Estudo da influência do solvente, carboidrato e ácido graxo na síntese enzimática de ésteres de açúcares

The aim of this work was to gain knowledge of enzymatic processes for the synthesis fatty acid esters of sugar, with the objective to develop an enzymatic process for the preparation of non-toxic biodegradable surface-active agents derived entirely from renewable resources. A wide range of data were collected for reaction conditions involving different sugars (glucose, fructose and sucrose), fatty acids (oleic, palmitic, lauric), solvents (hexane, heptane and t-butanol) and different sources of lipases in both free and immobilized forms. As a solvent t-butanol provided the best conditions to create a catalytic liquid phase in which the reaction occurs. Sugars were preferentially esterified in the following order: fructose > glucose > sucrose, depending on the enzyme preparation. For fructose no influence was found concerning de acyl donor and similar rates were achieved for all tested fatty acids. Ester synthesis was maximized for substrates containing fructose, lauric or oleic acids, t-butanol and lipase from porcine pancreas immobilized on polysiloxane-polyvinyl alcohol particles. Under such conditions molar conversions were higher than 50%.

Otimização das condições de produção de ésteres etílicos a partir de óleo de peixe com elevado teor de ácidos graxos ômega-3

The production of ethyl esters by alcoholysis is an alternative for splitting triacylglycerols due to the possibility of using low temperatures, which results in oxidative protection of the polyunsaturated fatty acids. Ethyl esters produced under mild conditions of temperature could be used as substrate for obtaining structured lipids. The reaction parameters of production of ethyl esters from fish oil with high content of omega-3 fatty acids by alcoholysis were optimized using response surface methodology. An experimental design (2³) (with levels +1 and -1, six axial points with levels -alpha and +alpha and three central points) was applied. The variables investigated were concentration of catalyst, amount of ethyl alcohol and temperature. Ethyl ester conversion was monitored by high performance size exclusion chromatography (HPSEC) and the best result obtained was 95% conversion rate. The optimal conditions were 40 °C, 1% of NaOH and 36% of ethanol.

Imobilização de lipases em filme de caseinato de sódio/glicerol: aplicação na síntese de ésteres

Lipases from different sources were immobilized in sodium caseinate/glycerol film and used in the esterification reactions of aliphatic acids with alcohols in the presence of organic solvents. Lipases from Pseudomonas sp and Rhizopus oryzae were selected and the influence of several parameters was analyzed, including: lipase loading, organic solvent polarity, reaction temperature, chain length of alcohol and acid and enzyme/support reuse. For comparison, free enzymes were used under similar experimental conditions.

Lipídios estruturados obtidos a partir da mistura de gordura de frango, sua estearina e triacilgliceróis de cadeia média: I- Composição em ácidos graxos e em triacilgliceróis

The purpose of this study is to analyze the interactions that occur in binary and ternary fat blends between medium and long chain triacylglycerols and their structured lipids obtained by chemical interesterification through the analysis of their physico-chemical properties. The synthesized structured triacylglycerols presented from 14.8 to 58.4% medium chain fatty acids, from 15.7 to 37.2% saturated fatty acids, from 19.2 to 47.5% monounsaturated fatty acids, and from 6.7 to 15.2% essential fatty acids. Chemical interesterification modified the behavior of binary and ternary mixtures and new types of triacylglycerol groups were formed.

Lipídios estruturados obtidos a partir da mistura de gordura de frango, sua estearina e triacilgliceróis de cadeia média: II- pontos de amolecimento e fusão

The aim of the present work is to investigate the effects of blending and chemical interesterification reactions on the softening and melting behavior of chicken fat, its stearin and medium chain triacylglycerols, and blends thereof in various ratios. Chemical interesterification is a promising alternative to the current processes of modifying the physical properties of fats. In the experimental design 7 samples corresponding to 7 different blend proportions were used. The results were represented in triangular diagrams. The addition of stearin influenced the softening and melting points. The mixture response surface methodology proved to be an extremely useful tool for the optimization of the fat mixtures.

Efeito do triacilglicerídeo de cadeia média, da fibra e do cálcio na disponibilidade de magnésio e de zinco pelo método in vitro e metodologia de superfície de resposta

Nutritional therapy with enteral diets became highly specialized in the last years. This work aims to study the effect of the components of a formulation, namely fiber, calcium and medium-chain triglycerides, for dialysability of minerals. Analysis of multiple variables was done using response surface methodology. The level curve showed that the tertiary interaction MCT-fiber-calcium was the one that presented the highest synergism in the formulation. The proportion of 33% MCT, 25% fiber and 42% calcium, gave the best formulation for availability of magnesium.

Síntese de padrões cromatográficos e estabelecimento de método para dosagem da composição de ésteres de ácidos graxos presentes no biodiesel a partir do óleo de babaçu

Several alkyl esters were synthesized, purified, characterized by ¹H NMR and employed as standards for establishing chromatographic methods to monitor their formation in the synthesis of biodiesel. The efficiency of the chromatographic methods was confirmed with the products of enzymatic transesterification of babassu oil with different alcohols (C2 to C4), using Lipozyme as catalyst.

Efeito do 1-metilciclopropeno sobre a emissão dos ésteres voláteis de bananas ao longo do amadurecimento

Fresh green bananas (Musa sp., subgroup Prata) were treated with a dose of only 90 ηg g-1 of 1-MCP for 13 hours and the evolution of the volatile compounds along the ripeness was studied. A method to quantify the emission of esters was developed by cryogenic headspace and gas chromatography. Esters of acetate, butyrate, isobutyrate and isovalerate were found as major compounds. The application of the 1-MCP for 13 hours delayed the appearance of the coloration 8 of the peel for 3 days and decreased quantitatively in about 46% the total production of esters in the banana until the 15° day of harvested.

Lipídios modificados obtidos a partir de gordura do leite, óleo de girassol e ésteres de fitosteróis para aplicação em spreads

The objective of this paper was to evaluate the modifications in milkfat properties with the addition of sunflower oil (SO) and phytosterol esters (PE) and chemical interesterification. Fatty acid composition, softening point and consistency were determined. The saturation degree of milkfat decreased with the addition of SO and PE. Consequently, milkfat presented lower softening point and consistency. Chemical interesterification caused an increase in softening point due to the formation of higher amounts of trissaturated triacylglycerols with rearrangement. The incorporation of unsaturated fatty acids from SO and PE by milkfat triacylglycerols after chemical reaction caused linearization of consistency curves.

Cadeia do biodiesel da bancada à indústria: uma visão geral com prospecção de tarefas e oportunidades para P&D&I

Contextualized overview of the Biodiesel Production Chain, from the lab bench to the industry, with critical evaluation of state-of-art and technological development through scientific articles and patents, focusing on feedstock, reaction/production, first and second generation processes, specification and quality, transport, storage, co-products (effluents and sub-products), and emissions. Challenges are identified and solutions are proposed based on the Brazilian feedstock, edaphoclimatic conditions, process monitoring in remote regions, state policy, and environment preservation, among others. Forecasts are made based on the technology assessment, identifying future trends and opportunities for R&D&I.

Polarizabilidades e primeira hiperpolarizabilidades elétricas dipolares de ésteres E-4-amino-trans-1,3-butadienil-(1',2'-di-hidroxibenzeno) de boro, alumínio e gálio

Static electric dipole polarizabilities and first hyperpolarizabilites have been calculated for the title molecules and their 3' and 4'-nitro derivatives at ab-initio Hartree- Fock/6-31G(d, p) level. The influence of the pivotal p vacant 3A elements (B, Al or Ga) substitution on the electrical properties of these molecules is detailed. The axial vector components of the first hyperpolarizabilities β(0) of the push-pull 4'-nitro derivatives, -18.2×10-32 esu (B), -21.1×10-32 esu (Al) and -20.8×10-32 esu (Ga) are calculated to be as much as fourfold larger then that calculated for the p-nitroaniline, a reference organic molecule for comparison for this type of molecular property.

Comparação de técnicas de determinação de ésteres em cachaça

An analytical comparison of three different techniques for quantitative profile of esters in cachaça is reported. The Ministério da Agricultura Pecuária e Abastecimento (MAPA) recommends the use of GC/FID or volumetry. Despite being laborious and lacking in chemical speciation, the volumetric technique for total ester content shows to be appropriate, reproducible, and accurate for the analysis of cachaça. However, the GC/FID suggested by MAPA, considering only ethyl acetate, shows inaccuracy, underestimating the total ester content by a median factor of 72%, mainly due to the absence of ethyl lactate analysis. On the other hand, the GC/MS technique that comprises the analysis and speciation of nine esters, including ethyl lactate, proved to be reproducible, simple, fast and accurate for the analysis of total ester content in cachaça. Thus, the total ester content results obtained using GC/FID must be considered with precaution.

Determinação do teor de ésteres graxos em biodiesel metílico de soja por cromatografia gasosa utilizando oleato de etila como padrão interno

A method for ester content determination in soybean methyl biodiesel was studied, using ethyl oleate as internal standard. A biodiesel sample was analyzed and had its purity estimated as 92.8%. Method accuracy was evaluated by comparison with the result obtained via EN14103, with a relative difference of 0.1%. Repetitivity and intermediate precision were estimated as 2 and 1.5%, respectively.

Síntese de novas amidas graxas a partir da aminólise de ésteres metílicos

Recent biochemical and pharmacological studies have led to the characterization of different fatty acid amides as a new family of biologically active lipids. Here, we describe the synthesis of new amides from C16:0, 18:0, 18:1 and 18:1, OH fatty acids (FFA) families with cyclic and acyclic amines and demonstrate for the first time that these compounds produce citotoxic effects. Application of this method to the synthesis of fatty acid amides was performed using the esters aminolysis as a key step and various carboxylic amides were prepared in good yield from fatty acid methyl esters (FAMEs).

Filmes ultrafinos de ésteres de celulose: preparo, caracterização e imobilização de proteínas

In this study cellulose acetate butyrate (CAB) and carboxymehtylcellulose acetate butyrate (CMCAB) films adsorbed onto silicon wafers were characterized by means of ellipsometry, atomic force microscopy (AFM), sum frequency generation spectroscopy (SFG) and contact angle measurements. The adsorption behavior of lysozyme (LIS) or bovine serum albumin (BSA) onto CAB and CMCAB films was investigated. The amounts of adsorbed LIS or BSA onto CMCAB films were more pronounced than those onto CAB films due to the presence of carboxymethyl group in the CMCAB structure. Besides, the adsorption of BSA molecules on CMCAB films was more favored than that of LIS molecules. Antimicrobial effect of LIS bound to CAB or CMCAB layers was evaluated using Micrococcus luteus as substrate.