H3PW12O40 (HPA), an efficient and reusable catalyst for biodiesel production related reactions: esterification of oleic acid and etherification of glycerol

In esterification of oleic acid with methanol at 25 °C HPA displayed the highest activity. Moreover the HPA could be reused after being transformed into its cesium salt. In the reaction of etherification of glycerol HPA and Amberlyst 35W showed similar initial activity levels. The results of acid properties demonstrate that HPA is a strong protonic acid and that both surface and bulk protons contribute to the acidity. Because of its strong affinity for polar compounds, HPA is also seemingly dissolved in both oleic acid and methanol. The reaction in this case proceeds with the catalyst in the homogenous phase.

Alkaline earth layered benzoates as reusable heterogeneous catalysts for the methyl esterification of benzoic acid

This paper describes the synthesis and characterization of layered barium, calcium and strontium benzoates and evaluates the potential of these materials as catalysts in the synthesis of methyl benzoate. The methyl esterification of benzoic acid was investigated, where the effects of temperature, alcohol:acid molar ratio and amount of catalyst were evaluated. Ester conversions of 65 to 70% were achieved for all the catalysts under the best reaction conditions. The possibility of recycling these metallic benzoates was also demonstrated, evidenced by unaltered catalytic activity for three consecutive reaction cycles.

Produção de lipases de Aspergillus niger e Aspergillus fumigatus através de fermentação em estado sólido, avaliação da especificidade do substrato e seu uso em reações de esterificação e alcoólise: evaluation of substrate specificity and use in esterification and alcoholysis reactions

Filamentous fungi were cultured under solid state fermentation of soybean residues to produce lipases. Enzymes produced by Aspergillus niger esterified oleic and butyric acids in the presence of ethanol, while enzymes produced by Aspergillus fumigatus demonstrated no esterification activity toward lauric acid. In case of A. niger, direct lyophilization of fermented bran led to higher esterification activity. The esterification of oleic acid by enzymes of A. fumigatus was neither influenced by pH adjustment nor by the extraction process. Conversions to ethyl esters were higher after pH adjustment with lyophilized liquid extract of A. niger.

Resistance of schistosomes to hycanthone and oxamniquine

Genetic crosses between phenotypically resistant and sensitive schistosomes demonstrated that resistance to hycanthone and oxamniquine behaves like a recessive trait, thus suggesting that resistance is due to the lack of some factor. We hypothesized that, in order to kill schistosomes, hycanthone and oxamniquine need to be converted into an active metabolite by some parasite enzyme wich, if inactive, results in drug resistance. Esterification of the drugs seemed to be the most likely event as it would lead to the production of an alkylating agent upon dissociation of the ester. An artificial ester of hycanthone was indeed active even in resistant worms, thus indirectly supporting our hypothesis. In addition, several lines of evidence demonstrated that exposure to hycanthone and oxamniquine results in alkylation of worm macromolecules. Thus, radioactive drugs formed covalent bonds with the DNA of sensitive (but not of resistant) schistosomes; an antiserum raised against hycanthone detected the presence of the drug in the purified DNA fraction of sensitive (but not of resistant) schistosomes; a drug-DNA adduct was isolated from hycanthone-treated worms and fully characterized as hycanthone-deoxyguanosine.

Organo-gel: um novo sistema para a imobilização de lipases e sua aplicação em síntese orgânica

Lipases have been immobilized in microemulsion-based organogels (MBG's) and successfully utilized for the enantioselective esterification, diesterification and transesterification reactions, in organic solvents at 25ºC. This methodology is described as a new alternative for the use of enzymes in organic solvents. High enzymic stability has been observed. We have also used this methodology for the successful resolution of chiral secondary alcohols. This is a convenient way of using this catalyst in organic solvents which employs small amounts of the enzyme (250mg/mL).

Síntese do butirato de n-butila empregando lipase microbiana imobilizada em copolímero de estireno-divinilbenzeno

This work investigates the reaction parameters of an immobilized lipase in the esterification reaction of n-butanol and butyric acid. Microbial lipase from Candida rugosa was immobilized onto styrene-divinylbenzene copolymer (STY-DVB) and subsequently introduced in an organic medium containing substrates in appropriate concentrations. Heptane was selected as solvent on the basis of its compatibility with the resin and the enzyme. The influence of molar ratio of acid to alcohol, amount of immobilized lipase and temperature on the butyl butyrate formation was determined. The results were compared with those achieved with free lipase and Lipozyme (commercially immobilized lipase) under the same operational conditions.

Aplicação de lipases microbianas na obtenção de concentrados de ácidos graxos poliinsaturados

Several polyunsaturated fatty acids (PUFA) belonging to the ômega 6 series, such as cis-6,9,12 gamma-linolenic acid, as well as those of the ômega 3 series, such as cis-5,8,11,14,17-eicosapentaenoic acid and cis-4,7,10,13,16,19-docosahexaenoic acid are of considerable interest due to their nutritional and therapeutic properties. Methods used for the concentration of PUFA from natural sources include urea adduct formation, solvent winterization, supercritical fluid extraction and lipase-catalyzed reaction. Lipases are known to have little reactivity on PUFA and these acids can be enriched by selective hydrolysis, direct esterification of glycerol with PUFA and interesterification. Since lipase reactions are advantageous with respect to fatty acid, positional specificities and mild incubation condition, these enzymes are considered to be suitable for the production of PUFA concentrates for medical purposes.

Efeito do polietilenoglicol e da albumina na imobilização de lipase microbiana e na catálise em meio orgânico

Poly (ethylene) glycol (PEG) and bovine serum albumin (BSA), as additive agents, were used to enhance the activity of immobilized microbial lipase in organic solvent. Controlled pore silica (CPS) was selected as matrix and different immobilization procedures were evaluated: directly lipase binding on CPS and simultaneous addition of lipase and additive agent on the same support. The highest coupling yield (59.6%) was attained when the immobilization procedure was performed at lipase loading of 150 U/g support in the presence of PEG-1.500. This immobilized system was used in esterification reactions under repeated batch cycles and the biocatalyst half-life was found to increase 2.7 times when compared with the control.

Potencial de biocatálise enantiosseletiva de lipases microbianas

Microbial lipases have a great potential for commercial applications due to their stability, selectivity and broad substrate specificity because many non-natural acids, alcohols or amines can be used as the substrate. Three microbial lipases isolated from Brazilian soil samples (Aspergillus niger; Geotrichum candidum; Penicillium solitum) were compared in terms of their stability and as biocatalysts in the enantioselective esterification using racemic substrates in organic medium. The lipase from Aspergillus niger showed the highest activity (18.2 U/mL) and was highly thermostable, retaining 90% and 60% activity at 50 ºC and 60 ºC after 1 hour, respectively. In organic medium, this lipase provided the best results in terms of enantiomeric excess of the (S)-active acid (ee = 6.1%) and conversion value (c = 20%) in the esterification of (R,S)-ibuprofen with 1-propanol in isooctane. The esterification reaction of the racemic mixture of (R,S)-2-octanol with decanoic acid proceeded with high enantioselectivity when lipase from Aspergillus niger (E = 13.2) and commercial lipase from Candida antarctica (E = 20) were employed.

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.

70º aniversário do biodiesel em 2007: evolução histórica e situação atual no brasil

Periodically, during petroleum shortages, vegetable oils and their derivatives have been proposed as alternatives to petroleum diesel fuel. Different approaches have been proposed, including the use of pure vegetable oils (or blends) or their derivatives. Indeed, the use of fatty-acid methyl or ethyl esters (usually known as "biodiesel") produced by alcoholysis of triacylglycerides or esterification of fatty acids was initially proposed in Belgium 70 years ago, when the first world patent was deposited. Recently, foreign dependence on diesel fuel and the petroleum crisis have increased the discussion in Brazil on starting to use alternatives to diesel fuel, being biodiesel the alternative of choice for a large petroleum diesel substitution program.

Comparação do desempenho da lipase de candida rugosa imobilizada em suporte híbrido de polissiloxano-polivinilálcool empregando diferentes metodologias

The efficiency for immobilizing microbial Candida rugosa lipase on a hybrid matrix of polysiloxane polyvinyl alcohol, by adsorption, covalent coupling and encapsulation was compared. The activities of immobilized derivatives were evaluated using p-nitrophenylpalmitate (hydrolysis) and butyric acid and butanol (esterification) as substrates. Operational stability and storage tests were also performed. Among the procedures tested, the proposed matrix was efficient for immobilizing C. rugosa lipase by adsorption and covalent coupling techniques and unsuitable for encapsulation purposes. The results reveal that better catalytic properties in both aqueous and organic media were demonstrated by the covalent coupling POS-PVA immobilized lipase, including also satisfactory half-life and good storage stability.

Monoglicerídeos: produção por via enzimática e algumas aplicações

Monoglycerides (MAG) are non-ionic surfactants, widely used in the pharmaceutical, food and cosmetic industries. Although MAGs are manufactured on an industrial scale by chemical glycerolysis of oils and fats, new developments in lipase catalyzed synthesis have been studied as an alternative to the classical method seeking to use clean technology and green chemistry. In this work, different methods such as glycerolysis, selective hydrolysis of fats and oils, and esterification of fatty acids or transesterification of esters with glycerol are presented. The properties and applications of the monoglycerides are also included in this review.

Cutinases fúngicas: propriedades e aplicações industriais

Cutinases (EC 3.1.1.74) are also known as cutin hidrolases. These enzymes share catalytic properties of lipases and esterases, presenting a unique feature of being active regardless the presence of an oil-water interface, making them interesting as biocatalysts in several industrial processes involving hydrolysis, esterification and trans-esterification reactions. They are also active in different reaction media, allowing their applications in different areas such as food industry, cosmetics, fine chemicals, pesticide and insecticide degradation, treatment and laundry of fiber textiles and polymer chemistry. The present review describes the characteristics, potential applications and new perspectives for these enzymes.

Biocombustíveis a partir de óleos e gorduras: desafios tecnológicos para viabilizá-los

Periodically, during petroleum shortage, fatty acids and their derivatives have been used as alternative fuels to those derived from petroleum. Different approaches have been proposed, including the use of neat fats and oils or their derivatives. Indeed, the utilization of biodiesel produced by alcoholysis of triacilglycerides or esterification of fatty acids, or hydrocarbons obtained from cracking of fatty materials were studied and used in several countries. Increasing concerns about energy security and climate changes have lead several countries, including Brazil, to start up biofuels programs. Different technologies are currently being developed in order to produce biofuels with economical feasibility. In this work are discussed alternative fatty raw-materials and processing technologies that are currently being studied in order to produce fuels suitable to sustainable substitute diesel fuel.