Even though edible oils undergo refining processes to remove undesirable components, commercial oils still contain small amounts of minor components that can contribute to either prooxidant and antioxidant pathways which ultimately affect the quality of the oils. The objective of this research was to determine the role of free fatty acids and mono- and diacylglycerols on the oxidative stability of oil-in-water emulsions. Free fatty acids acted as a strong prooxidants in stripped soybean oil-in-water emulsions. Concentrations as low as 0.1% of the lipid accelerated lipid oxidation rate by both shortening the lag phase of lipid hydroperoxide and hexanal formation. The results showed that the most likely mechanisms for the prooxidant activity of free fatty acids is through their ability to increase the negatively charge on emulsion droplets that in turn could attract the cationic transition metals to the emulsion droplet surface where they can interact with lipid and thus promote oxidation. The prooxidant activity of free fatty acids was dependent on fatty acid type with lipid oxidation rates being in the order of linolenic < linoleic < oleic. Surprisingly, an increase in the degree of unsaturation of the free fatty viii acids lowered the ability of the free fatty acids to promote oxidation which may be due to their differences in geometric shape thus influencing their ability to access the emulsion droplet interface and increase the negative charge. Overall, free fatty acids are strong prooxidants in oil-in-water emulsions. This prooxidant activity is dependent not only on their concentration but also on the molecular structure of the fatty acid. Addition of mono- and diacylglycerols in oil-in-water emulsions showed an antioxidative effect in both non-stripped and stripped soybean oil. Addition of 1-monooleoylglycerol only had a small impact on the oxidative stability of non-stripped soybean oil-in-water emulsions but did inhibit lipid oxidation in emulsions prepared with stripped soybean. Much stronger antioxidant activity was observed upon the addition of 1,2-dioleoyl-sn-glycerol to both non-stripped and stripped soybean oil-in-water emulsions. Both lipid hydroperoxide and hexanal formation decreased with increasing 1,2-dioleoyl-sn-glycerol concentrations with 2.5% 1,2-dioleoyl-sn-glycerol almost completely preventing hydroperoxide and hexanal production over the course of the study. Overall, these results suggest that diacylglycerols could be an effective antioxidant in oil-in-water emulsions which possibility due to their ability to form a liquid crystal phase which could form a physical barrier that decreases interactions between unsaturated fatty acids in the emulsion droplet core and prooxidants or oxygen in the aqueous phase of the emulsion. However, the antioxidant mechanism of diacylglycerols is not currently understood and needs further investigation.

Orientador: Lúcia Regina Durrant / Dissertação (mestrado) - Universidade Estadual de Campinas, Faculdade de Engenharia de Alimentos / Made available in DSpace on 2018-08-22T11:02:32Z (GMT). No. of bitstreams: 1 Pescumo_FernandaFranzoni_M.pdf: 1387373 bytes, checksum: baa6cd7b83f29182ab90172ebb03c248 (MD5) Previous issue date: 2013 / Resumo: Biossurfactantes e bioemulsificantes são compostos ativos de superfícies (CAS) produzidos por micro-organismos. Desempenham várias funções biológicas, e sua característica anfifílica, juntamente com baixa toxicidade, biodegradabilidade e resistência a extremos de pH, temperatura e salinidade, tem despertado o interesse para a aplicação dessas moléculas em processos biotecnológicos. Porém, o alto custo aliado à baixa produção ainda são impedimentos para a utilização em larga escala. Os desafios para se implementar a produção são: desenvolvimento de estratégias para tornar a produção economicamente viável e o isolamento de moléculas e microorganismos mais eficientes. Neste trabalho, foi estudada a produção, isolamento, extração e caracterização de um CAS por Gordonia amicalis. O micro-organismo foi cultivado em meio GYP (glucose, extracto de levedura, peptona) por 7 dias, e a extração foi feita por precipitação com sulfato de amônio, que resultou em uma concentração de 0,5 g/L do extrato bruto em meio líquido. O CAS não reduziu significativamente a tensão superficial do meio GYP, e apresentou um balanço hidrofílico-lipofílico (HBL) de caráter lipofílico, apresentando mais emulsões do tipo água em óleo (A/O) do que óleo em água (O/A). A molécula apresentou estabilidade a temperaturas de 25ºC a 100ºC, pH de 2 a 10 e salinidades de 5% a 15% quando cultivado por 7 dias, e foi capaz de modificar a interface água/superfície na análise de ângulo de contato. O extrato de 14 dias apresentou Atividade Emulsificante em 24 horas (AE24) reduzida em temperaturas acima de 50ºC, e ausente em pH ácido e salinidades de 5% e 10%. Análises de Cromatografia de Camada Delgada (CCD) revelaram presença de aminoácidos e açúcares na molécula e a análise do potencial zeta revelou que o CAS é um surfactante aniônico. Nas análises de Espectrometria no Infravermelho com Transformadas de Fourier (IR-TF) foram observados estiramentos indicativos de agrupamentos O-H e C-O, que podem indicar presença de grupos éter ou ésteres. O CAS produzido por Gordonia amicalis em meio sintético GYP mostrou-se um eficiente agente emulsificante, com potencial para aplicações biotecnológicas futuras / Abstract: Biosurfactants and bioemulssifiers are surface active compounds (SACs) produced by microorganisms. They have a wide variety of biological functions. Its amphiphilic characteristic, with low toxicity, biodegradability and resistance to extremes of pH, temperature and salinity, has increased the interest of these molecules for application biotechnological process. However, high costs and low production rates are restrictions to their widespread use. The challenges for implementing production are: developing strategies to turn the production economically feasible and isolating more efficient molecules and microorganisms. In this work, we studied the production, isolation, extraction and characterization of a SAC by a Gordonia amicalis. The microrganism was grown in GYP (Glucose, Yeast extract, Peptone) medium for 7 days, and the isolation was carried out by precipitation with ammonium sulfate, which resulted in 0.5 g / L of crude extract. The SAC did not significantly reduce the surface tension of GYP medium, and showed an hydrophilic-lipophilic balance (HLB) with lipophilic character, showing more water in oil (W/O) emulsions than oil in water (O/W) emulsions. The molecule extracted at 7 days was stable at temperatures ranging from 25 to 100 ° C, pH of 2-10 and salinities of 5-15%, and can modify the water/surface contact by the angle of contact analysis. The 14-day isolated extract showed EA24 reduced at temperatures above 50 ºC, and had no Emulsification Activity in 24 hours (EA24) in acid pH and salinity of 5% and 10%. Thin Layer Chromatography (TLC) analysis revealed the presence of sugars and amino acids in the molecule and the zeta potential analysis revealed the compound is an anionic surfactant. In the Fourier Transformed Infrared Spectrometry (FTIV) it were observed stretches indicatives of O-H and C-O groups, that might indicate ether or ester groups. The SAC produced by Gordonia amicalis in GYP medium proved to be an efficient emulsifier, with potential for biotechnological applications / Mestrado / Ciência de Alimentos / Mestra em Ciência de Alimentos

Charles University Faculty of Pharmacy in Hradec Králové Department of Biophysics and Physical Chemistry Consultant: PharmDr. Jan Marek, Ph.D. Supervisor: doc. PharmDr. Veronika Nováková, Ph.D. Student: Kateřina Pekařová Title of Thesis: Cationic surface active compounds and evaluation of its properties Quaternary ammonium salts are used as surfactants in many branches of the food, pharmaceutical and chemical industries. The basic properties of these substances were studied in the thesis. The critical micellar concentration of the homologous series of five substances was determined using the conductometric method. The theory of declining critical micellar concentration with the increasing length of the side alkyl chain has been verified. The hydrolytic activity of two commonly used cationic surfactants benzalconium chloride and benzoxonium chloride for the decomposition of the organophosphorus pesticide fenitrothion was tested. For these two substances, the effect of pH and temperature changes was evaluated. The influence of tenside concentration was also monitored. Benzoxonium chloride at 50 řC and pH 11was found as the most effective hydrolytic catalyst for the decomposition of the organophosphorus pesticide fenitrothione.