Metodologias para determinação de ácidos graxos em alimentos por técnicas cromatográficas, eletroforéticas e espectroscópicas

The addition of hydrogenated vegetable oils to food has been restricted worldwide due to the harmful effects that industrial trans fatty acids (TFA) can cause to human health. The development of new analytical methods is needed to attend legal requirements, and fast methodologies for TFA determination in foods were the focus of this thesis. Initially, a method for the determination of total TFA of octadecenoic acid in foods was optimized through Capillary Zone Electrophoresis with Direct Absorption Detection within the Ultraviolet Region. Optimum instrumental parameters were studied by using a background electrolyte previously described in the literature to direct detection, through an univariate evaluation of capillary length and a 32 factorial design having voltage and temperature as factors. Sample preparation was then studied, and comprised only alkaline hydrolysis of triacylglycerols. The validation of the developed method comprised the evaluation of linearity, specificity, precision, accuracy, robustness, and limits of detection and quantification. Relative standard deviation ≤ 5,72 % were obtained for instrumental precision when considering peak area, peak height and migration time, in a quadruplicate injection of standards. The calculated detection and quantification limits were 0,17 and 0,54 mmol L-1, respectively. In addition, no significant evidence was found within the 95% confidence interval when the methods by Capillary Electrophoresis and Gas Chromatography were compared. Among all the methods available in the literature for the determination of total TFA from octadecenoic acid using Capillary Electrophoresis, this is the method that provides the fastest result so far, with an analysis time less than 4 min. A new method for the separation of major TFA positional isomers of octadecenoic acid in food from natural and industrial origin (vaccenic and elaidic acids) was then developed using Capillary Zone Electrophoresis Modified with Cyclodextrins and Direct Absorption Detection within the Ultraviolet Region. The electrolyte was optimized univariately for this novel separation, and instrumental parameters, such as voltage and temperature, were optimized by a 22 factorial design. Sample preparation was evaluated for spreadable cheese, and only the alkaline hydrolysis of triacylglycerols was effective for the preparation of this matrix. The running time was less than 25 min and the estimated detection limit for elaidic and vaccenic acids was 0,02 mmol L-1. In addition, the mechanism of this separation was studied through molecular modeling. This approach presents a potential application in the discrimination of major isomeric TFA from natural and industrial origin, which is already required in legislations of several countries. Finally, other methodologies for the determination of fatty acids in food matrices were evaluated through chromatographic (Gas Chromatography with Flame Ionization Detector and Mass Spectrometry Detector, as well as Thin-layer Chromatography) and spectroscopic techniques (Infrared, Raman and Nuclear Magnetic Resonance) associated with chemometric tools, complementary to Capillary Electrophoresis, and were briefly discussed at the end of this thesis.A adição de gordura vegetal hidrogenada aos alimentos tem sido restrita mundialmente, devido aos malefícios que os ácidos graxos trans (AGT) de origem industrial podem causar a saúde humana. O desenvolvimento de novos métodos analíticos é necessário para atender aos requisitos legais e metodologias rápidas para determinação de AGT em alimentos foram o foco desta tese. Um método para quantificar AGT totais do ácido octadecenóico em alimentos foi otimizado inicialmente, empregando-se Eletroforese Capilar de zona com Detecção Direta por Absorção na Região do Ultravioleta. Estudou-se os parâmetros instrumentais ótimos para a análise utilizando um eletrólito já descrito na literatura para detecção direta, através de uma avaliação univariada do comprimento do capilar, e de um planejamento fatorial 32, tendo como fatores tensão e temperatura. O preparo das amostras foi então investigado, e compreendeu apenas hidrólise alcalina dos triacilgliceróis. A validação do método desenvolvido consistiu na avaliação da linearidade, especificidade, precisão, exatidão, robustez, e dos limites de detecção e quantificação. Desvios-padrão relativos ≤ 5,72 % foram obtidos para precisão instrumental considerando-se área do pico, altura do pico e tempo de migração, na injeção de padrões em quadruplicata. Os limites de detecção e quantificação calculados foram de 0,17 e 0,54 mmol L-1, respectivamente. Ademais, não foram evidenciadas diferenças significativas num intervalo de 95% de confiança quando os métodos por Eletroforese Capilar e Cromatografia Gasosa foram comparados para a determinação de AGT totais do ácido octadecenóico em diferentes amostras. Dentre os métodos disponíveis na literatura para quantificação de AGT totais do ácido octadecenóico empregando-se Eletroforese Capilar, este é o que fornece um resultado mais rápido até o momento, com tempo de análise menor que 4 minutos. Um novo método para a separação de AGT isoméricos posicionais do ácido octadecenóico majoritários em alimentos de ocorrência natural e industrial (ácido vacênico e ácido elaídico) também foi desenvolvido, usando Eletroforese Capilar de Zona Modificada por Ciclodextrinas e Detecção Direta por Absorção na Região do Ultravioleta. O eletrólito foi otimizado univariadamente para esta separação inédita e os parâmetros tensão e temperatura foram estudados através de um planejamento fatorial 22. O preparo de amostras foi avaliado para requeijões, e apenas hidrólise alcalina dos triacilgliceróis foi empregada no preparo desta matriz. O tempo de corrida foi menor que 25 min e o limite de detecção estimado para os ácidos elaídico e vacênico foi de 0,02 mmol L-1. Ademais, o mecanismo desta separação foi investigado através de modelagem molecular. Esta abordagem possui potencial aplicação na discriminação de isômeros de AGT majoritários de origem natural e industrial em alimentos, o que é exigido em legislações de vários países. Por fim, outros métodos para determinação de ácidos graxos em matrizes alimentícias foram avaliados, empregando-se técnicas cromatográficas (Cromatografia Gasosa com Detecção por Ionização em Chama e Espectrometria de Massas, bem como Cromatografia em Camada Delgada) e espectroscópicas (Infravermelho, Raman e Ressonância Magnética Nuclear) associadas a ferramentas quimiométricas, complementarmente a Eletroforese Capilar, e foram brevemente discutidas ao final desta tese.CAPES - Coordenação de Aperfeiçoamento de Pessoal de Nível Superio

Acesso e permanência na Educação Superior: o direito à educação em questão

This article aims to analyze access and retention in higher education, based on research developed by Axis 5 of Rede Universitas/Br. The methodology used was based on documentary and bibliographical research, in addition to the collection of data elucidated from the Higher Education Census organized by INEP. The analyzes are anchored in the perspective of dialectical historical materialism, identifying relationships that determine the concrete conditions presented. In the socio-political and economic period of the resurgence of neoconservatism in Brazil, in which scientific research has been discredited and public universities have suffered dismantling, the Pandemic generated by Covid-19 has interfered in the higher education scenario in several aspects, including with regard to access and retention of students. From this perspective, some conditions were identified that still remain as gaps to be overcome, such as the need to expand access for historically excluded groups and guarantee their permanence, the expansion of Student Assistance actions beyond PNAES, the diversification of pedagogical practices and the reinforcement of education beyond Capital

Severidade dos sintomas da doença de Parkinson

Objective: To analyze the severity of Parkinson ‘s disease symptoms in the elderly in the city of Vitória da Conquista - BA. Methodology: This is an exploratory, descriptive study with a quantitative approach, which was performed using the Bola de Neve technique, in the city of Vitória da Conquista - BA. Twenty-six elderly people participated in the study, signing the Informed Consent Term. The instruments for data collection were: Social-Biodemographic and Economic Questionnaire; Scale of Hoenh and Yahr, Mini Mental State Examination. The analysis of the quantitative data was performed using the statistical program StatisticalPackage for Social Science - SPSS. The project was approved by the ethics committee with approval opinion No. 2,418,868. Results: According to the data, the sociodemographic condition of the participants was described, revealing that the majority, 58.3% (14) were male, 50.0% (12) in the age group of 60 to 70 37.5% (9) had elementary school education level I. The analysis of this scale by Hoen and Yahr revealed that most participants are in stage 2 with 26.9% (7), followed by stage 4 with 23.1% (6). Conclusion: It was concluded that in the present study the majority of the interviewed elderly present a level of average dependence, according to the severity of the symptoms installed. In this sense, the data indicate that as PD evolves, greater health damages appear, retarding the mobility, the cognitive and leaving sequels in these individuals.Objetivo: Analisar a severidade dos sintomas da doença de Parkinson em idosos do município de Vitória da Conquista – BA. Metodologia: Trata-se de um estudo exploratório, descritivo, com abordagem quantitativa, que foi realizada por meio da técnica Bola de Neve, no município de Vitória da Conquista – BA. Aceitaram participar do estudo 26 idosos, assinando o Termo de Consentimento Livre Esclarecido. Os instrumentos para coleta dos dados foram: Questionário Sóciobiodemográfico e Econômico; Escala de Hoenh e Yahr, Mini Exame do Estado Mental. A análise dos dados quantitativos foi realizada com auxílio do programa estatístico Statistical Package for Social Science – SPSS. O projeto foi aprovado pelo comitê de ética com o parecer de aprovação nº2.418.868. Resultados: De acordo com os dados da pesquisa encontra-se descrita a condição sociodemográfica dos participantes, revelando que a maioria, 58,3% (14) é do sexo masculino, 50,0% (12) na faixa etária de 60 a 70 anos, 37,5% (9) tem nível de escolaridade de ensino fundamental I.A análise dessa escala de Hoen e Yahr revelou que maior parte dos participantes se encontram no estágio 2 com 26,9% (7), vindo em seguida o estágio 4 com 23,1% (6).  Conclusão: Concluiu-se que no presente estudo a maioria dos idosos entrevistados apresentam um nível de dependência média, de acordo a severidade dos sintomas instalados. Neste sentido, os dados indicam que conforme a DP evolui surgem maiores danos à saúde retardando a mobilidade, o cognitivo e deixando sequelas nesses indivíduos

Pumpkin seeds (Cucurbita moschata - Jacarezinho cultivar): characterization of the oil extracted by solvent and supercritical fluid and study of anti-parasitary activity / Sementes de abóbora (Cucurbita moschata - cultivar Jacarezinho): caracterização do óleo extraído por solvente e fluido supercrítico e estudo da atividade antiparasitária

The presence of many biologically active components makes pumpkins extremely attractive to the phytochemical manufacturing industry. Studies have demonstrated that the oil extracted from the seeds has different biological activities. This study aimed to determine the fatty acid composition and total tocopherol content of the pumpkin seed oil (Cucurbita moschata – Jacarezinho cultivar) extracted by supercritical carbon dioxide (Sc-CO2) and hexane/isopropanol. The fatty acids composition and content of total tocopherols were determined by GC, GC/FID, HPLC, respectively. We also evaluated in vitro schistosomicidal activities of the crude oil, which have been described with anti-parasitic activities. Sc-CO2 extracted pumpkin seed oil, with a maximum yield of 24.3 ± 0.4%, much higher than hexane/isopropanol extraction (8.3 ± 2.7%). Was not observe differences between the non-polar compounds present in the oil extracted by both methods. In the seed oil, unsaturated acids are dominant (oleic and linoleic). The results indicate that the oil has an excellent quality, with high contents of unsaturated fatty acids (73% of total fatty acids) and total tocopherols (14 mg100g-1 of oil). Although popularly reported as anti-parasitic activities caused no mortality, tegumental alterations or significant decrease in motor activity in all adult parasites. Sc-CO2 was able to extract pumpkin seed oil with a much higher yield than extraction with hexane/isopropanol and no differences were observe between the non-polar compounds present in the oil extracted by both methods. The oil is popularly used as an antiparasitic agent but in this study did not show antiparasitary actividies

IMPACTOS DA DOENÇA DE PARKINSON NA VIDA DOS IDOSOS

Population aging in Brazil has been increasing every decade and, coupled with this demographic growth, the incidence of neurodegenerative diseases such as Parkinson's disease (PD) has been increasing, especially among older . The aim of the study was to analyze the impacts of Parkinson's disease in the elderly. This is a descriptive, exploratory, qualitative study carried out in the city of Vitória da Conquista - BA, with 12 elderly people with Parkinson's Disease. The instruments for data collection were: Socio-demographic and Economic Questionnaire and the semi-structured interview. The data were analyzed applying the Thematic Content analysis emerging two thematic categories: Perception of the elderly on Parkinson's Disease and Impacts of Parkinson's Disease in the activities of daily living. Parkinson's disease impacts the lives of the elderly that can be perceived from feelings of sadness and worry, functional limitation, and resilience. Keywords: Elderly; Parkinson; Impacts; Aging.O envelhecimento populacional no Brasil vem crescendo a cada década e atrelado a esse crescimento demográfico foi observado o aumento da incidência das doenças neurodegenerativas, como a Doença de Parkinson que acomete, principalmente pessoas de mais idade. O objetivo do estudo foi analisar os impactos da Doença de Parkinson em idosos. Trata-se de estudo descritivo, exploratório, qualitativo realizado no município de Vitória da Conquista – BA, com 12 idosos com Doença de Parkinson. Os instrumentos para coleta dos dados foram: Questionário Sociobiodemográfico e Econômico e a Entrevista semiestruturada. Os dados foram analisados aplicando-se a análise de Conteúdo Temática emergindo duas categorias temáticas: Percepção dos idosos sobre a Doença de Parkinson, e Impactos da Doença de Parkinson nas atividades da vida diária. A doença de Parkinson gera impactos na vida dos idosos que podem ser percebidos a partir de sentimentos de tristeza e preocupação, limitação funcional e resiliência. Palavras-chave: Idosos; Parkinson; Impactos; Envelhecimento. &nbsp

Rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART): Study protocol for a randomized controlled trial

Background: Acute respiratory distress syndrome (ARDS) is associated with high in-hospital mortality. Alveolar recruitment followed by ventilation at optimal titrated PEEP may reduce ventilator-induced lung injury and improve oxygenation in patients with ARDS, but the effects on mortality and other clinical outcomes remain unknown. This article reports the rationale, study design, and analysis plan of the Alveolar Recruitment for ARDS Trial (ART). Methods/Design: ART is a pragmatic, multicenter, randomized (concealed), controlled trial, which aims to determine if maximum stepwise alveolar recruitment associated with PEEP titration is able to increase 28-day survival in patients with ARDS compared to conventional treatment (ARDSNet strategy). We will enroll adult patients with ARDS of less than 72 h duration. The intervention group will receive an alveolar recruitment maneuver, with stepwise increases of PEEP achieving 45 cmH(2)O and peak pressure of 60 cmH2O, followed by ventilation with optimal PEEP titrated according to the static compliance of the respiratory system. In the control group, mechanical ventilation will follow a conventional protocol (ARDSNet). In both groups, we will use controlled volume mode with low tidal volumes (4 to 6 mL/kg of predicted body weight) and targeting plateau pressure <= 30 cmH2O. The primary outcome is 28-day survival, and the secondary outcomes are: length of ICU stay; length of hospital stay; pneumothorax requiring chest tube during first 7 days; barotrauma during first 7 days; mechanical ventilation-free days from days 1 to 28; ICU, in-hospital, and 6-month survival. ART is an event-guided trial planned to last until 520 events (deaths within 28 days) are observed. These events allow detection of a hazard ratio of 0.75, with 90% power and two-tailed type I error of 5%. All analysis will follow the intention-to-treat principle. Discussion: If the ART strategy with maximum recruitment and PEEP titration improves 28-day survival, this will represent a notable advance to the care of ARDS patients. Conversely, if the ART strategy is similar or inferior to the current evidence-based strategy (ARDSNet), this should also change current practice as many institutions routinely employ recruitment maneuvers and set PEEP levels according to some titration method.Hospital do Coracao (HCor) as part of the Program 'Hospitais de Excelencia a Servico do SUS (PROADI-SUS)'Brazilian Ministry of Healt

Lipid composition of Brazilian chocolates and chocolate products with special emphasis on their fat origin and trans C18:1 Isomeric profile

The aim of this work was to provide recent fatty acid (FA) profiling of chocolates and chocolate products, principally C18:1 trans FAs (TFAs). Thirty-two samples were analyzed by gas chromatography and FAs were quantified. The total TFA content declared in chocolate labeling and the real TFA content were compared. The TFA content ranged from 0.04 to 2.51 g/100 g of sample, and it was noticed that several manufacturers were underestimating the total TFA content in their labeling. The main TFA isomers quantified were C18:1 trans-9 (0.006-0.244%), C18:1 trans-10 (0.009-0.392%), and C18:1 trans-11 (0.013-0.464%), expressed in g/100 g of sample. Principal component analysis was used to discriminate industrial fats from natural trans fats based on the isomeric TFA profile and dairy fat (DF) biomarkers allowing to group samples in four clusters: high TFA content and high DF content, high TFA content and low DF content, low TFA content and high DF content, and low TFA content and low DF content.This work was conducted during a scholarship at the Instituto de Investigación en Ciencias de la Alimentación (CIAL, CSIC-UAM) financed by CAPES—Brazilian Federal Agency for Support and Evaluation of Graduate Education within the Ministry of Education of Brazil (PDSE 88881187078/2018-01) and was supported by the Spanish Ministry of Economy and Competitiveness (Project AGL2016-75159-C2-2-R). GQAQ group also acknowledges CAPES (PNPD 23071022702/2018-43), Conselho Nacional de Desenvolvimento Científico e tecnológico—CNPq (303355/2017-4; 424032/2018-0), Instituto Nacional de Ciência e Tecnologia de Bioanalítica—INCTBio (FAPESP 2014/50867-3 and CNPq 465389/2014-7), Rede Mineira de Química—RQ-MG (CEX. RED-00010-14), and Fundação de Amparo a Pesquisa do Estado de Minas Gerais—FAPEMIG for fellowships and financial support.Peer reviewe

Evaluation of delivery form of eicosapentaenoic and docosahexaenoic acids during quality control of fish oil supplements

Fish oils (FO) omega-3 supplements containing eicosapentaenoic (EPA) and docosahexaenoic (DHA) acids are extensively consumed due to their beneficial health effects. Fatty acids (FA) are mainly available as triacylglycerols (TAG) and ethyl esters (EE) in FO supplements, and EE is known to be less bioavailable. Then, the evaluation of FA in FO should comprise not only omega-3 content but also the delivered form. This research aimed to approach in detail a set of chromatographic analytical methods employing TLC, GC-FID, and GC-MS for FO quality control, considering both FA contents and form. TAG and EE FA were differentiated by GC-FID, due to the difference in the retention times of compounds, and also by GC-MS, as a result of the different m/z spectra observed. TLC also distinguished both FA forms, but a mixture of TAG and EE in FO concentrates was not observed, as evidenced by GC techniques. Ten FO supplements available in the Brazilian market were analyzed, and the FA profiles of natural and concentrated FO were compared. EPA + DHA label claim compliance was also accessed. Their contents varied from 78 to 113% of labeled content, and only one supplement had FA in EE form. Brazilian FO supplements analyzed were a source of EPA and DHA and most products (except one sample) were accurately labeled according to current Brazilian regulation, which permits a variation in 20% of the declared content. Furthermore, the methodologies approached can be used in future researches considering FO analyses and bioavailability studies approaching the different FA forms.This study was financed in part by the “Coordenação de Aperfeiçoamento de Pessoal de Nível Superior” (CAPES), Brazil – Finance Code 001 and PDSE 8881187078/2018-01; Spanish Ministry of Economy and Competitiveness (AGL2016-75159-C2-2-R); “Conselho Nacional de Desenvolvimento Científico e Tecnológico” (CNPq), (303355/2017-4, 424032/2018-0); “Financiadora de Estudos e Projetos” (Finep), (CT-INFRA 01/2013-REF 0633/13); “Rede Mineira de Quimica” (RQ-MG), (CEX.RED- 00010-14), and “Instituto Nacional de Ciência e Tecnologia de Bioanalítica” (INCTBio), (FAPESP 2014/50867-3, CNPq 465389/2014-7).Peer reviewe

ATR-FTIR and raman spectroscopies associated with chemometrics for lipid form evaluation of fish oil supplements: A comparative study

Omega-3 fatty acids (FAs) are mainly available as triacylglycerols (TAGs) and ethyl esters (EEs) in fish oil supplements, and it is known that EEs are less bioavailable than TAGs in the human body. This study applied attenuated total reflectance with Fourier transform infrared (ATR-FTIR) and Raman spectroscopies associated with chemometrics to evaluate the supplements’ lipid form. Representative products were first characterized by reference chromatographic methods. Subsequently, principal component analysis (PCA) and partial least square discriminant analysis were performed in the spectral wavenumber ranges 1700–1780 (ATR-FTIR) and 1720–1770 cm–1 (Raman). TAGs and EEs were clearly distinguished along PC1 by employing both techniques, but a higher explained variance was obtained by ATR-FTIR. The prediction of TAG and EE fish oil samples was also better using ATR-FTIR (R2 = 0.99 versus 0.95 for Raman). However, both models correctly classified 100% of the samples, which indicates the suitability of these approaches to be used in quality control laboratories aiming for fish oil lipid form evaluation.This study was financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior – Brasil (CAPES) – Finance Code 001 and PDSE 88881187078/2018-01; Spanish Ministry of Economy and Competitiveness (AGL2016-75159-C2-2-R); Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq (Projects 303355/2017-4 and 424032/2018-0), Instituto Nacional de Ciência e Tecnologia de Bioanalítica - INCTBio (Projects FAPESP 2014/50867-3 and CNPq 465389/2014-7); Financiadora de Estudos e Projetos - Finep (CT-INFRA 01/2013-REF 0633/13); and Rede Mineira de Química - RQ-MG (Project CEX.RED-00010-14).Peer reviewe