annually, the highest numbers in Europe. While EDs provide a critical service, high use is indicative of inappropriate and inefficient healthcare. In Portugal, all ED have the Manchester Triage System (MTS), a clinical risk management tool to enable that patients are seen in order of clinical priority. In 2023, more than 40% of the ED visits were of non-urgent conditions (blue and green), that could be better managed in primary health care (PHC), meaning wrong use of resources and lack of health literacy. From 2017, the country has a phone line, SNS24 (Contact Centre of the National Health Service), for triage, counseling, and referral service, 24 hours/7 days a week. The pilot project ‘Call before, save lives’ was implemented in the municipalities of Póvoa de Varzim and Vila do Conde (around 150.000 residents), in May 2023, by the executive board of the Portuguese Health Service, with the support of the Shared Services of the Ministry of Health, and local authorities. This geographical area has short travel times, 99% of the population a family doctor and the region is organized in a health local unit (HLU), integrating PHC and the local hospital. The purposes of this project included to increase awareness to contact SNS 24, before going to an ED, and non-urgent conditions oriented to a family doctor, reducing ED visits. The implementation of the project involved two phases, beginning with: i) development of campaigns using local influencers (fishmonger, model, fireman) through local institutions and media; ii) provision of telephone installed on site to contact SNS24; iii) establishment of open consultation in PHC; iv) promotion of the use of SNS24; v) creation of acute consultations at the hospital for complex chronic patients; and vi) direct referral for home hospitalization by PHC. The results of this project showed an excellent level of access to SNS24, an increase in the number of users referred to ED, with great satisfaction of users and professionals. The second phase, initiated in January 2024, for access to the ED, the need for prior referral was established as an admission rule, except for certain situations, as trauma patients. If the patient refuses, their registration in the ED and subsequent screening in accordance with the MTS must be ensured. When the patient is non-urgent, shall not be observed in the ED, provided that, according to his clinical condition, is guaranteed to be referred to PHC or to consultation/day hospital, through effective scheduling of an appointment for the same or the following day. In terms of results, 8 weeks after beginning of phase 2, we assist of a decrease in self-reported patients to ED from 59% to 15%, and a reduction of around 7% of ED visits. The key for this success was an effective public campaign that increases the knowledge of the right use of the health system, and capable of changing behaviors.

Keywords: contact centre of the national health service, emergency department visits, public campaign, health literacy, SNS24

Procedia PDF Downloads 69

Authors: Andrés Quiroz, Emilio Hormazabal, Ana Mutis, Fernando Ortega, Manuel Chacón-Fuentes, Leonardo Parra

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Red clover (Trifolium pratense L.) is an important forage species in temperate regions of the world. The main limitation of this species worldwide is a lack of persistence related to the high mortality of plants due to a complex of biotic and abiotic factors, determining a life span of two or three seasons. Because of the importance of red clover in Chile, a red clover breeding program was started at INIA Carillanca Research Center in 1989, with the main objective of improving the survival of plants, forage yield, and persistence. The main selection criteria for selecting new varieties have been based on agronomical parameters and biotic factors. The main biotic factor associated with red clover mortality in Chile is Hylastinus obscurus (Coleoptera: Curculionidae). Both larval and adults feed on the roots, causing weakening and subsequent death of clover plants. Pesticides have not been successful for controlling infestations of this root borer. Therefore, alternative strategies for controlling this pest are a high priority for red clover producers. Currently, the role of semiochemical in the interaction between H. obscurus and red clover plants has been widely studied for our group. Specifically, from the red clover foliage has been identified limonene is eliciting repellency from the root borer. Limonene is generated in the plant from two independent biosynthetic pathways, the mevalonic acid, and deoxyxylulose pathway. Mevalonate pathway enzymes are localized in the cytosol, whereas the deoxyxylulose phosphate pathway enzymes are found in plastids. In summary, limonene can be determinated by enzymatic bioassay using GPP as substrate and by limonene synthase expression. Therefore, the main objective of this work was to study genetic variation of limonene in material provided by INIA´s Red Clover breeding program. Protein extraction was carried out homogenizing 250 mg of leave tissue and suspended in 6 mL of extraction buffer (PEG 1500, PVP-30, 20 mM MgCl2 and antioxidants) and stirred on ice for 20 min. After centrifugation, aliquots of 2.5 mL were desalted on PD-10 columns, resulting in a final volume of 3.5 mL. Protein determination was performed according to Bradford with BSA as a standard. Monoterpene synthase assays were performed with 50 µL of protein extracts transferred into gas-tight 2 mL crimp seal vials after addition of 4 µL MgCl₂ and 41 µL assay buffer. The assay was started by adding 5 µL of a GPP solution. The mixture was incubated for 30 min at 40 °C. Biosynthesized limonene was quantified in a GC equipped with a chiral column and using synthetic R and S-limonene standards. The enzymatic the production of R and S-limonene from different Superqueli-Carillanca genotypes is shown in this work. Preliminary results showed significant differences in limonene content among the genotypes analyzed. These results constitute an important base for selecting genotypes with a high content of this repellent monoterpene towards H. obscurus.

Keywords: head space, limonene enzymatic determination, red clover, Hylastinus obscurus

Procedia PDF Downloads 267

Authors: Catarina Ferreira Rebelo, Luis Madeira de Carvalho, Fernando González González

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The order Passeridae corresponds to the richest and most abundant group of birds, with approximately 6500 species, making it possible to assert that two out of every three bird species are passerines. They are globally distributed and exhibit remarkable morphological and ecological variability. While numerous species of parasites have been identified and described in wild birds, there has been little focus on passeriformes. Seventeen passerines admitted to GREFA, a Wildlife Rehabilitation Center, throughout the months of October, November and December 2022 were analyzed. The species included Aegithalos caudatus, Anthus pratensis, Carduelis chloris, Certhia brachydactyla, Erithacus rubecula, Fringilla coelebs, Parus ater, Passer domesticus, Sturnus unicolor, Sylvia atricapilla, Turdus merula and Turdus philomelos. Data regarding past history was collected, and necropsies were conducted to identify the cause of death and body condition and determine the presence of parasites. Additionally, samples of intestinal content were collected for direct/fecal smear, flotation and sedimentation techniques. Sixteen (94.1%) passerines were considered positive for the presence of parasitic forms in at least one of the techniques used, including parasites detected in necropsy. Adult specimens of both sexes and tritonymphs of Monojoubertia microhylla and ectoparasites of the genus Ornithonyssus were identified. Macroscopic adult endoparasitic forms were also found during necropsies, including Diplotriaena sp., Serratospiculum sp. and Porrocaecum sp.. Parasitism by coccidia was observed with no sporulation. Additionally, eggs of nematodes from various genera were detected, such as Diplotriaena sp., Capillaria sp., Porrocaecum sp., Syngamus sp. and Strongyloides sp., eggs of trematodes, specifically the genus Brachylecithum and cestode oncospheres, whose genera were not identified. To our knowledge, the respiratory nematode Serratospiculum sp. found in this study is being reported for the first time in passerines in the Iberian Peninsula, along with the application of common coprological techniques for the identification of eggs in the intestinal content. The majority of parasites identified utilize intermediary hosts present in the diet of the passerines sampled. Furthermore, the discovery of certain parasites with a direct life cycle could potentially exert greater influence, particularly in specific scenarios such as within nests or during the rehabilitation process in wildlife centers. These parasites may impact intraspecific competition, increase susceptibility to predators or lead to death. However, their cost to wild birds is often not clear, as individuals can endure various parasites without significant harm. Furthermore, wild birds serve as important sources of parasites across different animal groups, including humans and other mammals. This study provides invaluable insights into the parasitic fauna of these birds, not only serving as a cornerstone for future epidemiological investigations but also enhancing our comprehension of these avian species.

Keywords: birds, parasites, passerines, wild, spain

Procedia PDF Downloads 42

Authors: Eduardo Cabrera-Rode, Janet Rodriguez, Aimee Alvarez, Ragmila Echevarria, Antonio D. Reyes, Ileana Cubas-Duenas, Silvia E. Turcios, Oscar Diaz-Diaz

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Obex is a nutritional supplement to help weight loss naturally. In addition, this supplement has a satiating effect that helps control the craving to eat between meals. The purpose of this study was to evaluate the effect of Obex in the metabolic syndrome (MS). This was an open label pilot study conducted in 30 patients with MS and ages between 29 and 60 years old. Participants received Obex, at a dose of one sachet before (30 to 45 minutes) the two main meals (lunch and dinner) daily (mean two sachets per day) for 3 months. The content of the sachets was dissolved in a glass of water or fruit juice. Obex ingredients: Açai (Euterpe oleracea Mart.) berry, inulin, Phaseolus vulgaris, Caralluma fimbriata, inositol, choline, arginine, ornitine, zinc sulfate, carnitine fumarate, methionine, calcium pantothenate, pyridoxine and folic acid. In addition to anthropometric measures and blood pressure, fasting plasma glucose, total cholesterol, triglycerides and HDL-cholesterol and insulin were determined. Insulin resistance was assessed by HOMA-IR index. Three indirect indexes were used to calculate insulin sensitivity [QUICKI index (Quantitative insulin sensitivity check index), Bennett index and Raynaud index]. Metabolic syndrome was defined according to the Joint Interim Statement (JIS) criteria. The JIS criteria require at least three of the following components: (1) abdominal obesity (waist circumference major or equal major or equal 94 cm for men or 80 cm for women), (2) triglycerides major or equal 1.7 mmol/L, (3) HDL cholesterol minor 1.03 mmol/L for men or minor 1.30 mmol/L for women, (4) systolic/diastolic blood pressure major or equal 130/85mmHg or use antihypertensive drugs, and (5) fasting plasma glucose major or equal 5.6 mmol/L or known treatment for diabetes. This study was approved by the Ethical and Research Committee of the National Institute of Endocrinology, Cuba and conducted according to the Declaration of Helsinki. Obex is registered as a food supplement in the National Institute of Nutrition and Food, Havana, Cuba. Written consent was obtained from all patients before the study. The clinical trial had been registered at ClinicalTrials.gov. After three months of treatment, 43.3% (13/30) of participants decreased the frequency of MS. Compared to baseline, Obex significantly reduced body weight, BMI, waist circumference, and waist/hip ratio and improved HDL-c (p<0.0001) and in addition to lowering blood pressure (p<0.05). After Obex intake, subjects also have shown a reduction in fasting plasma glucose (p<0.0001) and insulin sensitivity was enhanced (p=0.001). No adverse effects were seen in any of the participants during the study. In this pilot study, consumption of Obex decreased the prevalence of MS due to the improved selected components of the metabolic syndrome, indicating that further studies are warranted. Obex emerges as an effective and well tolerated treatment for preventing or delaying MS and therefore potential reduction of cardiovascular risk.

Keywords: nutritional supplement, metabolic syndrome, weight loss, insulin resistance

Procedia PDF Downloads 298

Authors: Ana L. M. Pavan, Guilherme Giacomini, Allan F. F. Alves, Marcela De Oliveira, Fernando A. B. Neto, Maria E. D. Rosa, Andre P. Trindade, Diana R. De Pina

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Mammography is a worldwide image modality used to diagnose breast cancer, even in asymptomatic women. Due to its large availability, mammograms can be used to measure breast density and to predict cancer development. Women with increased mammographic density have a four- to sixfold increase in their risk of developing breast cancer. Therefore, studies have been made to accurately quantify mammographic breast density. In clinical routine, radiologists perform image evaluations through BIRADS (Breast Imaging Reporting and Data System) assessment. However, this method has inter and intraindividual variability. An automatic objective method to measure breast density could relieve radiologist’s workload by providing a first aid opinion. However, pectoral muscle is a high density tissue, with similar characteristics of fibroglandular tissues. It is consequently hard to automatically quantify mammographic breast density. Therefore, a pre-processing is needed to segment the pectoral muscle which may erroneously be quantified as fibroglandular tissue. The aim of this work was to develop an automatic algorithm to segment and extract pectoral muscle in digital mammograms. The database consisted of thirty medio-lateral oblique incidence digital mammography from São Paulo Medical School. This study was developed with ethical approval from the authors’ institutions and national review panels under protocol number 3720-2010. An algorithm was developed, in Matlab® platform, for the pre-processing of images. The algorithm uses image processing tools to automatically segment and extract the pectoral muscle of mammograms. Firstly, it was applied thresholding technique to remove non-biological information from image. Then, the Hough transform is applied, to find the limit of the pectoral muscle, followed by active contour method. Seed of active contour is applied in the limit of pectoral muscle found by Hough transform. An experienced radiologist also manually performed the pectoral muscle segmentation. Both methods, manual and automatic, were compared using the Jaccard index and Bland-Altman statistics. The comparison between manual and the developed automatic method presented a Jaccard similarity coefficient greater than 90% for all analyzed images, showing the efficiency and accuracy of segmentation of the proposed method. The Bland-Altman statistics compared both methods in relation to area (mm²) of segmented pectoral muscle. The statistic showed data within the 95% confidence interval, enhancing the accuracy of segmentation compared to the manual method. Thus, the method proved to be accurate and robust, segmenting rapidly and freely from intra and inter-observer variability. It is concluded that the proposed method may be used reliably to segment pectoral muscle in digital mammography in clinical routine. The segmentation of the pectoral muscle is very important for further quantifications of fibroglandular tissue volume present in the breast.

Keywords: active contour, fibroglandular tissue, hough transform, pectoral muscle

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Authors: M. A. C. S. Sampath Fernando, James M. Curran, Renate Meyer

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Model assessment, in the Bayesian context, involves evaluation of the goodness-of-fit and the comparison of several alternative candidate models for predictive accuracy and improvements. In posterior predictive checks, the data simulated under the fitted model is compared with the actual data. Predictive model accuracy is estimated using information criteria such as the Akaike information criterion (AIC), the Bayesian information criterion (BIC), the Deviance information criterion (DIC), and the Watanabe-Akaike information criterion (WAIC). The goal of an information criterion is to obtain an unbiased measure of out-of-sample prediction error. Since posterior checks use the data twice; once for model estimation and once for testing, a bias correction which penalises the model complexity is incorporated in these criteria. Cross-validation (CV) is another method used for examining out-of-sample prediction accuracy. Leave-one-out cross-validation (LOO-CV) is the most computationally expensive variant among the other CV methods, as it fits as many models as the number of observations. Importance sampling (IS), truncated importance sampling (TIS) and Pareto-smoothed importance sampling (PSIS) are generally used as approximations to the exact LOO-CV and utilise the existing MCMC results avoiding expensive computational issues. The reciprocals of the predictive densities calculated over posterior draws for each observation are treated as the raw importance weights. These are in turn used to calculate the approximate LOO-CV of the observation as a weighted average of posterior densities. In IS-LOO, the raw weights are directly used. In contrast, the larger weights are replaced by their modified truncated weights in calculating TIS-LOO and PSIS-LOO. Although, information criteria and LOO-CV are unable to reflect the goodness-of-fit in absolute sense, the differences can be used to measure the relative performance of the models of interest. However, the use of these measures is only valid under specific circumstances. This study has developed 11 models using normal, log-normal, gamma, and student’s t distributions to improve the PCR stutter prediction with forensic data. These models are comprised of four with profile-wide variances, four with locus specific variances, and three which are two-component mixture models. The mean stutter ratio in each model is modeled as a locus specific simple linear regression against a feature of the alleles under study known as the longest uninterrupted sequence (LUS). The use of AIC, BIC, DIC, and WAIC in model comparison has some practical limitations. Even though, IS-LOO, TIS-LOO, and PSIS-LOO are considered to be approximations of the exact LOO-CV, the study observed some drastic deviations in the results. However, there are some interesting relationships among the logarithms of pointwise predictive densities (lppd) calculated under WAIC and the LOO approximation methods. The estimated overall lppd is a relative measure that reflects the overall goodness-of-fit of the model. Parallel log-likelihood profiles for the models conditional on equal posterior variances in lppds were observed. This study illustrates the limitations of the information criteria in practical model comparison problems. In addition, the relationships among LOO-CV approximation methods and WAIC with their limitations are discussed. Finally, useful recommendations that may help in practical model comparisons with these methods are provided.

Keywords: cross-validation, importance sampling, information criteria, predictive accuracy

Procedia PDF Downloads 393

Authors: Natalia C. E. S. Nascimento, Mercia L. Oliveira, Fernando R. A. Lima, Leonardo T. C. do Nascimento, Marina B. Silveira, Brigida G. A. Schirmer, Andrea V. Ferreira, Carlos Malamut, Juliana B. da Silva

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Tissue hypoxia is a common characteristic of solid tumors leading to decreased sensitivity to radiotherapy and chemotherapy. In the clinical context, tumor hypoxia assessment employing the positron emission tomography (PET) tracer ¹⁸F-fluoromisonidazole ([¹⁸F]FMISO) is helpful for physicians for planning and therapy adjusting. The aim of this work was to implement the synthesis of 18F-FMISO in a TRACERlab® MXFDG module and also to establish the quality control procedure. [¹⁸F]FMISO was synthesized at Centro de Desenvolvimento da Tecnologia Nuclear (CDTN/CNEN/Brazil) using an automated synthesizer (TRACERlab® MXFDG, GE) adapted for the production of [¹⁸F]FMISO. The FMISO chemical standard was purchased from ABX. 18O- enriched water was acquired from Center of Molecular Research. Reagent kits containing eluent solution, acetonitrile, ethanol, 2.0 M HCl solution, buffer solution, water for injections and [¹⁸F]FMISO precursor (dissolved in 2 ml acetonitrile) were purchased from ABX. The [¹⁸F]FMISO samples were purified by Solid Phase Extraction method. The quality requirements of [¹⁸F]FMISO are established in the European Pharmacopeia. According to that reference, quality control of [¹⁸F]FMISO should include appearance, pH, radionuclidic identity and purity, radiochemical identity and purity, chemical purity, residual solvents, bacterial endotoxins, and sterility. The duration of the synthesis process was 53 min, with radiochemical yield of (37.00 ± 0.01) % and the specific activity was more than 70 GBq/µmol. The syntheses were reproducible and showed satisfactory results. In relation to the quality control analysis, the samples were clear and colorless at pH 6.0. The spectrum emission, measured by using a High-Purity Germanium Detector (HPGe), presented a single peak at 511 keV and the half-life, determined by the decay method in an activimeter, was (111.0 ± 0.5) min, indicating no presence of radioactive contaminants, besides the desirable radionuclide (¹⁸F). The samples showed concentration of tetrabutylammonium (TBA) < 50μg/mL, assessed by visual comparison to TBA standard applied in the same thin layer chromatographic plate. Radiochemical purity was determined by high performance liquid chromatography (HPLC) and the results were 100%. Regarding the residual solvents tested, ethanol and acetonitrile presented concentration lower than 10% and 0.04%, respectively. Healthy female mice were injected via lateral tail vein with [¹⁸F]FMISO, microPET imaging studies (15 min) were performed after 2 h post injection (p.i), and the biodistribution was analyzed in five-time points (30, 60, 90, 120 and 180 min) after injection. Subsequently, organs/tissues were assayed for radioactivity with a gamma counter. All parameters of quality control test were in agreement to quality criteria confirming that [¹⁸F]FMISO was suitable for use in non-clinical and clinical trials, following the legal requirements for the production of new radiopharmaceuticals in Brazil.

Keywords: automatic radiosynthesis, hypoxic tumors, pharmacopeia, positron emitters, quality requirements

Procedia PDF Downloads 194

Authors: Fernando Martinez Soto, Gaetano Di Mino

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The application of rubber into bituminous mixtures requires attention and care during mixing and compaction. Rubber modifies the properties because it reacts in the internal structure of bitumen at high temperatures changing the performance of the mixture (interaction process of solvents with binder-rubber aggregate). The main change is the increasing of the viscosity and elasticity of the binder due to the larger sizes of the rubber particles by dry process but, this positive effect is counteracted by short mixing times, compared to wet technology, and due to the transport processes, curing time and post-compaction of the mixtures. Therefore, negative effects as swelling of rubber particles, rebounding effect of the specimens and thermal changes by different expansion of the structure inside the mixtures, can change the mechanical properties of the rubberized blends. Based on the dry technology, different asphalt-rubber binders using devulcanized or natural rubber (truck and bus tread rubber), have served to demonstrate these effects and how to solve them into two dense-gap graded rubber modified asphalt concrete mixes (RUMAC) to enhance the stability, workability and durability of the compacted samples by Superpave gyratory compactor method. This paper specifies the procedures developed in the Department of Civil Engineering of the University of Palermo during September 2016 to March 2017, for characterizing the post-compaction and mix-stability of the one conventional mixture (hot mix asphalt without rubber) and two gap-graded rubberized asphalt mixes according granulometry for rail sub-ballast layers with nominal size of Ø22.4mm of aggregates according European standard. Thus, the main purpose of this laboratory research is the application of ambient ground rubber from scrap tires processed at conventional temperature (20ºC) inside hot bituminous mixtures (160-220ºC) as a substitute for 1.5%, 2% and 3% by weight of the total aggregates (3.2%, 4.2% and, 6.2% respectively by volumetric part of the limestone aggregates of bulk density equal to 2.81g/cm³) considered, not as a part of the asphalt binder. The reference bituminous mixture was designed with 4% of binder and ± 3% of air voids, manufactured for a conventional bitumen B50/70 at 160ºC-145ºC mix-compaction temperatures to guarantee the workability of the mixes. The proportions of rubber proposed are #60-40% for mixtures with 1.5 to 2% of rubber and, #20-80% for mixture with 3% of rubber (as example, a 60% of Ø0.4-2mm and 40% of Ø2-4mm). The temperature of the asphalt cement is between 160-180 ºC for mixing and 145-160 ºC for compaction, according to the optimal values for viscosity using Brookfield viscometer and 'ring and ball' - penetration tests. These crumb rubber particles act as a rubber-aggregate into the mixture, varying sizes between 0.4mm to 2mm in a first fraction, and 2-4mm as second proportion. Ambient ground rubber with a specific gravity of 1.154g/cm³ is used. The rubber is free of loose fabric, wire, and other contaminants. It was found optimal results in real beams and cylindrical specimens with each HMA mixture reducing the swelling effect. Different factors as temperature, particle sizes of rubber, number of cycles and pressures of compaction that affect the interaction process are explained.

Keywords: crumb-rubber, gyratory compactor, rebounding effect, superpave mix-design, swelling, sub-ballast railway

Procedia PDF Downloads 244

Authors: Eduardo Rodrigues, Gisela Mendes, José M. Torres, José E. Sousa

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In the sequence of the liberalisation of the electricity sector a progressive engagement of consumers has been considered and targeted by sector regulatory policies. With the objective of promoting market competition while protecting consumers interests, by transferring some of the upstream benefits to the end users while reaching a fair distribution of system costs, different market models to value consumers’ demand flexibility at the energy community level are envisioned. Local Energy and Flexibility Markets (LEFM) involve stakeholders interested in providing or procure local flexibility for community, services and markets’ value. Under the scope of DOMINOES, a European research project supported by Horizon 2020, the local market concept developed is expected to: • Enable consumers/prosumers empowerment, by allowing them to value their demand flexibility and Distributed Energy Resources (DER); • Value local liquid flexibility to support innovative distribution grid management, e.g., local balancing and congestion management, voltage control and grid restoration; • Ease the wholesale market uptake of DER, namely small-scale flexible loads aggregation as Virtual Power Plants (VPPs), facilitating Demand Response (DR) service provision; • Optimise the management and local sharing of Renewable Energy Sources (RES) in Medium Voltage (MV) and Low Voltage (LV) grids, trough energy transactions within an energy community; • Enhance the development of energy markets through innovative business models, compatible with ongoing policy developments, that promote the easy access of retailers and other service providers to the local markets, allowing them to take advantage of communities’ flexibility to optimise their portfolio and subsequently their participation in external markets. The general concept proposed foresees a flow of market actions, technical validations, subsequent deliveries of energy and/or flexibility and balance settlements. Since the market operation should be dynamic and capable of addressing different requests, either prioritising balancing and prosumer services or system’s operation, direct procurement of flexibility within the local market must also be considered. This paper aims to highlight the research on the definition of suitable DR models to be used by the Distribution System Operator (DSO), in case of technical needs, and by the retailer, mainly for portfolio optimisation and solve unbalances. The models to be proposed and implemented within relevant smart distribution grid and microgrid validation environments, are focused on day-ahead and intraday operation scenarios, for predictive management and near-real-time control respectively under the DSO’s perspective. At local level, the DSO will be able to procure flexibility in advance to tackle different grid constrains (e.g., demand peaks, forecasted voltage and current problems and maintenance works), or during the operating day-to-day, to answer unpredictable constraints (e.g., outages, frequency deviations and voltage problems). Due to the inherent risks of their active market participation retailers may resort to DR models to manage their portfolio, by optimising their market actions and solve unbalances. The interaction among the market actors involved in the DR activation and in flexibility exchange is explained by a set of sequence diagrams for the DR modes of use from the DSO and the energy provider perspectives. • DR for DSO’s predictive management – before the operating day; • DR for DSO’s real-time control – during the operating day; • DR for retailer’s day-ahead operation; • DR for retailer’s intraday operation.

Keywords: demand response, energy communities, flexible demand, local energy and flexibility markets

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Authors: Juliana A. B. Silva, Caio H. T. L. Albuquerque, Leonardo L. dos Santos, Cristiane K. Oliveira, Ivani Malvestiti, Fernando Hallwass, Ricardo L. Longo

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Complexes with lanthanide ions have been extensively studied due to their applications as luminescent, magnetic and catalytic materials as molecular or extended crystals, thin films, glasses, polymeric matrices, ionic liquids, and in solution. NMR chemical shift data in solution have been reported and suggest fluxional structures in a wide range of coordination compounds with rare earth ions. However, the fluxional mechanisms for these compounds are still not established. This structural fluxionality may affect the photophysical, catalytic and magnetic properties in solution. Thus, understanding the structural interconversion mechanisms may aid the design of coordination compounds with, for instance, improved (electro)luminescence, catalytic and magnetic behaviors. The [Eu(btfa)₃bipy] complex, where btfa= 4,4,4-trifluoro-1-phenyl-1,3-butanedionate and bipy= 2,2’-bipiridyl, has a well-defined X-ray crystallographic structure and preliminary 1H NMR data suggested a structural fluxionality. Thus, we have investigated a series of coordination compounds with lanthanide ions [Ln(btfa)₃L], where Ln = La, Eu, Gd or Yb and L= bipy or phen (phen=1,10-phenanthroline) using a combined theoretical-experimental approach. These complexes were synthesized and fully characterized, and detailed NMR measurements were obtained. They were also studied by quantum chemical computational methods (DFT-PBE0). The aim was to determine the relevant factors in the structure of these compounds that favor or not the fluxional behavior. Measurements of the 1H NMR signals at variable temperature in CD₂Cl₂ of the [Eu(btfa)₃L] complexes suggest that these compounds have a fluxional structure, because the crystal structure has non-equivalent btfa ligands that should lead to non-equivalent hydrogen atoms and thus to more signals in the NMR spectra than those obtained at room temperature, where all hydrogen atoms of the btfa ligands are equivalent, and phen ligand has an effective vertical symmetry plane. For the [Eu(btfa)₃bipy] complex, the broadening of the signals at –70°C provides a lower bound for the coalescence temperature, which indicates the energy barriers involved in the structural interconversion mechanisms are quite small. These barriers and, consequently, the coalescence temperature are dependent upon the radii of the lanthanide ion as well as to their paramagnetic effects. The PBE0 calculated structures are in very good agreement with the crystallographic data and, for the [Eu(btfa)₃bipy] complex, this method provided several distinct structures with almost the same energy. However, the energy barrier for structural interconversion via dissociative pathways were found to be quite high and could not explain the experimental observations. Whereas the pseudo-rotation pathways, involving the btfa and bipy ligands, have very small activation barriers, in excellent agreement with the NMR data. The results also showed an increase in the activation barrier along the lanthanide series due to the decrease of the ionic radii and consequent increase of the steric effects. TD-DFT calculations showed a dependence of the ligand donor state energy with different structures of the complex [Eu(btfa)₃phen], which can affect the energy transfer rates and the luminescence. The energy required to promote the structural fluxionality may also enhance the luminescence quenching in solution. These results can aid in the design of more luminescent compounds and more efficient devices.

Keywords: computational chemistry, lanthanide-based compounds, NMR, structural fluxionality

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