Thermal and physical properties of crude palm oil with higher oleic content

Interspecific hybridization of oil palms (E. guineensis × E. oleifera) was initially exploited to provide disease resistance and, consequently, increased oleic acid content. Besides the growing importance of this cultivar to the market, there is little information about this oil’s properties. In this context, this study aimed to determine a comprehensive physicochemical and thermal characterization of hybrid palm oil (HOPO) compared with the better-known African palm oil (APO). Differences in the distribution of fatty acids, carotenoids, and tocols were observed. Minor differences in density and viscosity were found between the oils, with no relevance for the materials’ processing design. Nevertheless, HOPO showed unique crystallization behavior, which potentially can affect industrial operations, such as fractionation. HOPO did not present the two thermal characteristic regions of APO, attributed to olein and stearin fractions. The HOPO demonstrated a decrease in the melting point of more than 3 °C in relation to APO, and a reduction in the crystallization point of more than 6 °C. Furthermore, besides the higher content of unsaturated fatty acids, HOPO was more stable than APO due to a higher antioxidant content. These results could be useful to establish operation conditions for processes using palm oil from hybrid oil palm

Análise e modelagem termodinâmica do equilíbrio sólido-líquido de sistemas binários contendo terpenóides ou líquidos iônicos com ácidos graxos

Orientadores: Eduardo Augusto Caldas Batista, Guilherme José MaximoDissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de AlimentosResumo: busca por solventes líquidos a temperaturas amenas e que sejam ambientalmente benignos, em substituição aos orgânicos amplamente usados, tem crescido e se tornado um dos principais focos da indústria e de órgãos de pesquisa. Terpenos e líquidos iônicos vêm sendo pesquisados por apresentarem potencial para serem utilizados como solventes, porém alguns apresentam altas temperaturas normais de fusão, dificultando as suas aplicações em técnicas e processos. A partir do problema exposto, esse estudo teve por objetivo investigar o equilíbrio sólido-líquido de misturas binárias contendo terpenóides (L(-)-mentol ou timol) com ácidos graxos saturados (C8:0-C18:0) e insaturado (C18:1) e líquidos iônicos ([N1111]Cl, [N2222]Cl, [N3333]Cl e [N4444]Cl) com ácidos graxos saturados (C10:0-C18:0), para avaliação do possível decréscimo da temperatura normal de fusão da mistura binária em relação às dos componentes puros. Foram analisados 14 sistemas binários contendo terpenóides e 20 contendo líquidos iônicos. As medidas experimentais foram realizadas pela técnica de Calorimetria Exploratória Diferencial. A modelagem termodinâmica, empregando o algoritmo Crystal-T, foi usada para a descrição e a predição da linha liquidus. Para os dois grupos de sistemas, o modelo molecular Margules de 3 sufixos foi o que melhor correlacionou os dados experimentais com desvio médio absoluto igual a 1,03 K para os sistemas contendo terpenóides e 10,32 K para os contendo líquidos iônicos. No geral, em ambos os sistemas, desvios positivos da idealidade foram observados para maiores concentrações de ácidos graxos, e com o aumento da concentração do terpenóide ou líquido iônico, o desvio foi negativo. Nos sistemas com terpenóides, foram obtidas misturas líquidas à temperatura ambiente (298,15 K) com ácidos graxos com menores temperaturas de fusão. O maior decréscimo na temperatura de fusão das misturas binárias em relação às dos componentes puros, foi observado para o sistema envolvendo timol + ácido caprílico (52,00 K) no ponto eutético calculado pela modelagem termodinâmica. Para os sistemas com líquidos iônicos, misturas com temperatura abaixo da temperatura ambiente foram observadas apenas para os sistemas contendo [N3333]Cl e [N4444]Cl, sendo esses os líquidos iônicos com menor temperatura de fusão. Para esse grupo, o maior decréscimo na temperatura de fusão da mistura binária (346,40 K) em relação às dos componentes puros foi observado para o sistema [N1111]Cl + ácido palmítico no ponto eutético calculado pela modelagem termodinâmica. A partir dos resultados obtidos, grandes reduções na temperatura de fusão foram observadas e que essas foram próximas ou abaixo da temperatura ambiente fortalecendo o potencial uso dessas misturas como solventesAbstract: The search for liquid solvents at mild temperatures and that are environmentally benign, replacing the widely used organic ones, has grown into one of the main foci of industry and research organizations. Terpenes and ionic liquids have been investigated because they have the potential to be used as solvents, however some of them have high normal melting temperatures, making difficult their applications in techniques and processes. Taking into account, the aim of this study was to investigate the solid-liquid equilibrium of binary mixtures containing terpenoids (L(-)-menthol or thymol) with saturated fatty acids (C8:0-C18:0) and a unsaturated one (C18:1) and ionic liquids ([N1111]Cl, [N2222]Cl [N3333]Cl and [N4444]Cl) with saturated fatty acids (C10:0-C18:0), for evaluation of the possible decrease of the normal melting temperature of the binary mixture in relation to those of the pure components. 14 binary systems containing terpenoids and 20 containing ionic liquids were analyzed. Experimental measurements were performed using the Differential Scanning Calorimetry technique. Thermodynamic modeling, employing the Crystal-T algorithm, was used to describe and predict the liquidus line. For both groups of systems, the three-suffix Margules molecular model was the one that best correlated the experimental data, with absolute average deviation equal to 1.03 K for systems containing terpenoids and 10.32 K for systems containing ionic liquids. In general, in both group of systems, positive deviations from ideality were observed for higher concentrations of fatty acids, and with the increase of the concentration of terpenoid or ionic liquid, the deviation was negative. In the terpenoid systems, liquid mixtures were obtained at room temperature (298.15 K) with fatty acids with lower melting temperatures. The highest decrease in the melting temperature of the binary mixtures in relation to those of the pure components was observed for the system involving thymol + caprylic acid (52.00 K) in the calculated eutectic point by thermodynamic modeling. For systems with ionic liquids, mixtures with temperature below room temperature were observed only for systems containing [N3333]Cl and [N4444]Cl, which are the ionic liquids with lower melting temperature. For this group, the highest decrease in the melting temperature of the binary mixture (346.40 K) in relation to those of the pure components was observed for the [N1111]Cl + palmitic acid system in the calculated eutectic point by thermodynamic modeling. From the obtained results, large reductions in the melting temperature were observed and these were near or below room temperature, strengthening the potential use of these mixtures as solventsMestradoEngenharia de AlimentosMestra em Engenharia de AlimentosCAPESFAPESPCNP

Phase equilibrium of fats and monoterpenes and how it affects chocolate quality

Due to triacylglycerol (TAG) polymorphism in cocoa butter, processes conditions or storage, chocolate can present a defect called "fat bloom", when the fat liquid fraction migrates to the chocolate surface resulting in a whitish and brittle appearance. The addition of essential oils, rich in monoterpenes, has been studied as an alternative to avoid it. Some theories have been considered to explain this phenomenon but no one elucidated what kind of thermodynamic interactions could rule such an effect. Therefore, this work was aimed at describing the solid-liquid equilibrium (SLE) behavior of monoterpenes + TAG mixtures, in order to comprehend how monoterpenes could affect the solid phase of a fat. Experimental SLE data were measured by differential scanning calorimetry and optical microscopy and also modeled by the SLE theory. Results showed that monoterpenes could promote significant changes in the TAG crystalline habit by forming solid solutions (SS). This profile varied with the composition of TAG and monoterpene. The SS increased the initial fat melting temperature which could partially explain why such compounds improve chocolate quality, mitigating the fat bloom, according literature. The SLE was here a powerful tool for evaluating the effects of addictives in food formulation, which is an inspiration for future works in this field64832313243CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESP305870/2014-9; 406963/2016-9; 308924/2017-7; 140702/2017-2sem informação2014/21252-0; 2016/08566-1The authors wish to acknowledge Prof. Dr. Priscilla Efraim,School of Food Engineering, UNICAMP, for important support and suggestions, and the national funding agencies: National Council for Scientific and Technological Develop-ment (CNPq), Brazil, Grant No. 305870/2014-9, Grant No.406963/2016-9, Grant No. 308924/2017-7, and Grant No.140702/2017-2; The São Paulo Research Foundation(FAPESP), Brazil, Grant No. 2014/21252-0 and Grant No.2016/08566-1; and The Teaching, Research and ExtensionSupport Fund (FAEPEX-UNICAMP), Brazil, Grant No. 125/16 for financial support and scholarships. This study was also financed in part by the Coordenação de Aperfeiçoamento de Pessoal de Nível Superior, Brasil (CAPES) - Finance Code00

Phospholipase cocktail : a new degumming technique for crude soybean oil

Enzymatic degumming (EDG) is an emerging alternative process for decreasing the phosphorus content, increasing the oil yield, and preserving the oil quality. Purifine (R) 3G is a cocktail of phospholipases composed of phospholipase A2 (PLA2), phospholipase C (PLC), and phosphatidylinositol phospholipase C (PI-PLC). In this study, Purifine (R) 3G was applied to crude soybean oil, and the optimum degumming conditions (enzyme con-centration, temperature, and water dosage) were determined using a central composite rotatable design (CCRD). The contents of diacylglycerols (DAGs) and free fatty acids (FFAs) in the studied system considerably increased at temperatures below 64 C and enzyme concentrations above 100 mg/kg, while the phosphorus content decreased with increasing water amount and enzyme concentration. In particular, EDG with 200 mg/kg of Purifine (R) 3G conducted for 120 min at a temperature of 60 C and water concentration of 3% (w/w) lowered the residual phosphorus content to 8.9 mg/kg and increased the FFA and DAG concentrations by 0.17% and 0.72%, respectively. Meanwhile, EDG retained the tocopherol content in crude soybean oil, maintaining its quality. Hence, Purifine (R) 3G increases the neutral oil yield (FFA and DAG), decreases the phosphorus content, and preserves the oil quality, which make it a commercially viable degumming agent

ABC₂-SPH risk score for in-hospital mortality in COVID-19 patients

Objectives: The majority of available scores to assess mortality risk of coronavirus disease 2019 (COVID-19) patients in the emergency department have high risk of bias. Therefore, this cohort aimed to develop and validate a score at hospital admission for predicting in-hospital mortality in COVID-19 patients and to compare this score with other existing ones. Methods: Consecutive patients (≥ 18 years) with confirmed COVID-19 admitted to the participating hospitals were included. Logistic regression analysis was performed to develop a prediction model for in-hospital mortality, based on the 3978 patients admitted between March–July, 2020. The model was validated in the 1054 patients admitted during August–September, as well as in an external cohort of 474 Spanish patients. Results: Median (25–75th percentile) age of the model-derivation cohort was 60 (48–72) years, and in-hospital mortality was 20.3%. The validation cohorts had similar age distribution and in-hospital mortality. Seven significant variables were included in the risk score: age, blood urea nitrogen, number of comorbidities, C-reactive protein, SpO2/FiO2 ratio, platelet count, and heart rate. The model had high discriminatory value (AUROC 0.844, 95% CI 0.829–0.859), which was confirmed in the Brazilian (0.859 [95% CI 0.833–0.885]) and Spanish (0.894 [95% CI 0.870–0.919]) validation cohorts, and displayed better discrimination ability than other existing scores. It is implemented in a freely available online risk calculator (https://abc2sph.com/). Conclusions: An easy-to-use rapid scoring system based on characteristics of COVID-19 patients commonly available at hospital presentation was designed and validated for early stratification of in-hospital mortality risk of patients with COVID-19.</p