Enzymatic synthesis of monoglycerides by esterification reaction using Penicillium camembertii lipase immobilized on epoxy SiO(2)-PVA composite

Glycerol-fatty acid esterification has been conducted with lipase from Penicillium camembertii lipase immobilized on epoxy SiO(2)-PVA in solvent-free media, with the major product being 1-monoglyceride, a useful food emulsifier. For a given set of initial conditions, the influence of reaction was measured in terms of product formation and selectivity using different fatty acids as acyl donors. Results were found to be relatively dependent of the chain length of the fatty acids, showing high specificity for both myristic and palmytic acids attaining final mixture that fulfills the requirements established by the World Health Organization to be used as food emulsifiers. (C) 2010 Elsevier B.V. All rights reserved.

Packed-Bed Reactor Running on Babassu Oil and Glycerol to Produce Monoglycerides by Enzymatic Route using Immobilized Burkholderia cepacia Lipase

The aim of this study was the glycerolysis of babassu oil catalyzed by immobilized lipase from Burkholderia cepacia, in a continuous packed-bed reactor. The best reaction conditions were previously established in batchwise via response surface methodology as a function of glycerol-to-oil molar ratio and reaction temperature. The reactor operated continuously for 22 days at 50 A degrees C, and during the first 6 days, no significant decrease on the initial lipase activity was observed. Monoglycerides concentration was in the range from 25 to 33 wt.%. Subsequently, a progressive decrease in the activity was detected, and an inactivation profile described by Arrhenius model estimated values of 50 days and 1.37 x 10(-2) h(-1), for the half-life and deactivation coefficient, respectively.

Multipoint covalent immobilization of lipase on chitosan hybrid hydrogels: influence of the polyelectrolyte complex type and chemical modification on the catalytic properties of the biocatalysts

This work aimed at the production of stabilized derivatives of Thermomyces lanuginosus lipase (TLL) by multipoint covalent immobilization of the enzyme on chitosan-based matrices. The resulting biocatalysts were tested for synthesis of biodiesel by ethanolysis of palm oil. Different hydrogels were prepared: chitosan alone and in polyelectrolyte complexes (PEC) with kappa-carrageenan, gelatin, alginate, and polyvinyl alcohol (PVA). The obtained supports were chemically modified with 2,4,6-trinitrobenzene sulfonic acid (TNBS) to increase support hydrophobicity, followed by activation with different agents such as glycidol (GLY), epichlorohydrin (EPI), and glutaraldehyde (GLU). The chitosan-alginate hydrogel, chemically modified with TNBS, provided derivatives with higher apparent hydrolytic activity (HA(app)) and thermal stability, being up to 45-fold more stable than soluble lipase. The maximum load of immobilized enzyme was 17.5 mg g(-1) of gel for GLU, 7.76 mg g(-1) of gel for GLY, and 7.65 mg g(-1) of gel for EPI derivatives, the latter presenting the maximum apparent hydrolytic activity (364.8 IU g(-1) of gel). The three derivatives catalyzed conversion of palm oil to biodiesel, but chitosan-alginate-TNBS activated via GLY and EPI led to higher recovered activities of the enzyme. Thus, this is a more attractive option for both hydrolysis and transesterification of vegetable oils using immobilized TLL, although industrial application of this biocatalyst still demands further improvements in its half-life to make the enzymatic process economically attractive.

Kinetics and Modeling of Fatty Alcohol Ethoxylation in an Industrial Spray Loop Reactor

The kinetics of the ethoxylation of fatty alcohols catalyzed by potassium hydroxide was studied to obtain the rate constants for modeling of the industrial process. Experimental data obtained in a lab-scale semibatch autoclave reactor were used to evaluate kinetic and equilibrium parameters. The kinetic model was employed to model the performance of an industrial-scale spray tower reactor for fatty alcohol ethoxylation. The reactor model considers that mass transfer and reaction occur independently in two distinct zones of the reactor. Good agreement between the model predictions and real data was found. These findings confirm the reliability of the kinetic and reactor model for simulating fatty alcohol ethoxylation processes under industrial conditions.

Statin regulation of CYP3A4 and CYP3A5 expression

CYP3A4 and CYP3A5 are cytochrome P450 enzymes that are highly expressed in the liver and gut and metabolize endogenous compounds and xenobiotics. Statins are cholesterol-lowering drugs that are extensively metabolized by CYP3A4 and CYP3A5. The bioavailability of statins is affected by CYP3A4 and CYP3A5 and glucuronidases metabolism as well as uptake and efflux transporters that affect drug disposition. CYP3A4 and CYP3A5 variants have been demonstrated to influence the pharmacokinetics, efficacy and safety of statins. Inducers and inhibitors of CYP3A4 and CYP3A5 play an important role in reducing statin efficacy and increase the risk of adverse effects, respectively. Statins have been demonstrated to increase CYP3A expression in vitro, most likely because they are ligands to nuclear receptors (pregnane X receptor and constitutive androsterone receptor) that form heterodimers with retinoid X receptors and bind to responsive elements in the CYP3A4 and CYP3A5 promoter regions. This special report outlines the earlier studies on variability of response to statins owing to CYP3A variants and highlights findings on the induction of CYP3A4 and CYP3A5 expression by statins.

Expanding cyclitol structural diversity by biocatalysis and metalocatalysis. A click chemistry approach

The palladium catalyzed cross-coupling reaction of phenyltrifluoroborate with a chemoenzymatically derived bromoazidoconduritol, combined with 1,3-dipolar cycloaddition, with a variety of alkynes is described. Fourteen new compounds were synthesized in moderate to good yields. The click chemistry reaction can be effected by using sodium ascorbate and CuSO(4) center dot 5H(2)O as catalyst in toluene-H(2)O at room temperature.

Consecutive biocatalysis-palladium catalysis II: Synthesis of conduritol-alkyne conjugates

The palladium-catalyzed cross-coupling reaction of potassium alkynyltrifluoroborates with a chemoenzymatically derived deoxyconduritol is described. Six new compounds were synthesized in moderate to good yields. The alkynyl cross-coupling reaction can be effected using 10 mol% of Pd(PPh(3))(4) as Catalyst in toluene-H(2)O in the presence Of Cs(2)CO(3) as the inorganic base. (C) 2009 Elsevier B.V. All rights reserved.

Nucleophilic addition of potassium organotrifluoroborates to chiral cyclic N-acyliminium ions: stereoselective synthesis of functionalized N-heterocycles

The stereoselective nucleophilic addition of potassium aryl- and alkynyltrifluoroborates to cyclic N-acyliminium ion derivatives from N-benzyl-3,4,5-triacetoxy-2-pyrrolidinone, affording the respective 5-substituted 2-pyrrolidinone is described. The products were obtained in moderate to good yields and with preference for the syn diastereomer. (C) 2008 Elsevier Ltd. All rights reserved.

Synthesis of unnatural cyclitols via a combined enzymatic-palladium catalysis approach

The Suzuki-Miyaura cross-coupling reaction of a hydroxylated vinyl bromide obtained by a chemoenzymatic approach with a diverse range of potassium organotrifluoroborates has been accomplished catalyzed by Pd(PPh(3))(4) in satisfactory yields. A variety of functional groups are tolerated in the nucleophilic partner. (C) 2008 Elsevier B.V. All rights reserved.

Structured lipids obtained by chemical interesterification of olive oil and palm stearin

Interesterification of palm stearin (PS) with liquid vegetable oils could yield a good solid fat stock that may impart desirable physical properties, because PS is a useful source of vegetable hard fat, providing beta` stable solid fats Dietary ingestion of olive oil (OO) has been reported to have physiological benefits such as lowering serum cholesterol levels Fat blends, formulated by binary blends of palm stearin and olive oil in different ratios, were subjected to chemical interesterification with sodium methoxide The original and interesterified blends were examined for fatty acid and triacylglycerol composition, melting point, solid fat content (SFC) and consistency. Interestenfication caused rearrangement of triacylglycerol species, reduction of trisaturated and triunsaturated triacylglycerols content and increase in diunsaturated-monosaturated triacylglycerols of all blends, resulting in lowering of melting point and solid fat content The incorporation of OO to PS reduced consistency, producing more plastic blends The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of palm stearin and olive oil (C) 2009 Elsevier Ltd All rights reserved

Effects of chemical interesterification on physicochemical properties of blends of palm stearin and palm olein

Chemical interesterification is an important technological option for the production of fats targeting commercial applications. Fat blends, formulated by binary blends of palm stearin and palm olein in different ratios, were subjected to chemical interesterification. The following determinations, before and after the interesterification reactions, were done: fatty acid composition, softening point, melting point, solid fat content and consistency. For the analytical responses a multiple regression statistical model was applied. This study has shown that blending and chemical interesterifications are an effective way to modify the physical and chemical properties of palm stearin, palm olein and their blends. The mixture and chemical interesterification allowed obtaining fats with various degrees of plasticity, increasing the possibilities for the commercial use of palm stearin and palm olein. (C) 2009 Elsevier Ltd. All rights reserved.

The effects of enzymatic interesterification on the physical-chemical properties of blends of lard and soybean oil

The main goal of the present research effort was to evaluate the physical-chemical properties of blends of lard and soybean oil following enzymatic interesterification catalyzed by an immobilized lipase from Thermomyces lanuginosa (Lipozyme (TM) TL IM). Lipase-catalyzed interesterification produced new tri-acylglycerols that changed the physical-chemical properties of the fat blends under study. Solid fat content (31.3 vs 31.5 g/100 g), consistency (104.7 vs 167.6 kPa), crystallized area (0.6 vs 11.8) and softening point (31.8 vs 32.2 degrees C) of lard increased after interesterification, and this was mostly due to the increase of SSS (saturated) + SSU (disaturated-monounsaturated) triacylglycerols. These contents (SSU + SSS) increased in lard after interesterification from 42.9 to 46.7 g/100 g. The interesterified blends exhibited lower values for the physical properties when compared with their counterparts before enzymatic interesterification. The interesterification of blends of lard with soybean oil increased the amounts of UUU (triunsaturated) and SSS triacylglycerols and reduced the amounts of UUS (diunsaturated-monosaturated) triacylglycerols. The interesterified blends of lard and soybean oil demonstrated physical properties and chemical composition similar to human milk fat and they could be used for the production of a human milk fat substitute. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis of 2-Aryl- and 2,5-Diarylfurans and Thiophenes by Suzuki-Miyaura Reactions Using Potassium Trifluoroborate Salts and Heteroaryltellurides

The Suzuki-Miyaura cross-coupling reaction of 2-(butyltellanyl) or 2,5-bis-(butyltellanyl)furans and thiophenes with potassium aryltrifluoroborate salts catalyzed by palladium afforded 2-aryl- or 2,5-diaryl-furans and thiophenes in moderate to good yields.

LC-MS-MS determination of ibuprofen, 2-hydroxyibuprofen enantiomers, and carboxyibuprofen stereoisomers for application in biotransformation studies employing endophytic fungi

The purpose of this study was the development and validation of an LC-MS-MS method for simultaneous analysis of ibuprofen (IBP), 2-hydroxyibuprofen (2-OH-IBP) enantiomers, and carboxyibuprofen (COOH-IBP) stereoisomers in fungi culture medium, to investigate the ability of some endophytic fungi to biotransform the chiral drug IBP into its metabolites. Resolution of IBP and the stereoisomers of its main metabolites was achieved by use of a Chiralpak AS-H column (150 x 4.6 mm, 5 mu m particle size), column temperature 8 degrees C, and the mobile phase hexane-isopropanol-trifluoroacetic acid (95: 5: 0.1, v/v) at a flow rate of 1.2 mL min(-1). Post-column infusion with 10 mmol L(-1) ammonium acetate in methanol at a flow rate of 0.3 mL min(-1) was performed to enhance MS detection (positive electrospray ionization). Liquid-liquid extraction was used for sample preparation with hexane-ethyl acetate (1:1, v/v) as extraction solvent. Linearity was obtained in the range 0.1-20 mu g mL(-1) for IBP, 0.05-7.5 mu g mL(-1) for each 2-OH-IBP enantiomer, and 0.025-5.0 mu g mL(-1) for each COOH-IBP stereoisomer (r >= 0.99). The coefficients of variation and relative errors obtained in precision and accuracy studies (within-day and between-day) were below 15%. The stability studies showed that the samples were stable (p > 0.05) during freeze and thaw cycles, short-term exposure to room temperature, storage at -20 degrees C, and biotransformation conditions. Among the six fungi studied, only the strains Nigrospora sphaerica (SS67) and Chaetomium globosum (VR10) biotransformed IBP enantioselectively, with greater formation of the metabolite (+)-(S)-2-OH-IBP. Formation of the COOH-IBP stereoisomers, which involves hydroxylation at C3 and further oxidation to form the carboxyl group, was not observed.

In vitro metabolism study of a new nitrosyl ruthenium complex [Ru(NH center dot NHq)(terpy)NO](3+) nitric oxide donor using rat microsomes

A new nitrosyl ruthenium complex [Ru(NH center dot NHq)(terpy)NO](3+) nitric oxide donor was recently developed and due to its excellent vasodilator activity, it has been considered as a potential drug candidate. Drug metabolism is one of the main parameters that should be evaluated in the early drug development, so the biotransformation of this complex by rat hepatic microsomes was investigated. In order to perform the biotransformation study, a simple, sensitive and selective HPLC method was developed and carefully validated. The parameters evaluated in the validation procedure were: linearity, recovery, precision, accuracy, selectivity and stability. Except for the stability study, all the parameters evaluated presented values below the recommended by FDA guidelines. The stability study showed a time-dependent degradation profile. After method validation, the biotransformation study was accomplished and the kinetic parameters were determined. The biotransformation study obeyed the Michaelis-Menten kinetics. The V(max) and K(m) were, respectively, 0.1625 +/- 0.010 mu mol/mg protein/min and 79.97 +/- 11.52 mu M. These results indicate that the nitrosyl complex is metabolized by CYP450. (C) 2009 Elsevier Inc. All rights reserved.