Search results for: Anderson A. Oliveira
Commenced in January 2007
Frequency: Monthly
Edition: International
Paper Count: 350

Search results for: Anderson A. Oliveira

20 Vieira Da Silva's Tiles at Universidade Federal Rural Do Rio de Janeiro: A Conservation and Restoration Project

Authors: Adriana Anselmo Oliveira

Abstract:

The present project showcases a tile work from the Franco-Portuguese artist Maria Helena Vieira da Silva (1908-1992). It is a set of 8 panels composed of figurative and geometric tiles, with extra tiles framing nearby doors and windows in a study room in the (UFRRJ, Universidade Federal Rural do Rio de Janeiro). The aforementioned work was created between 1942 and 1943, during the artist's 6 year exile in the Brazilian city. This one-of-a-kind tileset was designed and made by Vieira da Silva between 1942 and 1943. Over the years, several units were lost, which led to their replacement in the nineties. However, these replacements don't do justice to the original work of art. In 2007, a project was initiated to fully repair and maintain the set. Three panels are removed and restored, but the project is halted. To this day, the three fully restored panels remain in boxes. In 2016 a new restoration project is submitted by the (Faculdade de Belas Artes da Universidade de Lisboa) in collaboration with de (Fundacão Árpád Szenes-Vieira da Silva). There are many varied opinions on restoring and conserving older pieces of art, however, we have the moral duty to safeguard the original materials used by the artist along with the artists original vision and also to care for the future generations of students who will use the space in which the tile-work was inserted. Many tiles have been replaced by white tiles, tiles with a divergent colour pallet and technique, and in a few cases, the incorrect place or way around. These many factors make it increasingly difficult to maintain the artists original vision and destroy and chance of coherence within the artwork itself. The conservative technician cannot make new images to fill the empty spaces or mark the remaining images with their own creative input. with reliable photographic documentation that can provide us with the necessary vision to allow us to proceed with an accurate reconstruction, we have the obligation to proceed and return the piece of art to its true form, as in its current state, it is impossible to maintain its original glory. Using the information we have, we must find a way to differentiate the original tiles from the reconstructions in order to recreate and reclaim the original message from the artist. The objective of this project is to understand the significance of tiles in Vieira da Silva's art as well as the influence they had on the artist's pictorial language since the colour definition on tile work is vastly different from the painting process as the materials change during their merger. Another primary goal is to understand what the previous interventions achieved besides increasing the artworks durability. The main objective is to submit a proposal that can salvage the artist's visual intention and supports it for posteriority. In summary, this proposal goes further than the usual conservative interventions as it intends to recreate the original artistic worth, prioritising the aesthetics and keeping its soul alive.

Keywords: Vieira da Silva, tiles, conservation, restoration

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19 Electrophysiological Correlates of Statistical Learning in Children with and without Developmental Language Disorder

Authors: Ana Paula Soares, Alexandrina Lages, Helena Oliveira, Francisco-Javier Gutiérrez-Domínguez, Marisa Lousada

Abstract:

From an early age, exposure to a spoken language allows us to implicitly capture the structure underlying the succession of the speech sounds in that language and to segment it into meaningful units (words). Statistical learning (SL), i.e., the ability to pick up patterns in the sensory environment even without intention or consciousness of doing it, is thus assumed to play a central role in the acquisition of the rule-governed aspects of language and possibly to lie behind the language difficulties exhibited by children with development language disorder (DLD). The research conducted so far has, however, led to inconsistent results, which might stem from the behavioral tasks used to test SL. In a classic SL experiment, participants are first exposed to a continuous stream (e.g., syllables) in which, unbeknownst to the participants, stimuli are grouped into triplets that always appear together in the stream (e.g., ‘tokibu’, ‘tipolu’), with no pauses between each other (e.g., ‘tokibutipolugopilatokibu’) and without any information regarding the task or the stimuli. Following exposure, SL is assessed by asking participants to discriminate between triplets previously presented (‘tokibu’) from new sequences never presented together during exposure (‘kipopi’), i.e., to perform a two-alternative-forced-choice (2-AFC) task. Despite the widespread use of the 2-AFC to test SL, it has come under increasing criticism as it is an offline post-learning task that only assesses the result of the learning that had occurred during the previous exposure phase and that might be affected by other factors beyond the computation of regularities embedded in the input, typically the likelihood two syllables occurring together, a statistic known as transitional probability (TP). One solution to overcome these limitations is to assess SL as exposure to the stream unfolds using online techniques such as event-related potentials (ERP) that is highly sensitive to the time-course of the learning in the brain. Here we collected ERPs to examine the neurofunctional correlates of SL in preschool children with DLD, and chronological-age typical language development (TLD) controls who were exposed to an auditory stream in which eight three-syllable nonsense words, four of which presenting high-TPs and the other four low-TPs, to further analyze whether the ability of DLD and TLD children to extract-word-like units from the steam was modulated by words’ predictability. Moreover, to ascertain if the previous knowledge of the to-be-learned-regularities affected the neural responses to high- and low-TP words, children performed the auditory SL task, firstly, under implicit, and, subsequently, under explicit conditions. Although behavioral evidence of SL was not obtained in either group, the neural responses elicited during the exposure phases of the SL tasks differentiated children with DLD from children with TLD. Specifically, the results indicated that only children from the TDL group showed neural evidence of SL, particularly in the SL task performed under explicit conditions, firstly, for the low-TP, and, subsequently, for the high-TP ‘words’. Taken together, these findings support the view that children with DLD showed deficits in the extraction of the regularities embedded in the auditory input which might underlie the language difficulties.

Keywords: development language disorder, statistical learning, transitional probabilities, word segmentation

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18 Influence of Mandrel’s Surface on the Properties of Joints Produced by Magnetic Pulse Welding

Authors: Ines Oliveira, Ana Reis

Abstract:

Magnetic Pulse Welding (MPW) is a cold solid-state welding process, accomplished by the electromagnetically driven, high-speed and low-angle impact between two metallic surfaces. It has the same working principle of Explosive Welding (EXW), i.e. is based on the collision of two parts at high impact speed, in this case, propelled by electromagnetic force. Under proper conditions, i.e., flyer velocity and collision point angle, a permanent metallurgical bond can be achieved between widely dissimilar metals. MPW has been considered a promising alternative to the conventional welding processes and advantageous when compared to other impact processes. Nevertheless, MPW current applications are mostly academic. Despite the existing knowledge, the lack of consensus regarding several aspects of the process calls for further investigation. As a result, the mechanical resistance, morphology and structure of the weld interface in MPW of Al/Cu dissimilar pair were investigated. The effect of process parameters, namely gap, standoff distance and energy, were studied. It was shown that welding only takes place if the process parameters are within an optimal range. Additionally, the formation of intermetallic phases cannot be completely avoided in the weld of Al/Cu dissimilar pair by MPW. Depending on the process parameters, the intermetallic compounds can appear as continuous layer or small pockets. The thickness and the composition of the intermetallic layer depend on the processing parameters. Different intermetallic phases can be identified, meaning that different temperature-time regimes can occur during the process. It is also found that lower pulse energies are preferred. The relationship between energy increase and melting is possibly related to multiple sources of heating. Higher values of pulse energy are associated with higher induced currents in the part, meaning that more Joule heating will be generated. In addition, more energy means higher flyer velocity, the air existing in the gap between the parts to be welded is expelled, and this aerodynamic drag (fluid friction) is proportional to the square of the velocity, further contributing to the generation of heat. As the kinetic energy also increases with the square of velocity, the dissipation of this energy through plastic work and jet generation will also contribute to an increase in temperature. To reduce intermetallic phases, porosity, and melt pockets, pulse energy should be minimized. The bond formation is affected not only by the gap, standoff distance, and energy but also by the mandrel’s surface conditions. No correlation was clearly identified between surface roughness/scratch orientation and joint strength. Nevertheless, the aspect of the interface (thickness of the intermetallic layer, porosity, presence of macro/microcracks) is clearly affected by the surface topology. Welding was not established on oil contaminated surfaces, meaning that the jet action is not enough to completely clean the surface.

Keywords: bonding mechanisms, impact welding, intermetallic compounds, magnetic pulse welding, wave formation

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17 Impact Analysis of a School-Based Oral Health Program in Brazil

Authors: Fabio L. Vieira, Micaelle F. C. Lemos, Luciano C. Lemos, Rafaela S. Oliveira, Ian A. Cunha

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Brazil has some challenges ahead related to population oral health, most of them associated with the need of expanding into the local level its promotion and prevention activities, offer equal access to services and promote changes in the lifestyle of the population. The program implemented an oral health initiative in public schools in the city of Salvador, Bahia. The mission was to improve oral health among students on primary and secondary education, from 2 to 15 years old, using the school as a pathway to increase access to healthcare. The main actions consisted of a team's visit to the schools with educational sessions for dental cavity prevention and individual assessment. The program incorporated a clinical surveillance component through a dental evaluation of every student searching for dental disease and caries, standardization of the dentists’ team to reach uniform classification on the assessments, and the use of an online platform to register data directly from the schools. Sequentially, the students with caries were referred for free clinical treatment on the program’s Health Centre. The primary purpose of this study was to analyze the effects and outcomes of this school-based oral health program. The study sample was composed by data of a period of 3 years - 2015 to 2017 - from 13 public schools on the suburb of the city of Salvador with a total number of assessments of 9,278 on this period. From the data collected the prevalence of children with decay on permanent teeth was chosen as the most reliable indicator. The prevalence was calculated for each one of the 13 schools using the number of children with 1 or more dental caries on permanent teeth divided by the total number of students assessed for school each year. Then the percentage change per year was calculated for each school. Some schools presented a higher variation on the total number of assessments in one of the three years, so for these, the percentage change calculation was done using the two years with less variation. The results show that 10 of the 13 schools presented significative improvements for the indicator of caries in permanent teeth. The mean for the number of students with caries percentage reduction on the 13 schools was 26.8%, and the median was 32.2% caries in permanent teeth institution. The highest percentage of improvement reached a decrease of 65.6% on the indicator. Three schools presented a rise in caries prevalence (8.9, 18.9 and 37.2% increase) that, on an initial analysis, seems to be explained with the students’ cohort rotation among other schools, as well as absenteeism on the treatment. In conclusion, the program shows a relevant impact on the reduction of caries in permanent teeth among students and the need for the continuity and expansion of this integrated healthcare approach. It has also been evident the significative of the articulation between health and educational systems representing a fundamental approach to improve healthcare access for children especially in scenarios such as presented in Brazil.

Keywords: primary care, public health, oral health, school-based oral health, data management

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16 Association between Obstetric Factors with Affected Areas of Health-Related Quality of Life of Pregnant Women

Authors: Cinthia G. P. Calou, Franz J. Antezana, Ana I. O. Nicolau, Eveliny S. Martins, Paula R. A. L. Soares, Glauberto S. Quirino, Dayanne R. Oliveira, Priscila S. Aquino, Régia C. M. B. Castro, Ana K. B. Pinheiro

Abstract:

Introduction: As an integral part of the health-disease process, gestation is a period in which the social insertion of women can influence, in a positive or negative way, the course of the pregnancy-puerperal cycle. Thus, evaluating the quality of life of this population can redirect the implementation of innovative practices in the quest to make them more effective and real for the promotion of a more humanized care. This study explores the associations between the obstetric factors with affected areas of health-related quality of life of pregnant women with habitual risk. Methods: This is a cross-sectional, quantitative study conducted in three public facilities and a private service that provides prenatal care in the city of Fortaleza, Ceara, Brazil. The sample consisted of 261 pregnant women who underwent low-risk prenatal care and were interviewed from September to November 2014. The collection instruments were a questionnaire containing socio-demographic and obstetric variables, in addition to the Brazilian version of the Mother scale Generated Index (MGI) characterized by being a specific and objective instrument, consisting of a single sheet and subdivided into three stages. It allows identifying the areas of life of the pregnant woman that are most affected, which could go unnoticed by the pre-formulated measurement instruments. The obstetric data, as well as the data concerning the application of the MGI scale, were compiled and analyzed through the statistical program Statistical Package for the Social Sciences (SPSS), version 20.0. After the compilation, a descriptive analysis was carried out. Then, associations were made between some variables. The tests applied were the Pearson Chi-Square and the Fisher's exact test. The odds ratio was also calculated. These associations were considered statistically significant when the p (probability) value was less than or equal to a level of 5% (α = 0.05) in the tests performed. Results: The variables that negatively reflected the quality of life of the pregnant women and presented a significant association with the polaciuria were: gestational age (p = 0.022) and parity (p = 0.048). Episodes of nausea and vomiting also showed significant with gestational age correlation (p = 0.0001). Evaluating the crossing of stress, we observed a significant association with parity (p = 0.0001). In turn, emotional lability revealed dependence on the variable type of delivery (p = 0.009). Conclusion: The health professionals involved in the assistance to the pregnant woman can understand how the process of gestation is experienced, considering all its peculiar transformations; to meet their individual needs, stimulating their autonomy and their power of choice, envisaging the achievement of a better quality of life related to health in the perspective of health promotion.

Keywords: health-related quality of life, obstetric nursing, pregnant women, prenatal care

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15 Validation of an Educative Manual for Patients with Breast Cancer Submitted to Radiation Therapy

Authors: Flavia Oliveira de A. M. Cruz, Edison Tostes Faria, Paula Elaine D. Reis

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When the breast is submitted to radiation therapy (RT), the most common effects are pain, skin changes, mobility restrictions, local sensory alteration, and fatigue. These effects, if not managed properly, may reduce the quality of life of cancer patients and may lead to the treatment discontinuation. Therefore, promoting knowledge and guidelines for symptom management remain a high priority for patients and a challenge for health professionals, due to the need to handle side effects in a population with a life-threatening disease. Printed materials are important strategies for supporting educative activities since they help the individual to assimilate and understand the amount of information transmitted. Nurses' behavior can be systematized through the use of an educative manual, which may be effective in promoting information regarding the treatment, self-care and how to control the effects of RT at home. In view of the importance of guaranteeing the validity of the material before its use, the objective of this research was to validate the content and appearance of an educative manual for breast cancer patients undergoing RT. The Theory of Psychometrics was used for the validation process in this descriptive methodological research. A minimum agreement rate (AR) of 80% was considered to guarantee the validity of the material. The data were collected from October to December 2017, by means of two assessments tools, constructed in the form of a Likert scale, with five levels of understanding. These instruments addressed different aspects of the evaluation, in view of two different groups of participants; 17 experts in the theme area of the educative manual, and 12 women that received RT previously to treat breast cancer. The manual was titled 'Orientation Manual: radiation therapy in breast', and was focused on breast cancer patients attended at the Department of Oncology of the Brasília University Hospital (UNACON/HUB). The research project was submitted to the Research Ethics Committee at the School of Health Sciences of the University of Brasília (CAAE: 24592213.1.0000.0030). Only two items of the assessment tool for the experts, one related to the manual's ability to promote behavioral and attitude changes and the other related to the extent of its use for other health services, obtained AR < 80% and were reformulated based on the participants' suggestions and in the literature. All other items were considered appropriate and/or complete appropriate in the three blocks proposed for the experts: objectives - 89%, structure and form - 93%, and relevance - 93%; and good and/or very good in the five blocks of analysis proposed for patients: objectives - 100%, organization - 100%, writing style - 100%, appearance - 100%, and motivation. The appearance and content validation of the educative manual proposed were attended to. The educative manual was considered relevant and pertinent and may contribute to the understanding of the therapeutic process by breast cancer patients during RT, as well as support clinical practice through the nursing consultation.

Keywords: oncology nursing, nursing care, validation studies, educational technology

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14 Chronic Fatigue Syndrome/Myalgic Encephalomyelitis in Younger Children: A Qualitative Analysis of Families’ Experiences of the Condition and Perspective on Treatment

Authors: Amberly Brigden, Ali Heawood, Emma C. Anderson, Richard Morris, Esther Crawley

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Background: Paediatric chronic fatigue syndrome (CFS)/myalgic encephalomyelitis (ME) is characterised by persistent, disabling fatigue. Health services see patients below the age of 12. This age group experience high levels of disability, with low levels of school attendance, high levels of fatigue, anxiety, functional disability and pain. CFS/ME interventions have been developed for adolescents, but the developmental needs of younger children suggest treatment should be tailored to this age group. Little is known about how intervention should be delivered to this age group, and further work is needed to explore this. Qualitative research aids patient-centered design of health intervention. Methods: Five to 11-year-olds and their parents were recruited from a specialist CFS/ME service. Semi-structured interviews explored the families’ experience of the condition and perspectives on treatment. Interactive and arts-based methods were used. Interviews were audio-recorded, transcribed and analysed thematically. Qualitative Results: 14 parents and 7 children were interviewed. Early analysis of the interviews revealed the importance of the social-ecological setting of the child, which led to themes being developed in the context of Systems Theory. Theme one relates to the level of the child, theme two the family system, theme three the organisational and societal systems, and theme four cuts-across all levels. Theme1: The child’s capacity to describe, understand and manage their condition. Younger children struggled to describe their internal experiences, such as physical symptoms. Parents felt younger children did not understand some concepts of CFS/ME and did not have the capabilities to monitor and self-regulate their behaviour, as required by treatment. A spectrum of abilities was described; older children (10-11-year-olds) were more involved in clinical sessions and had more responsibility for self-management. Theme2: Parents’ responsibility for managing their child’s condition. Parents took responsibility for regulating their child’s behaviour in accordance with the treatment programme. They structured their child’s environment, gave direct instructions to their child, and communicated the needs of their child to others involved in care. Parents wanted their child to experience a 'normal' childhood and took steps to shield their child from medicalization, including diagnostic labels and clinical discussions. Theme3: Parental isolation and the role of organisational and societal systems. Parents felt unsupported in their role of managing the condition and felt negative responses from primary care health services and schools were underpinned by a lack of awareness and knowledge about CFS/ME in younger children. This sometimes led to a protracted time to diagnosis. Parents felt that schools have the potential important role in managing the child’s condition. Theme4: Complexity and uncertainty. Many parents valued specialist treatment (which included activity management, physiotherapy, sleep management, dietary advice, medical management and psychological support), but felt it needed to account for the complexity of the condition in younger children. Some parents expressed uncertainty about the diagnosis and the treatment programme. Conclusions: Interventions for younger children need to consider the 'systems' (family, organisational and societal) involved in the child’s care. Future research will include interviews with clinicians and schools supporting younger children with CFS/ME.

Keywords: chronic fatigue syndrome (CFS)/myalgic encephalomyelitis (ME), pediatric, qualitative, treatment

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13 Analysis of the Evolution of Techniques and Review in Cleft Surgery

Authors: Tomaz Oliveira, Rui Medeiros, André Lacerda

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Introduction: Cleft lip and/or palate are the most frequent forms of congenital craniofacial anomalies, affecting mainly the middle third of the face and manifesting by functional and aesthetic changes. Bilateral cleft lip represents a reconstructive surgical challenge, not only for the labial component but also for the associated nasal deformation. Recently, the paradigm of the approach to this pathology has changed, placing the focus on muscle reconstruction and anatomical repositioning of the nasal cartilages in order to obtain the best aesthetic and functional results. The aim of this study is to carry out a systematic review of the surgical approach to bilateral cleft lip, retrospectively analyzing the case series of Plastic Surgery Service at Hospital Santa Maria (Lisbon, Portugal) regarding this pathology, the global assessment of the characteristics of the operated patients and the study of the different surgical approaches and their complications in the last 20 years. Methods: The present work demonstrates a retrospective and descriptive study of patients who underwent at least one reconstructive surgery for cleft lip and/or palate, in the CPRE service of the HSM, in the period between January 1 of 1997 and December 31 of 2017, in which the data relating to 361 individuals were analyzed who, after applying the exclusion criteria, constituted a sample of 212 participants. The variables analyzed were the year of the first surgery, gender, age, type of orofacial cleft, surgical approach, and its complications. Results: There was a higher overall prevalence in males, with cleft lip and cleft palate occurring in greater proportion in males, with the cleft palate being more common in females. The most frequently recorded malformation was cleft lip and palate, which is complete in most cases. Regarding laterality, alterations with a unilateral labial component were the most commonly observed, with the left lip being described as the most affected. It was found that the vast majority of patients underwent primary intervention up to 12 months of age. The surgical techniques used in the approach to this pathology showed an important chronological variation over the years. Discussion: Cleft lip and/or palate is a medical condition associated with high aesthetic and functional morbidity, which requires early treatment in order to optimize the long-term outcome. The existence of a nasolabial component and its respective surgical correction plays a central role in the treatment of this pathology. The high rates of post-surgical complications and unconvincing aesthetic results have motivated an evolution of the surgical technique, increasingly evident in recent years, allowing today to achieve satisfactory aesthetic results, even in bilateral cleft lip with high deformation complexity. The introduction of techniques that favor nasolabial reconstruction based on anatomical principles has been producing increasingly convincing results. The analyzed sample shows that most of the results obtained in this study are, in general, compatible with the results published in the literature. Conclusion: This work showed that the existence of small variations in the surgical technique can bring significant improvements in the functional and aesthetic results in the treatment of bilateral cleft lip.

Keywords: cleft lip, palate lip, congenital abnormalities, cranofacial malformations

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12 Associated Factors the Safety of the Patient in Hemodialysis Clinics of a Brazilian Municipality: Cross-Sectional Study

Authors: Magda Milleyde de Sousa Lima, Letícia Lima Aguiar, Marina Guerra Martins, Erika Veríssimo Dias Sousa, Lizandra Sampaio de Oliveira, Lívia Moreira Barros, Joselany Áfio Caetano

Abstract:

Patients with chronic kidney disease are vulnerable to episodes which make the safety of their health vulnerable, mainly due to the treatment process that exposes them to high rates of interventions during hemodialysis sessions. Some factors associated with health care contribute to the risk of death and complications. However, there are a small number of scientific studies evaluating the level of safety of hemodialysis clinics, and the sociodemographic characteristics of patients and professionals associated with this safety. Therefore, the present study aims to examine the level of patient safety in hemodialysis clinics in the Brazilian capital, to identify the sociodemographic and clinical factors of patients and nursing staff associated with the level of safety. This is an observational, descriptive and quantitative research conducted in three hemodialysis clinics placed in the city of Fortaleza-CE, Brazil, from September to November 2019. The sample was formed after a sample calculation for finite inhabitants of correlation with 200 chronic renal patients, 30 nursing technicians and seven nurses. Conventional sampling was used based on the inclusion criteria: being present at the hemodialysis session on the day the researcher performed the data collection and being 18 years of age or older. Participants who presented communication difficulties to listen to and/or answer the sociodemographic and clinical questionnaire were excluded. Two instruments were applied: sociodemographic and clinical characterization form and Chronic Renal Patient Safety Assessment Scale on Hemodialysis (EASPRCH). The data were analyzed using the Kruskal Walls Test for categorical variables and Spearman correlation coefficient for non-categorical variables, using the Statistical Package SPSS version 20.0. The present study respected the ethical and legal principles determined by resolution 466/2012 of the National Health Council, under the approval of the Ethics and Research Committee with an opinion number: 3,255,635. The results showed that a hemodialysis clinic presented unsafe care practices of 32 points in the EASPRCH (p=0.001). A statistical association was identified between the level of safety and the variables of the patients: level of education (p=0.018), family income (p=0.049), type of employment (p=0.012), venous access site (p=0.009), use of medication during the session (p=0.008) and time of hemodialysis (p=0.002). When evaluating the profile of nurses, a statistical association was evidenced between the level of safety with the variables: marital status (p=0.000), race (p=0.017), schooling (p= 0.000), income (p=0.013), age (p=0.000), clinic workload (p=0.000), time working with hemodialysis (p=0.000), time working in the clinic (p= 0.007) and clinic sizing (p=0.000). In order, the sociodemographic factors of nursing technicians associated with the level of patient safety were: race (p= 0.001) and weekly workload at (p=0.010). Therefore, it is concluded that there is a non-conformity in the level of patient safety in one of the clinics studied and, that sociodemographic and clinical factors of patients and health professionals corroborate the level of safety of the health unit.

Keywords: hemodialysis, nursing, patient safety, quality improvement

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11 Mechanical Properties of Poly(Propylene)-Based Graphene Nanocomposites

Authors: Luiza Melo De Lima, Tito Trindade, Jose M. Oliveira

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The development of thermoplastic-based graphene nanocomposites has been of great interest not only to the scientific community but also to different industrial sectors. Due to the possible improvement of performance and weight reduction, thermoplastic nanocomposites are a great promise as a new class of materials. These nanocomposites are of relevance for the automotive industry, namely because the emission limits of CO2 emissions imposed by the European Commission (EC) regulations can be fulfilled without compromising the car’s performance but by reducing its weight. Thermoplastic polymers have some advantages over thermosetting polymers such as higher productivity, lower density, and recyclability. In the automotive industry, for example, poly(propylene) (PP) is a common thermoplastic polymer, which represents more than half of the polymeric raw material used in automotive parts. Graphene-based materials (GBM) are potential nanofillers that can improve the properties of polymer matrices at very low loading. In comparison to other composites, such as fiber-based composites, weight reduction can positively affect their processing and future applications. However, the properties and performance of GBM/polymer nanocomposites depend on the type of GBM and polymer matrix, the degree of dispersion, and especially the type of interactions between the fillers and the polymer matrix. In order to take advantage of the superior mechanical strength of GBM, strong interfacial strength between GBM and the polymer matrix is required for efficient stress transfer from GBM to the polymer. Thus, chemical compatibilizers and physicochemical modifications have been reported as important tools during the processing of these nanocomposites. In this study, PP-based nanocomposites were obtained by a simple melt blending technique, using a Brabender type mixer machine. Graphene nanoplatelets (GnPs) were applied as structural reinforcement. Two compatibilizers were used to improve the interaction between PP matrix and GnPs: PP graft maleic anhydride (PPgMA) and PPgMA modified with tertiary amine alcohol (PPgDM). The samples for tensile and Charpy impact tests were obtained by injection molding. The results suggested the GnPs presence can increase the mechanical strength of the polymer. However, it was verified that the GnPs presence can promote a decrease of impact resistance, turning the nanocomposites more fragile than neat PP. The compatibilizers’ incorporation increases the impact resistance, suggesting that the compatibilizers can enhance the adhesion between PP and GnPs. Compared to neat PP, Young’s modulus of non-compatibilized nanocomposite increase demonstrated that GnPs incorporation can promote a stiffness improvement of the polymer. This trend can be related to the several physical crosslinking points between the PP matrix and the GnPs. Furthermore, the decrease of strain at a yield of PP/GnPs, together with the enhancement of Young’s modulus, confirms that the GnPs incorporation led to an increase in stiffness but to a decrease in toughness. Moreover, the results demonstrated that incorporation of compatibilizers did not affect Young’s modulus and strain at yield results compared to non-compatibilized nanocomposite. The incorporation of these compatibilizers showed an improvement of nanocomposites’ mechanical properties compared both to those the non-compatibilized nanocomposite and to a PP sample used as reference.

Keywords: graphene nanoplatelets, mechanical properties, melt blending processing, poly(propylene)-based nanocomposites

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10 Automatic Identification of Pectoral Muscle

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

Abstract:

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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9 Oat Bran Associated with Nutritional Counseling in Treating Obesity and Other Risk Factors for Cardiovascular Disease

Authors: Simone Raimondi De Souza, Glaucia Maria Moraes De Oliveira, Ronir Raggio Luiz, Glorimar Rosa

Abstract:

Introduction: Obesity is among the main risk factors for cardiovascular disease (CVD). Genesis is multifactorial, including genetic, hormonal and environmental factors disorders, among which inadequate feeding pattern, for which nutritional counseling strategies have proven effective. The consumption of beta-glucans (soluble fibers that reportedly promote satiety) present in oat bran can be an effective strategy for preventing and treating obesity. Other benefits have been observed with oat bran consumption, such as reduction of hypercholesterolemia and hyperglycemia, two other risk factors for CVD. Objectives: To analyze the effect of oat bran consumption associated with nutritional counseling in reducing body mass index (BMI), blood cholesterol, glucose profile, waist and neck circumference in obese individuals, and to evaluate the change in eating pattern. Methods: clinical trial, randomized, double-blind, placebo-controlled, lasting 90 days with adults of both genders, with BMI ≥30kg/m2. The study was approved by the Ethics in Research involving human beings in a public institute of cardiology, in Rio de Janeiro, Brazil. Individuals were invited to participate and accepted formally by signing the Terms of Consent. Participants were randomized into oat bran group (gOB) or placebo group (gPCB) and received, respectively: morning prepared consisting of 40g oat bran, 30g of skimmed milk powder and 1g sweetener sucralose; refined flour 40g rice, 30g of milk powder and 1g sweetener sucralose. The Ten Steps to Healthy Eating, of Brazilian Ministry of Health were used to support the nutritional counseling. Variables analyzed: gender; age; BMI, waist circumference (WC) neck circumference (NC); systolic blood pressure (SBP); diastolic blood pressure (DBP); food consumption, total cholesterol (TC), LDL-cholesterol (LDL-c), HDL-cholesterol (HDL-c), non-HDL cholesterol (nHDLc), triglycerides (TG), fasting glucose (FG), fasting insulin (FI) and HOMA-IR. Dietary intake was assessed by 24-hour dietary recall. The Diet Quality Index revised for the Brazilian population (IQD-R) assessed quality of feeding pattern. Statistical analyzes were performed using SPSS version 21, considering statistically significant p-value less than 0.05. Results: A total of 38 participants were included, age = 50 ± 7,6years, 63% women. 19 subjects were placed in gOB and 19 in gPCB. After intervention, statistically significant reductions were observed in the following parameters: in gOB: IQD-R, TC, LDL-c, nHDL-c, FI, SBP, DBP, BMI, WC, NC; in gPCB: IQD-R, LDL-c, SBP, DBP, BMI, WC, NC. No statistically significant differences were observed in the results between groups. Conclusion: Our results reinforce nutritional counseling as important strategy for prevention and treatment of obesity and suggest that inclusion of oat bran in daily diet can bring additional benefits controlling risk factors for CVD. More studies are needed to establish all benefits of oat bran to human health as well as the ideal daily dose for consumption.

Keywords: oat bran, cardiovascular disease, nutritional counseling, obesity

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8 Implementation of Synthesis and Quality Control Procedures of ¹⁸F-Fluoromisonidazole Radiopharmaceutical

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

Abstract:

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

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7 Rheolaser: Light Scattering Characterization of Viscoelastic Properties of Hair Cosmetics That Are Related to Performance and Stability of the Respective Colloidal Soft Materials

Authors: Heitor Oliveira, Gabriele De-Waal, Juergen Schmenger, Lynsey Godfrey, Tibor Kovacs

Abstract:

Rheolaser MASTER™ makes use of multiple scattering of light, caused by scattering objects in a continuous medium (such as droplets and particles in colloids), to characterize the viscoelasticity of soft materials. It offers an alternative to conventional rheometers to characterize viscoelasticity of products such as hair cosmetics. Up to six simultaneous measurements at controlled temperature can be carried out simultaneously (10-15 min), and the method requires only minor sample preparation work. Conversely to conventional rheometer based methods, no mechanical stress is applied to the material during the measurements. Therefore, the properties of the exact same sample can be monitored over time, like in aging and stability studies. We determined the elastic index (EI) of water/emulsion mixtures (1 ≤ fat alcohols (FA) ≤ 5 wt%) and emulsion/gel-network mixtures (8 ≤ FA ≤ 17 wt%) and compared with the elastic/sorage mudulus (G’) for the respective samples using a TA conventional rheometer with flat plates geometry. As expected, it was found that log(EI) vs log(G’) presents a linear behavior. Moreover, log(EI) increased in a linear fashion with solids level in the entire range of compositions (1 ≤ FA ≤ 17 wt%), while rheometer measurements were limited to samples down to 4 wt% solids level. Alternatively, a concentric cilinder geometry would be required for more diluted samples (FA > 4 wt%) and rheometer results from different sample holder geometries are not comparable. The plot of the rheolaser output parameters solid-liquid balance (SLB) vs EI were suitable to monitor product aging processes. These data could quantitatively describe some observations such as formation of lumps over aging time. Moreover, this method allowed to identify that the different specifications of a key raw material (RM < 0.4 wt%) in the respective gel-network (GN) product has minor impact on product viscoelastic properties and it is not consumer perceivable after a short aging time. Broadening of a RM spec range typically has a positive impact on cost savings. Last but not least, the photon path length (λ*)—proportional to droplet size and inversely proportional to volume fraction of scattering objects, accordingly to the Mie theory—and the EI were suitable to characterize product destabilization processes (e.g., coalescence and creaming) and to predict product stability about eight times faster than our standard methods. Using these parameters we could successfully identify formulation and process parameters that resulted in unstable products. In conclusion, Rheolaser allows quick and reliable characterization of viscoelastic properties of hair cosmetics that are related to their performance and stability. It operates in a broad range of product compositions and has applications spanning from the formulation of our hair cosmetics to fast release criteria in our production sites. Last but not least, this powerful tool has positive impact on R&D development time—faster delivery of new products to the market—and consequently on cost savings.

Keywords: colloids, hair cosmetics, light scattering, performance and stability, soft materials, viscoelastic properties

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6 Media, Myth and Hero: Sacred Political Narrative in Semiotic and Anthropological Analysis

Authors: Guilherme Oliveira

Abstract:

The assimilation of images and their potential symbolism into lived experiences is inherent. It is through this exercise of recognition via imagistic records that the questioning of the origins of a constant narrative stimulated by the media arises. The construction of the "Man" archetype and the reflections of active masculine imagery in the 21st century, when conveyed through media channels, could potentially have detrimental effects. Addressing this systematic behavioral chronology of virile cisgender, permeated imagistically through these means, involves exploring potential resolutions. Thus, an investigation process is initiated into the potential representation of the 'hero' in this media emulation through idols contextualized in the political sphere, with the purpose of elucidating the processes of simulation and emulation of narratives based on mythical, historical, and sacred accounts. In this process of sharing, the narratives contained in the imagistic structuring offered by information dissemination channels seek validation through a process of public acceptance. To achieve this consensus, a visual set adorned with mythological and sacred symbolisms adapted to the intended environment is promoted, thus utilizing sociocultural characteristics in favor of political marketing. Visual recognition, therefore, becomes a direct reflection of a cultural heritage acquired through lived human experience, stimulated by continuous representations throughout history. Echoes of imagery and narratives undergo a constant process of resignification of their concepts, sharpened by their premises, and adapted to the environment in which they seek to establish themselves. Political figures analyzed in this article employ the practice of taking possession of symbolisms, mythological stories, and heroisms and adapt their visual construction through a continuous praxis of emulation. Thus, they utilize iconic mythological narratives to gain credibility through belief. Utilizing iconic mythological narratives for credibility through belief, the idol becomes the very act of release of trauma, offering believers liberation from preconceived concepts and allowing for the attribution of new meanings. To dissolve this issue and highlight the subjectivities within the intention of the image, a linguistic, semiotic, and anthropological methodology is created. Linguistics uses expressions like 'Blaming the Image' to create a mechanism of expressive action in questioning why to blame a construction or visual composition and thus seek answers in the first act. Semiotics and anthropology develop an imagistic atlas of graphic analysis, seeking to make connections, comparisons, and relations between modern and sacred/mystical narratives, emphasizing the different subjective layers of embedded symbolism. Thus, it constitutes a performative act of disarming the image. It creates a disenchantment of the superficial gaze under the constant reproduction of visual content stimulated by virtual networks, enabling a discussion about the acceptance of caricatures characterized by past fables.

Keywords: image, heroic narrative, media heroism, virile politics, political, myth, sacred performance, visual mythmaking, characterization dynamics

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5 Propagation of Ultra-High Energy Cosmic Rays through Extragalactic Magnetic Fields: An Exploratory Study of the Distance Amplification from Rectilinear Propagation

Authors: Rubens P. Costa, Marcelo A. Leigui de Oliveira

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The comprehension of features on the energy spectra, the chemical compositions, and the origins of Ultra-High Energy Cosmic Rays (UHECRs) - mainly atomic nuclei with energies above ~1.0 EeV (exa-electron volts) - are intrinsically linked to the problem of determining the magnitude of their deflections in cosmic magnetic fields on cosmological scales. In addition, as they propagate from the source to the observer, modifications are expected in their original energy spectra, anisotropy, and the chemical compositions due to interactions with low energy photons and matter. This means that any consistent interpretation of the nature and origin of UHECRs has to include the detailed knowledge of their propagation in a three-dimensional environment, taking into account the magnetic deflections and energy losses. The parameter space range for the magnetic fields in the universe is very large because the field strength and especially their orientation have big uncertainties. Particularly, the strength and morphology of the Extragalactic Magnetic Fields (EGMFs) remain largely unknown, because of the intrinsic difficulty of observing them. Monte Carlo simulations of charged particles traveling through a simulated magnetized universe is the straightforward way to study the influence of extragalactic magnetic fields on UHECRs propagation. However, this brings two major difficulties: an accurate numerical modeling of charged particles diffusion in magnetic fields, and an accurate numerical modeling of the magnetized Universe. Since magnetic fields do not cause energy losses, it is important to impose that the particle tracking method conserve the particle’s total energy and that the energy changes are results of the interactions with background photons only. Hence, special attention should be paid to computational effects. Additionally, because of the number of particles necessary to obtain a relevant statistical sample, the particle tracking method must be computationally efficient. In this work, we present an analysis of the propagation of ultra-high energy charged particles in the intergalactic medium. The EGMFs are considered to be coherent within cells of 1 Mpc (mega parsec) diameter, wherein they have uniform intensities of 1 nG (nano Gauss). Moreover, each cell has its field orientation randomly chosen, and a border region is defined such that at distances beyond 95% of the cell radius from the cell center smooth transitions have been applied in order to avoid discontinuities. The smooth transitions are simulated by weighting the magnetic field orientation by the particle's distance to the two nearby cells. The energy losses have been treated in the continuous approximation parameterizing the mean energy loss per unit path length by the energy loss length. We have shown, for a particle with the typical energy of interest the integration method performance in the relative error of Larmor radius, without energy losses and the relative error of energy. Additionally, we plotted the distance amplification from rectilinear propagation as a function of the traveled distance, particle's magnetic rigidity, without energy losses, and particle's energy, with energy losses, to study the influence of particle's species on these calculations. The results clearly show when it is necessary to use a full three-dimensional simulation.

Keywords: cosmic rays propagation, extragalactic magnetic fields, magnetic deflections, ultra-high energy

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4 Saving Lives from a Laptop: How to Produce a Live Virtual Media Briefing That Will Inform, Educate, and Protect Communities in Crisis

Authors: Cory B. Portner, Julie A. Grauert, Lisa M. Stromme, Shelby D. Anderson, Franji H. Mayes

Abstract:

Introduction: WASHINGTON state in the Pacific Northwest of the United States is internationally known for its technology industry, fisheries, agriculture, and vistas. On January 21, 2020, Washington state also became known as the first state with a confirmed COVID-19 case in the United States, thrusting the state into the international spotlight as the world came to grips with the global threat of this disease presented. Tourism is Washington state’s fourth-largest industry. Tourism to the state generates over 1.8 billion dollars (USD) in local and state tax revenue and employs over 180,000 people. Communicating with residents, stakeholders, and visitors on the status of disease activity, prevention measures, and response updates was vital to stopping the pandemic and increasing compliance and awareness. Significance: In order to communicate vital public health updates, guidance implementation, and safety measures to the public, the Washington State Department of Health established routine live virtual media briefings to reach audiences via social media, internet television, and broadcast television. Through close partnership with regional broadcast news stations and the state public affairs news network, the Washington State Department of Health hosted 95 media briefings from January 2020 through September 2022 and continues to regularly host live virtual media briefings to accommodate the needs of the public and media. Methods: Our methods quickly evolved from hosting briefings in the cement closet of a military base to being able to produce and stream the briefings live from any home-office location. The content was tailored to the hot topic of the day and to the reporter's questions and needs. Virtual media briefings hosted through inexpensive or free platforms online are extremely cost-effective: the only mandatory components are WiFi, a laptop, and a monitor. There is no longer a need for a fancy studio or expensive production software to achieve the goal of communicating credible, reliable information promptly. With minimal investment and a small learning curve, facilitators and panelists are able to host highly produced and engaging media availabilities from their living rooms. Results: The briefings quickly developed a reputation as the best source for local and national journalists to get the latest and most factually accurate information about the pandemic. In the height of the COVID-19 response, 135 unique media outlets logged on to participate in the briefing. The briefings typically featured 4-5 panelists, with as many as 9 experts in attendance to provide information and respond to media questions. Preparation was always a priority: Public Affairs staff for the Washington State Department of Health produced over 170 presenter remarks, including guidance on talking points for 63 expert guest panelists. Implication For Practice: Information is today’s most valuable currency. The ability to disseminate correct information urgently and on a wide scale is the most effective tool in crisis communication. Due to our role as the first state with a confirmed COVID-19 case, we were forced to develop the most accurate and effective way to get life-saving information to the public. The cost-effective, web-based methods we developed can be applied in any crisis to educate and protect communities under threat, ultimately saving lives from a laptop.

Keywords: crisis communications, public relations, media management, news media

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3 Water Monitoring Sentinel Cloud Platform: Water Monitoring Platform Based on Satellite Imagery and Modeling Data

Authors: Alberto Azevedo, Ricardo Martins, André B. Fortunato, Anabela Oliveira

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Water is under severe threat today because of the rising population, increased agricultural and industrial needs, and the intensifying effects of climate change. Due to sea-level rise, erosion, and demographic pressure, the coastal regions are of significant concern to the scientific community. The Water Monitoring Sentinel Cloud platform (WORSICA) service is focused on providing new tools for monitoring water in coastal and inland areas, taking advantage of remote sensing, in situ and tidal modeling data. WORSICA is a service that can be used to determine the coastline, coastal inundation areas, and the limits of inland water bodies using remote sensing (satellite and Unmanned Aerial Vehicles - UAVs) and in situ data (from field surveys). It applies to various purposes, from determining flooded areas (from rainfall, storms, hurricanes, or tsunamis) to detecting large water leaks in major water distribution networks. This service was built on components developed in national and European projects, integrated to provide a one-stop-shop service for remote sensing information, integrating data from the Copernicus satellite and drone/unmanned aerial vehicles, validated by existing online in-situ data. Since WORSICA is operational using the European Open Science Cloud (EOSC) computational infrastructures, the service can be accessed via a web browser and is freely available to all European public research groups without additional costs. In addition, the private sector will be able to use the service, but some usage costs may be applied, depending on the type of computational resources needed by each application/user. Although the service has three main sub-services i) coastline detection; ii) inland water detection; iii) water leak detection in irrigation networks, in the present study, an application of the service to Óbidos lagoon in Portugal is shown, where the user can monitor the evolution of the lagoon inlet and estimate the topography of the intertidal areas without any additional costs. The service has several distinct methodologies implemented based on the computations of the water indexes (e.g., NDWI, MNDWI, AWEI, and AWEIsh) retrieved from the satellite image processing. In conjunction with the tidal data obtained from the FES model, the system can estimate a coastline with the corresponding level or even topography of the inter-tidal areas based on the Flood2Topo methodology. The outcomes of the WORSICA service can be helpful for several intervention areas such as i) emergency by providing fast access to inundated areas to support emergency rescue operations; ii) support of management decisions on hydraulic infrastructures operation to minimize damage downstream; iii) climate change mitigation by minimizing water losses and reduce water mains operation costs; iv) early detection of water leakages in difficult-to-access water irrigation networks, promoting their fast repair.

Keywords: remote sensing, coastline detection, water detection, satellite data, sentinel, Copernicus, EOSC

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2 Structural Fluxionality of Luminescent Coordination Compounds with Lanthanide Ions

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

Abstract:

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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1 Cultivation of Halophytes: Effect of Salinity on Nutritional and Functional Properties

Authors: Luisa Barreira, Viana Castaneda, Maria J. Rodrigues, Florinda Gama, Tamara Santos, Marta Oliveira, Catarina Pereira, Maribela Pestana, Pedro Correia, Miguel Salazar, Carla Nunes, Luisa Custodio, Joao Varela

Abstract:

In the last century, the world witnessed an exponential demographic increase that has put an enormous pressure on agriculture and food production. Associated also with climate changes, there has been a decrease in the amount of available freshwater and an increased salinization of soils which can affect the production of most food crops. Halophytes, however, are plants able to withstand high salinities while maintaining a good growth productivity. To cope with the excess salt, they produce secondary metabolites (e.g. vitamins and phenolic compounds) which, along with the natural presence of some minerals, makes them not only nutritionally rich but also functional foods. Some halophytes, as quinoa or salicornia, are already used in some countries, mostly as gourmet food. Hydroponic cultivation of halophytes using seawater or diluted seawater for watering can decrease the pressure on freshwater resources while producing a nutritional and functional food. The XtremeGourmet project funded by the EU aims to develop and optimize the production of different halophytes by hydroponics. One of the more specific objectives of this project is the study of halophytes’ productivity and chemical composition under different abiotic conditions, e.g. salt and nutrient concentration and light intensity. Three species of halophytes commonly occurring in saltmarshes of the South of Portugal (Inula chrithmoides, Salicornia ramosissima and Mesembryanthemum nodiflorum) were cultivated using hydroponics under different salinities, ranging from 5 to 45 dS/m. For each condition, several parameters were assessed namely: total and commercial productivity, electrical conductivity, total soluble solids, proximal composition, mineral profile, total phenolics, flavonoids and condensed tannins content and antioxidant activity. Results show that productivity was significantly reduced for all plants with increasing salinity up to salinity 29 dS/m and remained low onwards. Oppositely, the electrical conductivity and the total soluble solids content of the produced plants increased with salinity, reaching a plateau at 29 dS/m. It seems that plants reflect the salt concentration of the water up to some point, being able to regulate their salt content for higher salinities. The same tendency was observed for the ash content of these plants, which is related to the mineral uptake from the cultivating media and the plants’ capacity to both accumulate and regulate ions’ concentration in their tissues. Nonetheless, this comes with a metabolic cost which is observed by a decrease in productivity. The mineral profile of these plants shows high concentrations of sodium but also high amounts of potassium. In what concerns the microelements, these plants appear to be a good source of manganese and iron and the low amounts of toxic metals account for their safe consumption in moderate amounts. Concerning the phenolics composition, plants presented moderate concentrations of phenolics but high amounts of condensed tannins, particularly I. crithmoides which accounts for its characteristic sour and spicy taste. Contrary to some studies in which higher amounts of phenolics were found in plants cultivated under higher salinities, in this study, the highest amount of phenolic compounds were found in plants grown at the lowest or intermediate salinities. Nonetheless, there was a positive correlation between the concentration of these compounds and the antioxidant capacity of the plants’ extracts.

Keywords: functional properties, halophytes, hydroponics, nutritional composition, salinity effect

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