Search results for: Pedro Gomes
122 The Romero-System Clarinet: A Milestone in the 19th Century Clarinet Manufacture
Authors: Pedro Rubio
Abstract:
Antonio Romero y Andía, was one of the most active and interesting figures in 19th century Spanish music. He was not only an exceptional clarinetist, he was also a publisher, a brilliant oboist, a music critic, and he revitalized Madrid’s musical scene by promoting orchestras and a national opera. In 1849, Romero was appointed Professor of Clarinet at the Conservatory of Madrid. Shortly after, Romero introduced to Spain the Boehm-System clarinet recently appeared in France. However, when initial interest in that system waned, he conceived his own system in 1853. The clarinet was manufactured in Paris by Lefêvre, who registered its first patent in 1862. In 1867 a second version was patented, and a year earlier, in 1866, the Romero clarinet was adopted as an official instrument for teaching the clarinet at the Conservatory of Madrid. The Romero-System clarinet mechanism has incorporated numerous additional devices and several extra keys, its skillful combination in a single instrument represents not only one of the pinnacles in the manufacture of musical instruments of the 19th century, but also an authentic synthesis of knowledge and practice in an era in which woodwind instruments were shaped as we know them today. Through the description and analysis of the data related to the aforementioned historical period, this lecture will try to show a crucial time in the history of all woodwind instruments, a period of technological effervescence in which the Romero-System clarinet emerged. The different stages of conception of the clarinet will be described, as well as its manufacturing and marketing process. Romero played with his clarinet system over twenty-five years. The research has identified the repertoire associated with this instrument whose conclusions will be presented in its case in the Congress.Keywords: Antonio Romero, clarinet, keywork, 19th century
Procedia PDF Downloads 126121 Utility of Optical Coherence Tomography (OCT) and Visual Field Assessment in Neurosurgical Patients
Authors: Ana Ferreira, Ines Costa, Patricia Polónia, Josué Pereira, Olinda Faria, Pedro Alberto Silva
Abstract:
Introduction: Optical coherence tomography (OCT) and visual field tools are pivotal in evaluating neurological deficits and predicting potential visual improvement following surgical decompression in neurosurgical patients. Despite their clinical significance, a comprehensive understanding of their utility in this context is lacking in the literature. This study aims to elucidate the applications of OCT and visual field assessment, delineating distinct patterns of visual deficit presentations within the studied cohort. Methods: This retrospective analysis considered all adult patients who underwent a single surgery for pituitary adenoma or anterior skull base meningioma with optic nerve involvement, coupled with neuro-ophthalmology evaluation, between July 2020 and January 2023. A minimum follow-up period of 6 months was deemed essential. Results: A total of 24 patients, with a median age of 61, were included in the analysis. Three primary patterns emerged: 1) Low visual field involvement with compromised OCT, 2) High visual field involvement with relatively unaffected OCT, and 3) Significant compromise observed in both OCT and visual fields. Conclusion: This study delineates various findings in OCT and visual field assessments with illustrative examples. Based on the current findings, a prospective cohort will be systematically collected to further investigate and validate these patterns and their prognostic significance, enhancing our understanding of the utility of OCT and visual fields in neurosurgical patients.Keywords: OCT, neurosurgery, visual field, optic nerve
Procedia PDF Downloads 78120 Current Status and Future Trends of Mechanized Fruit Thinning Devices and Sensor Technology
Authors: Marco Lopes, Pedro D. Gaspar, Maria P. Simões
Abstract:
This paper reviews the different concepts that have been investigated concerning the mechanization of fruit thinning as well as multiple working principles and solutions that have been developed for feature extraction of horticultural products, both in the field and industrial environments. The research should be committed towards selective methods, which inevitably need to incorporate some kinds of sensor technology. Computer vision often comes out as an obvious solution for unstructured detection problems, although leaves despite the chosen point of view frequently occlude fruits. Further research on non-traditional sensors that are capable of object differentiation is needed. Ultrasonic and Near Infrared (NIR) technologies have been investigated for applications related to horticultural produce and show a potential to satisfy this need while simultaneously providing spatial information as time of flight sensors. Light Detection and Ranging (LIDAR) technology also shows a huge potential but it implies much greater costs and the related equipment is usually much larger, making it less suitable for portable devices, which may serve a purpose on smaller unstructured orchards. Portable devices may serve a purpose on these types of orchards. In what concerns sensor methods, on-tree fruit detection, major challenge is to overcome the problem of fruits’ occlusion by leaves and branches. Hence, nontraditional sensors capable of providing some type of differentiation should be investigated.Keywords: fruit thinning, horticultural field, portable devices, sensor technologies
Procedia PDF Downloads 139119 Pellegrini-Stieda Syndrome: A Physical Medicine and Rehabilitation Approach
Authors: Pedro Ferraz-Gameiro
Abstract:
Introduction: The Pellegrini-Stieda lesion is the result of post-traumatic calcification and/or ossification on the medial collateral ligament (MCL) of the knee. When this calcification is accompanied by gonalgia and limitation of knee flexion, it is called Pellegrini-Stieda syndrome. The pathogenesis is probably the calcification of a post-traumatic hematoma at least three weeks after the initial trauma or secondary to repetitive microtrauma. On anteroposterior radiographs, a Pellegrini-Stieda lesion is a linear vertical ossification or calcification of the proximal portion of the MCL and usually near the medial femoral condyle. Patients with Pellegrini-Stieda syndrome present knee pain associated with loss of range of motion. The treatment is usually conservative with analgesic and anti-inflammatory drugs, either systemic or intra-articular. Physical medicine and rehabilitation techniques associated with shock wave therapy can be a way of reduction of pain/inflammation. Patients who maintain instability with significant limitation of knee mobility may require surgical excision. Methods: Research was done using PubMed central using the terms Pellegrini-Stieda syndrome. Discussion/conclusion: Medical treatment is the rule, with initial rest, anti-inflammatory, and physiotherapy. If left untreated, this ossification can potentially form a significant bone mass, which can compromise the range of motion of the knee. Physical medicine and rehabilitation techniques associated with shock wave therapy are a way of reduction of pain/inflammation.Keywords: knee, Pellegrini-Stieda syndrome, rehabilitation, shock waves therapy
Procedia PDF Downloads 140118 Improving Trainings of Mineral Processing Operators Through Gamification and Modelling and Simulation
Authors: Pedro A. S. Bergamo, Emilia S. Streng, Jan Rosenkranz, Yousef Ghorbani
Abstract:
Within the often-hazardous mineral industry, simulation training has speedily gained appreciation as an important method of increasing site safety and productivity through enhanced operator skill and knowledge. Performance calculations related to froth flotation, one of the most important concentration methods, is probably the hardest topic taught during the training of plant operators. Currently, most training teach those skills by traditional methods like slide presentations and hand-written exercises with a heavy focus on memorization. To optimize certain aspects of these pieces of training, we developed “MinFloat”, which teaches the operation formulas of the froth flotation process with the help of gamification. The simulation core based on a first-principles flotation model was implemented in Unity3D and an instructor tutoring system was developed, which presents didactic content and reviews the selected answers. The game was tested by 25 professionals with extensive experience in the mining industry based on a questionnaire formulated for training evaluations. According to their feedback, the game scored well in terms of quality, didactic efficacy and inspiring character. The feedback of the testers on the main target audience and the outlook of the mentioned solution is presented. This paper aims to provide technical background on the construction of educational games for the mining industry besides showing how feedback from experts can more efficiently be gathered thanks to new technologies such as online forms.Keywords: training evaluation, simulation based training, modelling, and simulation, froth flotation
Procedia PDF Downloads 113117 Investigation of Multiple Dynamic Vibration Absorbers' Performance in Overhead Transmission Lines
Authors: Pedro F. D. Oliveira, Rangel S. Maia, Aline S. Paula
Abstract:
As the electric energy consumption grows, the necessity of energy transmission lines increases. One of the problems caused by an oscillatory response to dynamical loads (such as wind effects) in transmission lines is the cable fatigue. Thus, the dynamical behavior of transmission cables understanding and its control is extremely important. The socioeconomic damage caused by a failure in these cables can be quite significant, from large economic losses to energy supply interruption in large regions. Dynamic Vibration Absorbers (DVA) are oscillatory elements used to mitigate the vibration of a primary system subjected to harmonic excitation. The positioning of Stockbridge (DVA for overhead transmission lines) plays an important role in mitigating oscillations of transmission lines caused by airflows. Nowadays, the positioning is defined by technical standards or commercial software. The aim of this paper is to conduct an analysis of multiple DVAs performances in cable conductors of overhead transmission lines. The cable is analyzed by a finite element method and the model is calibrated by experimental results. DVAs performance is analyzed by evaluating total cable energy, and a study of multiple DVAs positioning is conducted. The results are compared to the existing regulations showing situations where proper positioning, different from the standard, can lead to better performance of the DVA. Results also show situations where the use of multiple DVAs is appropriate.Keywords: dynamical vibration absorber, finite element method, overhead transmission lines, structural dynamics
Procedia PDF Downloads 127116 Crossing Narrative Waters in World Cinema: Alamar (2009) and Kaili Blues (2015)
Authors: Dustin Dill
Abstract:
The physical movement of crossing over water points to both developing narrative tropes and innovative cinematography in World Cinema today. Two prime examples, Alamar (2009) by Pedro González-Rubio and Kaili Blues (2015) by Bi Gan, demonstrate how contemporary storytelling in a film not only rests upon these water shots but also emerges from them. The range of symbolism that these episodes in the story provoke goes hand in hand with the diverse filming sequences found in the respective productions. While González-Rubio decides to cut the scene into long and longer shots, Gan uses a single take. The differing angles depict equally unique directors and film projects: Alamar runs parallel to many definitions of the essay film, and Kaili Blues resonates much more with mystery and art film. Nonetheless, the crossing of water scenes influence the narratives’ subjects despite the generic consequences, and it is within the essay, mystery, and art film genres which allows for a better understanding of World Cinema. Tiago de Luca explains World Cinema’s prerogative of giving form to a certain type of spectator does not always line up. Given the immense number of interpretations of crossing water —the escape from suffering to find nirvana, rebirth, and colonization— underline the difficulty of categorizing it. If before this type of cross-genre was a trait that defined World Cinema in its beginning, this study observes that González-Rubio and Gan question the all-encompassing genre with their experimental shots of a universal narrative trope, the crossing of water.Keywords: cinematography, genre, narrative, world cinema
Procedia PDF Downloads 292115 Performance Study of Experimental Ferritic Alloy with High Content of Molybdenum in Corrosive Environment of Soybean Methyl Biodiesel
Authors: Maurício N. Kleinberg, Ana P. R. N. Barroso, Frederico R. Silva, Natasha l. Gomes, Rodrigo F. Guimarães, Marcelo M. V. Parente, Jackson Q. Malveira
Abstract:
Increased production of biofuels, especially biodiesel, as an option to replace the diesel derived from oil is already a reality in countries seeking a renewable and environmentally friendly fuel, as is the case in Brazil. However, it is known that the use of fuels, renewable or not, implies that it is in contact with various metallic materials which may cause corrosion. In the search for more corrosion resistant materials has been experimentally observed that the addition of molybdenum in ferritic steels increases their protective character without significantly burdening the cost of production. In order to evaluate the effect of adding molybdenum, samples of commercial steel (austenitic, ferritic and carbon steel) and the experimental ferritic alloy with a high molybdenum content (5.3%) were immersed separately into biodiesel derived from transesterification of soy oil to monitor the corrosion process of these metal samples, and in parallel to analyze the oxidative degradation of biodiesel itself. During the immersion time of 258 days, biodiesel samples were taken for analysis of acidity, kinematic viscosity, density and refraction. Likewise, the metal samples were taken from the biodiesel to be weighed and microstructurally analyzed by light microscopy. The results obtained at the end of 258 days shown that biodiesel presented a considerable increase on the values of the studied parameters for all the samples. However, this increase was not able to produce significant mass loss in metallic samples. As regards the microstructural analysis, it showed the onset of surface oxidation on the carbon steel sample. As for the other samples, no significant surface changes were shown. These results are consistent with literature for short immersion times. It is concluded that the increase in the values of the studied parameters is not significant yet, probably due to the low time of immersion and exposure of the samples. Thus, it is necessary to continue the tests so that the objectives of this work are achieved.Keywords: biodiesel, corrosion, immersion, experimental alloy
Procedia PDF Downloads 439114 Co-payment Strategies for Chronic Medications: A Qualitative and Comparative Analysis at European Level
Authors: Pedro M. Abreu, Bruno R. Mendes
Abstract:
The management of pharmacotherapy and the process of dispensing medicines is becoming critical in clinical pharmacy due to the increase of incidence and prevalence of chronic diseases, the complexity and customization of therapeutic regimens, the introduction of innovative and more expensive medicines, the unbalanced relation between expenditure and revenue as well as due to the lack of rationalization associated with medication use. For these reasons, co-payments emerged in Europe in the 70s and have been applied over the past few years in healthcare. Co-payments lead to a rationing and rationalization of user’s access under healthcare services and products, and simultaneously, to a qualification and improvement of the services and products for the end-user. This analysis, under hospital practices particularly and co-payment strategies in general, was carried out on all the European regions and identified four reference countries, that apply repeatedly this tool and with different approaches. The structure, content and adaptation of European co-payments were analyzed through 7 qualitative attributes and 19 performance indicators, and the results expressed in a scorecard, allowing to conclude that the German models (total score of 68,2% and 63,6% in both elected co-payments) can collect more compliance and effectiveness, the English models (total score of 50%) can be more accessible, and the French models (total score of 50%) can be more adequate to the socio-economic and legal framework. Other European models did not show the same quality and/or performance, so were not taken as a standard in the future design of co-payments strategies. In this sense, we can see in the co-payments a strategy not only to moderate the consumption of healthcare products and services, but especially to improve them, as well as a strategy to increment the value that the end-user assigns to these services and products, such as medicines.Keywords: clinical pharmacy, co-payments, healthcare, medicines
Procedia PDF Downloads 251113 Using Deep Learning for the Detection of Faulty RJ45 Connectors on a Radio Base Station
Authors: Djamel Fawzi Hadj Sadok, Marrone Silvério Melo Dantas Pedro Henrique Dreyer, Gabriel Fonseca Reis de Souza, Daniel Bezerra, Ricardo Souza, Silvia Lins, Judith Kelner
Abstract:
A radio base station (RBS), part of the radio access network, is a particular type of equipment that supports the connection between a wide range of cellular user devices and an operator network access infrastructure. Nowadays, most of the RBS maintenance is carried out manually, resulting in a time consuming and costly task. A suitable candidate for RBS maintenance automation is repairing faulty links between devices caused by missing or unplugged connectors. A suitable candidate for RBS maintenance automation is repairing faulty links between devices caused by missing or unplugged connectors. This paper proposes and compares two deep learning solutions to identify attached RJ45 connectors on network ports. We named connector detection, the solution based on object detection, and connector classification, the one based on object classification. With the connector detection, we get an accuracy of 0:934, mean average precision 0:903. Connector classification, get a maximum accuracy of 0:981 and an AUC of 0:989. Although connector detection was outperformed in this study, this should not be viewed as an overall result as connector detection is more flexible for scenarios where there is no precise information about the environment and the possible devices. At the same time, the connector classification requires that information to be well-defined.Keywords: radio base station, maintenance, classification, detection, deep learning, automation
Procedia PDF Downloads 201112 Fast Return Path Planning for Agricultural Autonomous Terrestrial Robot in a Known Field
Authors: Carlo Cernicchiaro, Pedro D. Gaspar, Martim L. Aguiar
Abstract:
The agricultural sector is becoming more critical than ever in view of the expected overpopulation of the Earth. The introduction of robotic solutions in this field is an increasingly researched topic to make the most of the Earth's resources, thus going to avoid the problems of wear and tear of the human body due to the harsh agricultural work, and open the possibility of a constant careful processing 24 hours a day. This project is realized for a terrestrial autonomous robot aimed to navigate in an orchard collecting fallen peaches below the trees. When it receives the signal indicating the low battery, it has to return to the docking station where it will replace its battery and then return to the last work point and resume its routine. Considering a preset path in orchards with tree rows with variable length by which the robot goes iteratively using the algorithm D*. In case of low battery, the D* algorithm is still used to determine the fastest return path to the docking station as well as to come back from the docking station to the last work point. MATLAB simulations were performed to analyze the flexibility and adaptability of the developed algorithm. The simulation results show an enormous potential for adaptability, particularly in view of the irregularity of orchard field, since it is not flat and undergoes modifications over time from fallen branch as well as from other obstacles and constraints. The D* algorithm determines the best route in spite of the irregularity of the terrain. Moreover, in this work, it will be shown a possible solution to improve the initial points tracking and reduce time between movements.Keywords: path planning, fastest return path, agricultural autonomous terrestrial robot, docking station
Procedia PDF Downloads 134111 The Relation between Sports Practice and the Academic Performance
Authors: Albert Perez-Bellmunt, Eila Rivera, Aida Valls, Berta Estragues, Sara Ortiz, Roberto Seijas, Pedro Alvarez
Abstract:
INTRODUCTION: Physical and sports activity on a regular basis present numerous health benefits such as the prevention of cardiovascular and metabolic diseases. Also, there is a relation between sport and the psychological or the cognitive process of children and young people. The objective of the present study is to know if the sports practice has any positive influence on the university academic performance. MATERIALS AND METHODS: The level of the physical activity of 220 students of different degrees in health science was evaluated and compared with the academic results (grades). To assess the level of physical and sports activity, the Global Physical Activity Questionnaire (to calculate the sporting level in a general way) and the International Physical Activity Questionnaire (to estimate the physical activity carried out during the days leading up to the academic exams) were used. RESULTS: The students that realized an average level of sports activity the days before the exam obtained better grades than the rest of their classmate and the result was statistically significant. Controversially, if the sports level was analyzed in a general way, no relationship was observed between academic performance and the level of sport realized. CONCLUSION: A moderate physical activity, on the days leading up to an assessment, can be a positive factor for the university academic performance. Despite the fact that a regular sports activity improves many cognitive and physiological processes, the present study did not observe a direct relationship between sport/physical activity and academic performance.Keywords: academic performance, academic results, global physical activity questionnaire, physical activity questionnaire, sport, sport practice
Procedia PDF Downloads 189110 Competition Law as a “Must Have” Course in Legal Education
Authors: Noemia Bessa Vilela, Jose Caramelo Gomes
Abstract:
All law student are familiarized, in the first years of their bachelor of laws with the concepts of “public goods” and “ private goods”; often, such legal concept does not exactly match such economic concept, and there are consequences are some sort of confusion being created. The list of goods that follow under each category is not exhaustive, nor are students given proper mechanisms to acknowledge that some legal fields can, on its own, be considered as a “public good”; this is the case of Competition. Legal authors consider that “competition law is used to promote public interest” and, as such, it is a “public good”; in economics theory, Competition is the first public good in a market economy, as the enabler of allocation efficiency. Competition law is the legal tool to support the proper functioning of the market economy and democracy itself. It is fact that Competition Law only applies to economic activities, still, competition is object of private litigation as an integral part of Public Law. Still, regardless of the importance of Competition Law in the economic activity and market regulation, most student complete their studies in law, join the Bar Associations and engage in their professional activities never having been given sufficient tools to deal with the increasing demands of a globalized world. The lack of knowledge of economics, market functioning and the mechanisms at their reach in order to ensure proper realization of their duties as lawyers/ attorneys-at-law would be tackled if Competition Law would be included as part of the curricula of Law Schools. Proper teaching of Competition Law would combine the foundations of Competition Law, doctrine, case solving and Case Law study. Students should to understand and apply the analytical model. Special emphasis should be given to EU Competition Law, namely the TFEU Articles 101 to 106. Damages Directive should also be part of the curriculum. Students must in the first place acquire and master the economic rationale as competition and the world of competition law are the cornerstone of sound and efficient market. The teaching of Competition Law in undergraduate programs in Law would contribute to fulfill the potential of the students who will deal with matters related to consumer protection, economic and commercial law issues both in private practice and as in-house lawyers for companies.Keywords: higher education, competition law, legal education, law, market economy, industrial economics
Procedia PDF Downloads 142109 Methodological Proposal, Archival Thesaurus in Colombian Sign Language
Authors: Pedro A. Medina-Rios, Marly Yolie Quintana-Daza
Abstract:
Having the opportunity to communicate in a social, academic and work context is very relevant for any individual and more for a deaf person when oral language is not their natural language, and written language is their second language. Currently, in Colombia, there is not a specialized dictionary for our best knowledge in sign language archiving. Archival is one of the areas that the deaf community has a greater chance of performing. Nourishing new signs in dictionaries for deaf people extends the possibility that they have the appropriate signs to communicate and improve their performance. The aim of this work was to illustrate the importance of designing pedagogical and technological strategies of knowledge management, for the academic inclusion of deaf people through proposals of lexicon in Colombian sign language (LSC) in the area of archival. As a method, the analytical study was used to identify relevant words in the technical area of the archival and its counterpart with the LSC, 30 deaf people, apprentices - students of the Servicio Nacional de Aprendizaje (SENA) in Documentary or Archival Management programs, were evaluated through direct interviews in LSC. For the analysis tools were maintained to evaluate correlation patterns and linguistic methods of visual, gestural analysis and corpus; besides, methods of linear regression were used. Among the results, significant data were found among the variables socioeconomic stratum, academic level, labor location. The need to generate new signals on the subject of the file to improve communication between the deaf person, listener and the sign language interpreter. It is concluded that the generation of new signs to nourish the LSC dictionary in archival subjects is necessary to improve the labor inclusion of deaf people in Colombia.Keywords: archival, inclusion, deaf, thesaurus
Procedia PDF Downloads 278108 The Use of Microalgae Cultivation for Improving the Effluent Behavior of Anaerobic Digestion of Food Wastes at Psychrophilic Range
Authors: Pedro M. Velasco, Cecilia C. Alday, Oscar C. Avello, Ximena T. Faundez, Luis M. Velasco
Abstract:
Anaerobic digestion (AD) plants of food waste (FW) produced by agro-industry, have been widely developed from last decade to nowadays, because of the advantages over aerobic active sludge systems. Despite several bioreactor configurations and operation modes have been successfully improved and implemented at industrial scale in a wide range of applications, effluent behavior, after AD, does not commonly meet requirements for direct disposal into the environment without further treatments. In addition, literature has rarely shown AD of food waste at psychrophilic range. This temperature range may be of interest for making AD plant operation easier and increasing the stability of digestion. In spite of literature shows several methods for post-treatment, such as the use of microalgae, these have not been cultivated on effluents from AD at psychrophilic range. Hence, with the aim of showing the potential use of AD of FW at the psychrophilic range (25ºC) and the viability of microalgae post-treatment, single batch reactors have been used for methane potential tests at laboratory scale. Afterwards, digestates, derived from this AD of FW sludge, were diluted with fresh water at different ratios (1:0, 1:1; 1:4) and used as culture media for photoautotrophic microalgae. Several parameters, such as pH, biogas production, and chemical oxygen demand, were measured periodically over several months. Results show that methane potential is 150 ml g-1 per volatile solid with up to 57.7 % of methane content. Moreover, microalgae has been successfully cultivated on all tested effluents and in case of 1:1 and 1:4 rates, the resulting effluents meet the quality levels required for irrigation water.Keywords: anaerobic digestion, biogas, food waste, microalgae, psychrophilic range
Procedia PDF Downloads 304107 The Effects of Transcranial Direct Current Stimulation on Brain Oxygenation and Pleasure during Exercise
Authors: Alexandre H. Okano, Pedro M. D. Agrícola, Daniel G. Da S. Machado, Luiz I. Do N. Neto, Luiz F. Farias Junior, Paulo H. D. Nascimento, Rickson C. Mesquita, John F. Araujo, Eduardo B. Fontes, Hassan M. Elsangedy, Shinsuke Shimojo, Li M. Li
Abstract:
The prefrontal cortex is involved in the reward system and the insular cortex integrates the afferent inputs arriving from the body’ systems and turns into feelings. Therefore, modulating neuronal activity in these regions may change individuals’ perception in a given situation such as exercise. We tested whether transcranial direct current stimulation (tDCS) change cerebral oxygenation and pleasure during exercise. Fourteen volunteer healthy adult men were assessed into five different sessions. First, subjects underwent to a maximum incremental test on a cycle ergometer. Then, subjects were randomly assigned to a transcranial direct current stimulation (2mA for 15 min) intervention in a cross over design in four different conditions: anode and cathode electrodes on T3 and Fp2 targeting the insular cortex, and Fpz and F4 targeting prefrontal cortex, respectively; and their respective sham. These sessions were followed by 30 min of moderate intensity exercise. Brain oxygenation was measured in prefrontal cortex with a near infrared spectroscopy. Perceived exertion and pleasure were also measured during exercise. The asymmetry in prefrontal cortex oxygenation before the stimulation decreased only when it was applied over this region which did not occur after insular cortex or sham stimulation. Furthermore, pleasure was maintained during exercise only after prefrontal cortex stimulation (P > 0.7), while there was a decrease throughout exercise (P < 0.03) during the other conditions. We conclude that tDCS over the prefrontal cortex changes brain oxygenation in ventromedial prefrontal cortex and maintains perceived pleasure during exercise. Therefore, this technique might be used to enhance effective responses related to exercise.Keywords: affect, brain stimulation, dopamine neuromodulation, pleasure, reward, transcranial direct current stimulation
Procedia PDF Downloads 326106 Formation Flying Design Applied for an Aurora Borealis Monitoring Mission
Authors: Thais Cardoso Franco, Caio Nahuel Sousa Fagonde, Willer Gomes dos Santos
Abstract:
Aurora Borealis is an optical phenomenon composed of luminous events observed in the night skies in the polar regions resulting from disturbances in the magnetosphere due to the impact of solar wind particles with the Earth's upper atmosphere, channeled by the Earth's magnetic field, which causes atmospheric molecules to become excited and emit electromagnetic spectrum, leading to the display of lights in the sky. However, there are still different implications of this phenomenon under study: high intensity auroras are often accompanied by geomagnetic storms that cause blackouts on Earth and impair the transmission of signals from the Global Navigation Satellite Systems (GNSS). Auroras are also known to occur on other planets and exoplanets, so the activity is an indication of active space weather conditions that can aid in learning about the planetary environment. In order to improve understanding of the phenomenon, this research aims to design a satellite formation flying solution for collecting and transmitting data for monitoring aurora borealis in northern hemisphere, an approach that allows studying the event with multipoint data collection in a reduced time interval, in order to allow analysis from the beginning of the phenomenon until its decline. To this end, the ideal number of satellites, the spacing between them, as well as the ideal topology to be used will be analyzed. From an orbital study, approaches from different altitudes, eccentricities and inclinations will also be considered. Given that at large relative distances between satellites in formation, controllers tend to fail, a study on the efficiency of nonlinear adaptive control methods from the point of view of position maintenance and propellant consumption will be carried out. The main orbital perturbations considered in the simulation: non-homogeneity terrestrial, atmospheric drag, gravitational action of the Sun and the Moon, accelerations due to solar radiation pressure and relativistic effects.Keywords: formation flying, nonlinear adaptive control method, aurora borealis, adaptive SDRE method
Procedia PDF Downloads 38105 Quality of Life and Renal Biomarkers in Feline Chronic Kidney Disease
Authors: Bárbara Durão, Pedro Almeida, David Ramilo, André Meneses, Rute Canejo-Teixeira
Abstract:
The importance of quality of life (QoL) assessment in veterinary medicine is an integral part of patient care. This is especially true in cases of chronic diseases, such as chronic kidney disease (CKD), where the ever more advanced treatment options prolong the patient’s life. Whether this prolongment of life comes with an acceptable quality of life remains has been called into question. The aim of this study was to evaluate the relationship between CKD disease biomarkers and QoL in cats. Thirty-seven cats diagnosed with CKD and with no known concurrent illness were enrolled in an observational study. Through the course of several evaluations, renal biomarkers were assessed in blood and urine samples, and owners retrospectively described their cat’s quality of life using a validated instrument for this disease. Correlations between QoL scores (AWIS) and the biomarkers were assessed using Spearman’s rank test. Statistical significance was set at p-value < 0.05, and every serial sample was considered independent. Thirty-seven cats met the inclusion criteria, and all owners completed the questionnaire every time their pet was evaluated, giving a total of eighty-four questionnaires, and the average-weighted-impact-score was –0.5. Results showed there was a statistically significant correlation between the quality of life and most of 17 the studied biomarkers and confirmed that CKD has a negative impact on QoL in cats especially due to the management of the disease and secondary appetite disorders. To our knowledge, this is the attempt to assess the correlation between renal biomarkers and QoL in cats. Our results reveal a strong potential of this type of approach in clinical management, mainly in situations where it is not possible to measure biomarkers. Whilst health-related QoL is a reliable predictor of mortality and morbidity in humans; our findings can help improve the clinical practice in cats with CKD.Keywords: chronic kidney disease, biomarkers, quality of life, feline
Procedia PDF Downloads 180104 Microwave-Assisted Alginate Extraction from Portuguese Saccorhiza polyschides – Influence of Acid Pretreatment
Authors: Mário Silva, Filipa Gomes, Filipa Oliveira, Simone Morais, Cristina Delerue-Matos
Abstract:
Brown seaweeds are abundant in Portuguese coastline and represent an almost unexploited marine economic resource. One of the most common species, easily available for harvesting in the northwest coast, is Saccorhiza polyschides grows in the lowest shore and costal rocky reefs. It is almost exclusively used by local farmers as natural fertilizer, but contains a substantial amount of valuable compounds, particularly alginates, natural biopolymers of high interest for many industrial applications. Alginates are natural polysaccharides present in cell walls of brown seaweed, highly biocompatible, with particular properties that make them of high interest for the food, biotechnology, cosmetics and pharmaceutical industries. Conventional extraction processes are based on thermal treatment. They are lengthy and consume high amounts of energy and solvents. In recent years, microwave-assisted extraction (MAE) has shown enormous potential to overcome major drawbacks that outcome from conventional plant material extraction (thermal and/or solvent based) techniques, being also successfully applied to the extraction of agar, fucoidans and alginates. In the present study, acid pretreatment of brown seaweed Saccorhiza polyschides for subsequent microwave-assisted extraction (MAE) of alginate was optimized. Seaweeds were collected in Northwest Portuguese coastal waters of the Atlantic Ocean between May and August, 2014. Experimental design was used to assess the effect of temperature and acid pretreatment time in alginate extraction. Response surface methodology allowed the determination of the optimum MAE conditions: 40 mL of HCl 0.1 M per g of dried seaweed with constant stirring at 20ºC during 14h. Optimal acid pretreatment conditions have enhanced significantly MAE of alginates from Saccorhiza polyschides, thus contributing for the development of a viable, more environmental friendly alternative to conventional processes.Keywords: acid pretreatment, alginate, brown seaweed, microwave-assisted extraction, response surface methodology
Procedia PDF Downloads 381103 New Insights into Ethylene and Auxin Interplay during Tomato Ripening
Authors: Bruna Lima Gomes, Vanessa Caroline De Barros Bonato, Luciano Freschi, Eduardo Purgatto
Abstract:
Plant hormones are long known to be tightly associated with fruit development and are involved in controlling various aspects of fruit ripening. For fleshy fruits, ripening is characterized for changes in texture, color, aroma and other parameters that markedly contribute to its quality. Ethylene is one of the major players regulating the ripening-related processes, but emerging evidences suggest that auxin is also part of this dynamic control. Thus, the aim of this study was providing new insights into the auxin role during ripening and the hormonal interplay between auxin and ethylene. For that, tomato fruits (Micro-Tom) were collected at mature green stage and separated in four groups: one for indole-3-acetic acid (IAA) treatment, one for ethylene, one for a combination of IAA and ethylene, and one for control. Hormone solution was injected through the stylar apex, while mock samples were injected with buffer only. For ethylene treatments, fruits were exposed to gaseous hormone. Then, fruits were left to ripen under standard conditions and to assess ripening development, hue angle was reported as color indicator and ethylene production was measured by gas chromatography. The transcript levels of three ripening-related ethylene receptors (LeETR3, LeETR4 and LeETR6) were evaluated by RT-qPCR. Results showed that ethylene treatment induced ripening, stimulated ethylene production, accelerated color changes and induced receptor expression, as expected. Nonetheless, auxin treatment showed the opposite effect once fruits remained green for longer time than control group and ethylene perception has changed, taking account the reduced levels of receptor transcripts. Further, treatment with both hormones revealed that auxin effect in delaying ripening was predominant, even with higher levels of ethylene. Altogether, the data suggest that auxin modulates several aspects of the tomato fruit ripening modifying the ethylene perception. The knowledge about hormonal control of fruit development will help design new strategies for effective manipulation of ripening regarding fruit quality and brings a new level of complexity on fruit ripening regulation.Keywords: ethylene, auxin, fruit ripening, hormonal crosstalk
Procedia PDF Downloads 461102 Establishment of Virtual Fracture Clinic in Princess Royal Hospital Telford: Experience and Recommendations during the First 9 Months
Authors: Tahir Khaleeq, Patrick Lancaster, Keji Fakoya, Pedro Ferreira, Usman Ahmed
Abstract:
Introduction: Virtual fracture clinics (VFC) have been shown to be a safe and cost-effective way of managing outpatient referrals to the orthopaedic department. During the coronavirus pandemic there has been a push to reduce unnecessary patient contact whilst maintaining patient safety. Materials and Methods: A protocol was developed by the clinical team in collaboration with Advanced Physiotherapy Practitioners (APP) on how to manage common musculoskeletal presentations to A&E prior to COVID as part of routine service development. Patients broadly triaged into 4 categories; discharge with advice, referral to VFC, referral to face to face clinic or discussion with on call team. The first 9 months of data were analysed to assess types of injury seen and outcomes. Results: In total 2489 patients were referred to VFC from internal and external sources. 734 patients were discharged without follow-up and 182 patients were discharged for physiotherapy review. Only 3 patients required admission. Regarding follow-ups, 431 patients had a virtual follow-up while 1036 of patients required further face to face follow up. 87 patients were triaged into subspecialty clinics. 37 patients were felt to have been referred inappropriately. Discussion: BOA guidelines suggest all patients need to be reviewed within 72 hours of their orthopaedic injury. Implementation of a VFC allows this target to be achieved and at the same time reduce patient contact. Almost half the patients were discharged following VFC review, the remaining patients were appropriately followed up. This is especially relevant in the current pandemic where reducing unnecessary trips to hospital will benefit the patient as well as make the most of the resources available.Keywords: virtual fracture clinic, lockdown, trauma and orthopaedics, Covid- 19
Procedia PDF Downloads 201101 A Deep Learning Model with Greedy Layer-Wise Pretraining Approach for Optimal Syngas Production by Dry Reforming of Methane
Authors: Maryam Zarabian, Hector Guzman, Pedro Pereira-Almao, Abraham Fapojuwo
Abstract:
Dry reforming of methane (DRM) has sparked significant industrial and scientific interest not only as a viable alternative for addressing the environmental concerns of two main contributors of the greenhouse effect, i.e., carbon dioxide (CO₂) and methane (CH₄), but also produces syngas, i.e., a mixture of hydrogen (H₂) and carbon monoxide (CO) utilized by a wide range of downstream processes as a feedstock for other chemical productions. In this study, we develop an AI-enable syngas production model to tackle the problem of achieving an equivalent H₂/CO ratio [1:1] with respect to the most efficient conversion. Firstly, the unsupervised density-based spatial clustering of applications with noise (DBSAN) algorithm removes outlier data points from the original experimental dataset. Then, random forest (RF) and deep neural network (DNN) models employ the error-free dataset to predict the DRM results. DNN models inherently would not be able to obtain accurate predictions without a huge dataset. To cope with this limitation, we employ reusing pre-trained layers’ approaches such as transfer learning and greedy layer-wise pretraining. Compared to the other deep models (i.e., pure deep model and transferred deep model), the greedy layer-wise pre-trained deep model provides the most accurate prediction as well as similar accuracy to the RF model with R² values 1.00, 0.999, 0.999, 0.999, 0.999, and 0.999 for the total outlet flow, H₂/CO ratio, H₂ yield, CO yield, CH₄ conversion, and CO₂ conversion outputs, respectively.Keywords: artificial intelligence, dry reforming of methane, artificial neural network, deep learning, machine learning, transfer learning, greedy layer-wise pretraining
Procedia PDF Downloads 86100 Family Firms Performance: Examining the Impact of Digital and Technological Capabilities using Partial Least Squares Structural Equation Modeling and Necessary Condition Analysis
Authors: Pedro Mota Veiga
Abstract:
This study comprehensively evaluates the repercussions of innovation, digital advancements, and technological capabilities on the operational performance of companies across fifteen European Union countries following the initial wave of the COVID-19 pandemic. Drawing insights from longitudinal data sourced from the 2019 World Bank business surveys and subsequent 2020 World Bank COVID-19 follow-up business surveys, our extensive examination involves a diverse sample of 5763 family businesses. In exploring the relationships between these variables, we adopt a nuanced approach to assess the impact of innovation and digital and technological capabilities on performance. This analysis unfolds along two distinct perspectives: one rooted in necessity and the other insufficiency. The methodological framework employed integrates partial least squares structural equation modeling (PLS-SEM) with condition analysis (NCA), providing a robust foundation for drawing meaningful conclusions. The findings of the study underscore a positive influence on the performance of family firms stemming from both technological capabilities and digital advancements. Furthermore, it is pertinent to highlight the indirect contribution of innovation to enhanced performance, operating through its impact on digital capabilities. This research contributes valuable insights to the broader understanding of how innovation, coupled with digital and technological capabilities, can serve as pivotal factors in shaping the post-COVID-19 landscape for businesses across the European Union. The intricate analysis of family businesses, in particular adds depth to the comprehension of the dynamics at play in diverse economic contexts within the European Union.Keywords: digital capabilities, technological capabilities, family firms performance, innovation, NCA, PLS-SEM
Procedia PDF Downloads 6399 TutorBot+: Automatic Programming Assistant with Positive Feedback based on LLMs
Authors: Claudia Martínez-Araneda, Mariella Gutiérrez, Pedro Gómez, Diego Maldonado, Alejandra Segura, Christian Vidal-Castro
Abstract:
The purpose of this document is to showcase the preliminary work in developing an EduChatbot-type tool and measuring the effects of its use aimed at providing effective feedback to students in programming courses. This bot, hereinafter referred to as tutorBot+, was constructed based on chatGPT and is tasked with assisting and delivering timely positive feedback to students in the field of computer science at the Universidad Católica de Concepción. The proposed working method consists of four stages: (1) Immersion in the domain of Large Language Models (LLMs), (2) Development of the tutorBot+ prototype and integration, (3) Experiment design, and (4) Intervention. The first stage involves a literature review on the use of artificial intelligence in education and the evaluation of intelligent tutors, as well as research on types of feedback for learning and the domain of chatGPT. The second stage encompasses the development of tutorBot+, and the final stage involves a quasi-experimental study with students from the Programming and Database labs, where the learning outcome involves the development of computational thinking skills, enabling the use and measurement of the tool's effects. The preliminary results of this work are promising, as a functional chatBot prototype has been developed in both conversational and non-conversational versions integrated into an open-source online judge and programming contest platform system. There is also an exploration of the possibility of generating a custom model based on a pre-trained one tailored to the domain of programming. This includes the integration of the created tool and the design of the experiment to measure its utility.Keywords: assessment, chatGPT, learning strategies, LLMs, timely feedback
Procedia PDF Downloads 6898 A Protein-Wave Alignment Tool for Frequency Related Homologies Identification in Polypeptide Sequences
Authors: Victor Prevost, Solene Landerneau, Michel Duhamel, Joel Sternheimer, Olivier Gallet, Pedro Ferrandiz, Marwa Mokni
Abstract:
The search for homologous proteins is one of the ongoing challenges in biology and bioinformatics. Traditionally, a pair of proteins is thought to be homologous when they originate from the same ancestral protein. In such a case, their sequences share similarities, and advanced scientific research effort is spent to investigate this question. On this basis, we propose the Protein-Wave Alignment Tool (”P-WAT”) developed within the framework of the France Relance 2030 plan. Our work takes into consideration the mass-related wave aspect of protein biosynthesis, by associating specific frequencies to each amino acid according to its mass. Amino acids are then regrouped within their mass category. This way, our algorithm produces specific alignments in addition to those obtained with a common amino acid coding system. For this purpose, we develop the ”P-WAT” original algorithm, able to address large protein databases, with different attributes such as species, protein names, etc. that allow us to align user’s requests with a set of specific protein sequences. The primary intent of this algorithm is to achieve efficient alignments, in this specific conceptual frame, by minimizing execution costs and information loss. Our algorithm identifies sequence similarities by searching for matches of sub-sequences of different sizes, referred to as primers. Our algorithm relies on Boolean operations upon a dot plot matrix to identify primer amino acids common to both proteins which are likely to be part of a significant alignment of peptides. From those primers, dynamic programming-like traceback operations generate alignments and alignment scores based on an adjusted PAM250 matrix.Keywords: protein, alignment, homologous, Genodic
Procedia PDF Downloads 11397 Combined Effect of Gluten-Free Superfoods and by-Products from Ecuador to Evaluate the Functional and Sensory Properties of Breadmaking
Authors: Andrea Vasquez, Pedro Maldonado-Alvarado
Abstract:
In general, 'gluten-free' foods like breadmaking products provide functional or nutraceutical benefits for the consumer's health and increased their demand on the market. In Ecuador, there is an overproduction of superfoods, and the food by-products are undervalued. For the first time, to the author's best knowledge, gluten-free bread mixtures from quinoa and banana flour, cassava starch, lupine flour (LF), or whey protein (WP) with hydroxypropylmethylcellulose (HPMC) and transglutaminase (TG) were evaluated on their functional and sensory properties. Free amino groups and thiols, rheology, and electrophoresis SDS PAGE were performed to analyze the crosslinking of TG at different concentrations with HC or PL proteins. Dough characterization, pasting properties were evaluated, respectively, by a MIXOLAB and a rheometer with a pasting cell. The texture, porosity, and loaf volume were characterized using a texturometer, ImageJ software, and breadmaking ability, respectively. Finally, a breadmaking aptitude and sensorial bread acceptability were performed. A significant decrease in the content of free amino groups (0.16 to 0.11 and 0.46 to 0.36 mM/mg of protein) and free thiol groups (0.37 to 0.21 and 1.79 to 1.32 mM/mg protein) was observed when 1.0% and 0.5% TG were added to LF and WP, respectively. In apparent viscosity analysis, the action of TG on HC proteins changes their viscosity, while the viscosity of LF is not modified by TG. Results of electrophoresis in PL showed bands of higher molecular weight of different fragments of proteins with 1% TG. Formulation with 59.8, 39.9, 160.8, 6.0, 1.0, and 1.5% of, respectively, QF, BF, CS, LF or WP, TG, and HPMC had the best properties in dough parameters, pasting parameters (lower pasting temperature and higher peak viscosity), best crumb structure, lower crumb hardness and higher loaf volume (2.24 and 2.28 mL/g). All the loaves of bread were acceptable in baking aptitude and general acceptability.Keywords: breadmaking, gluten-free, superfoods, by-products, Ecuador
Procedia PDF Downloads 13396 National Scope Study on Resilience of Nursing Teams During the COVID-19 Pandemic: Brazilian Experience
Authors: Elucir Gir, Laelson Rochelle Milanês Sousa, Pedro Henrique Tertuliano Leoni, Carla Aparecida Arena Ventura, Ana Cristina de Oliveira e Silva, Renata Karina Reis
Abstract:
Context and significance: Resilience is a protective agent for the physical and mental well-being of nursing professionals. Team members are constantly subjected to high levels of work stress that can negatively impact care performance and users of health services. Stress levels have been exacerbated with the COVID-19 pandemic. Objective: The aim of this study was to analyze the resilience of nursing professionals in Brazil during the COVID-19 pandemic. Method: Cross-sectional study with a quantitative approach carried out with professionals from nursing teams from all regions of Brazil. Data collection took place in the first year of the pandemic between October and December 2020. Data were obtained through an online questionnaire posted on social networks. The information collected included the sociodemographic characterization of the nursing professionals and the Brief Resilient Coping Scale was applied. Student's t-test for independent samples and analysis of variance (ANOVA) were used to compare resilience scores with sociodemographic variables. Results: 8,792 nursing professionals participated in the study, 5,767 (65.6%) were nurses, 7,437 (84.6%) were female and 2,643 (30.1%) were from the Northeast region of Brazil, 5,124 (58.8% ) had low levels of resilience. The results showed a statistically significant difference between the resilience score and the variables: professional category (p<0.001); sex (p = 0.003); age range (p<0.001); region of Brazil (p<0.001); marital status (p=0.029) and providing assistance in a field hospital (p<0.001). Conclusion: Participants in this study had, in general, low levels of resilience. There is an urgent need for actions aimed at promoting the psychological health of nursing professionals inserted in pandemic contexts. Descriptors: Psychological Resilience; Nursing professionals; COVID-19; SARSCoV-2.Keywords: psychological resilience, nursing professionals, COVID-19, SARS-CoV-2
Procedia PDF Downloads 8795 Sustainable Solutions for Urban Problems: Industrial Container Housing for Endangered Communities in Maranhao, Brazil
Authors: Helida Thays Gomes Soares, Conceicao De Maria Pinheiro Correia, Fabiano Maciel Soares, Kleymer Silva
Abstract:
There is great discussion around populational increase in urban areas of the global south, and, consequently, the growth of inappropriate housing and the different ways humans have found to solve housing problems around the world. Sao Luís, the capital of the state of Maranhao is a good example. The 1.6 million inhabitant metropole is a colonial tropical city that shelters 22% of the population of Maranhão, brazilian state that still carries the scars of slavery in past centuries. In 2016, Brazilian Institute of Geography and Statistic found that 20% of Maranhão’s inhabitants were living in houses with external walls made of non-durable materials, like recycled wood, cardboard or soil. Out of this problematic, this study aims to propose interventions not only in the physical structure of irregular housing, but also to serve as a guide to intervene in the way eco-friendly, communitarian housing is seen by extreme poor zones inside metropolitan regions around big cities in the global south. The adaptation and reuse of industrial containers from the Harbor of Itaqui for housing is also an aim of the project. The great volume of discarded industrial containers may be an opportunity to solve housing deficit in the city. That way, through field research in São Luís’ neighborhoods mostly occupied by inappropriate housing, the study intends to raise ethnographical and physical values that help to shape new uses of industrial containers and recycled building materials, bringing the community into the process of shaping new-housing for local housing programs, changing the mindset of a concrete/brick model of building. The study used a general feasibility analysis of local engineers regarding strength of the locally used container for construction purposes, and also researched in-loco the current impressions of risky areas inhabitants of housing, traditional housing and the role they played as city shapers, evaluating their perceptions of what means to live and how their houses represent their personality.Keywords: container housing, civil construction, housing deficit, participatory design, sustainability
Procedia PDF Downloads 19194 Performance Management in Public Administration on Chile and Portugal
Authors: Lilian Bambirra De Assis, Patricia Albuquerque Gomes, Kamila Pagel De Oliveira, Deborah Oliveira Santos, Marcelo Esteves Chaves Campos
Abstract:
This paper aimed to analyze how performance management occurs in the context of the modernization of the federal public sector in Chile and Portugal. To do so, the study was based on a theoretical framework that covers the modernization of public administration to performance management, passing on people management. The work consisted of qualitative-descriptive research in which 16 semi-structured interviews were applied in the countries of study and documents and legislation were used referring to the subject. Performance management, as well as other people management subsystems, is criticized for using private sector management tools, based on a results-driven logic. From this point of view, it is understood that certain practices of the private sector, regarding the measurement of performance, can not be simply inserted in the scenario of the public administration. Beyond this criticism, performance management can contribute to the achievement of the strategic objectives of the countries and its focus is upward, a trend that can be verified through the manuals produced; by the interest of consultants and professional organizations, both public and private; and OECD (Organization for Economic Cooperation and Development) evaluations. In Portugal, public administration reform was implemented during the Constitutional Government (2005-2009) and had as its objective the restructuring of human resources management, with an emphasis on its integration with budget management, which is an inclination of the OECD, while in Chile HRM (Human Resource Management) practices are directed to ministries to a lesser extent than the OECD average. The central human resources management sector, for the most part, coordinates policy but is also responsible for other issues, including payment and classification systems. Chile makes less use of strategic Human Resource Management practices than the average of OECD countries, and its prominence lies in the decentralization of public bodies, which may grant autonomy, but fragments the implementation of policies and practices in that country since they are not adopted by all organs. Through the analysis, it was possible to identify that Chile and Portugal have practices and personnel management policies that make reference to performance management, which is similar to other OECD countries. The study countries also have limitations to implement performance management and the results indicate that there are still processes to be perfected, such as performance appraisal and compensation.Keywords: management of people in the public sector, modernization of public administration, performance management in the public sector, HRM, OECD
Procedia PDF Downloads 15293 Vanadium (V) Complexes of a Tripodal Ligand, Their Characterization and Biological Implications
Authors: Mannar R. Maurya, Bhawna Uprety, Fernando Avecilla, Pedro Adão, J. Costa Pessoa
Abstract:
The reaction of the tripodal tetradentate dibasic ligand 6,6'–(2–(pyridin–2–yl)ethylazanediyl)bis(methylene)bis(2,4–di–tert–butylphenol), H2L1 I, with [VIVO(acac)2] in CH3CN gives the VVO–complex, [VVO(acac)(L1)] 1. Crystallization of 1 in CH3CN at ~0 ºC, gives dark blue crystals of 1, while at room temperature it affords dark green crystals of [{VVO(L1)}2µ–O] 3. Upon prolonged treatment of 1 in MeOH [VVO(OMe)(MeOH)(L1)] 2 is obtained. All three complexes are analyzed by single–crystal X–ray diffraction, depicting distorted octahedral geometry around vanadium. In the reaction of H2L1 with VIVOSO4 partial hydrolysis of the tripodal ligand results in elimination of the pyridyl fragment of L1 and the formation of H[VVO2(L2)] 4, containing the ONO tridentate ligand 6,6'–azanediylbis(methylene)bis(2,4–di–tert–butylphenol), H2L2 II. Compound 4, which was not fully characterized, undergoes dimerization in acetone yielding the hydroxido–bridged [{VVO(L2)}2µ–(HO)2] 5, having distorted octahedral geometry around each vanadium. In contrast, from a solution of 4 in acetonitrile, the dinuclear compound [{VVO(L2)}2µ–O] 6 is obtained, with trigonal bipyramidal geometry around each vanadium. The methoxido complex 2 is successfully employed as a functional catechol–oxidase mimic in the oxidation of catechol to o–quinone under air. The process is confirmed to follow a Michaelis–Menten type kinetics with respect to catechol, the Vmax and KM values obtained being 7.66×10–6 M min -1 and 0.0557 M, respectively, and the turnover frequency is 0.0541 min–1. Complex 2 is also used as a catalyst precursor for the oxidative bromination of thymol in aqueous medium. The selectivity shows quite interesting trends, namely when not using excess of primary oxidizing agent, H2O2 the para mono–brominated product corresponds to ~93 % of the products and no dibromo derivative is formed.Keywords: oxidovanadium (V) complexes, tripodal ligand, crystal structure, catechol oxidase mimetic activity
Procedia PDF Downloads 341