Triacylglycerols Oxidation in Oils and Fats Monitored by Easy Ambient Sonic-Spray Ionization Mass Spectrometry

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Oxidation is the major cause of fat and oil deterioration which produces rancid and unpleasant flavors that drastically reduces their quality and nutritional value. The primary oxidation products are triacylglycerols (TAG) containing unsaturated fatty acyl hydroperoxides formed by a chain process occurring through free radical intermediates. The Rancimat method is currently the gold standard for measuring the oxidative stability of oils and fats. In this report, easy ambient sonic-spray ionization mass spectrometry (EASI-MS) is demonstrated to function as a direct (no pre-separation or sample preparation steps), fast and accurate method to monitor oils and fats oxidation, providing detailed overviews of the most immediate TAG hydroperoxide products. The EASI-MS results were compared to those obtained via the classical Rancimat test.89711931200Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Financing Agency of Studies and Projects (FINEP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Quantitation of triacylglycerols in vegetable oils and fats by easy ambient sonic-spray ionization mass spectrometry

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)This innovative mass spectrometric technique provides simple, quick, and reliable quantitative analysis of triacylglycerols in vegetable oils and fats. The easy ambient sonic-spray ionization mass spectrometry (EASI-MS) technique provides simple, quick, and reliable qualitative analysis of triacylglycerols (TAG) in vegetable oils. The use of this ambient mass spectrometry technique, which does not require separation or derivatization before analysis, for precise quantitative analyses has yet to be demonstrated. In this study, the TAG composition of edible vegetable oils, hydrogenated vegetable oils and cocoa butter was quantitated by EASI-MS. The results were compared with those obtained by theoretical predictions of the TAG composition performed by a software projection, which uses a mathematical algorithm of distribution of the fatty acids (FA) in the TAG molecule, and by the direct gas chromatography method (GC-FID). Acceptable correlation coefficients were observed between the three methods during the analysis of vegetable oils and hydrogenated vegetable oils. EASI-MS offers not only simplicity, speed and selectivity for oil analysis but also precise quantitation of the TAG composition. Therefore, EASI-MS is a promising substitute for the more demanding and time-consuming standard protocols, which require separation and sometimes derivatization before analysis.52469696975Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

Synthesis of potentially bioactive PABA-related N-(aminoalkyl)lactamic amino acids and esters via selective SNAr reactions

Potentially bioactive N-(aminoalkyl)lactamic amino acids and esters were synthesized in satisfactory to good yields by SNAr reactions of aromatic acids with N-(3-aminopropyl)lactams followed by esterification with tertiary amino alcohols. The addition-elimination SNAr mechanism was confirmed by NMR and MS measurements.40119720

Brazil Nut Oil: Quality Control via Triacylglycerol Profiles Provided by Easy Ambient Sonic-Spray Ionization Mass Spectrometry

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Brazil nut oil is one of the important Amazonian natural products in the global market. Despite its health benefits and applications in food and cosmetic industries, authentication and quality control of the oil are far from satisfactory. Several sample's of Amazonian Brazil nut oil (authentic oils of different geographic origins,, commercial Oil's; and oils adulterated with soybean oil) were evaluated by easy. ambient sonic spray ionization mass spectrometry (EASI-MS). The samples were characterized on the basis of triacylglycerol profiles, and their major ions. were subjected to chemometric treatment (principal component analysis). The ambient mass spectrometry analysis and the set of major bans allowed the characterization of authentic oils, commercial oils, and adulterated oils (5% soybean oil) in a few minutes and without sample preparation. Therefore, it is shown that quality control of Amazonian vegetable oils can be readily accomplished by EASI-MS.60451126311267Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Brazilian Science Foundation FAPEAMBrazilian Science Foundation INCT/CEABFundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP

A Highly Effective Antioxidant and Artificial Marker for Biodiesel

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Biodiesel is composed of saturated and unsaturated methyl esters of fatty acids formed via transesterification of vegetable oil or animal fat. This chemical nature makes biodiesd much more susceptible to oxidation or autoxidation during long-term storage than conventional petrodiesel. Increasing resistance to oxidation therefore requires the use of antioxidants. This paper investigates the effectiveness of the N,N'-di-sec-butyl-p-phenylenediamine (I) as a antioxidant to improve the oxidative stability of soybean, sunflower and canola biodiesel. Results indicate that the induction period for oxidation of soybean and canola biodiesel is significantly improved with the addition of only 0.2 ppm of the 1, reaching the oxidative stability specification (6 h by the Rancimat test). For sunflower biodiesel, 2.0 ppm of the I was necessary. This additive is also shown to be efficiently detected by the easy ambient sonic-spray ionization mass spectrometry technique, indicating that I and its analogues and derivatives could also be used as versatile artificial markers of biodiesel.2465226526Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Studies and Projects Financing Agency (FINEP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Response surface modelling of the production of structured lipids from soybean oil using Rhizomucor miehei lipase

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)The production of structured lipids (SLs) by the acidolysis of soybean oil (SO) with a free fatty acid (FFA) mixture obtained from Brazilian sardine oil, catalysed by Rhizomucor miehei lipase (Lipozyme RM IM) in a solvent-free medium, was optimised by response surface methodology (RSM) using a three-factor central composite rotatable design. The best reaction conditions to achieve an adequate n-6/n-3 FA ratio were: sardine-FFA:SO mole ratio of 3:1, initial water content of the enzyme of 0.87% w/w, reaction time of 12 h, reaction temperature of 40 C and 10% by weight of the enzyme (% w/w). Under these conditions, the incorporation of eicosapentaenoic acid (EPA) + docosahexaenoic acid (DHA) into the soybean oil reached 9.2% (% of the total FAs), leading to a significant reduction in the n-6/n-3 FA ratio from 11:1 to 3:1. Analysis of variance (ANOVA) showed that 95% (R(2) = 0.95) of the observed variation was explained by the model. Lack of fit analysis revealed a non-significant value for the model equation, indicating that the regression equation was adequate for predicting the degree of EPA + DHA incorporation under any combination of values of the variables. Easy ambient sonic-spray ionisation mass spectrometry (EASI-MS) was used for instantaneous characterisation of TAGs. After the enzymatic reaction, a great variety of new TAGs were formed containing EPA, DHA or both in the same molecule. (C) 2011 Elsevier Ltd. All rights reserved.12712833Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [FAPESP 2008/01235-3

Assessing melatonin and its oxidative metabolites amounts in biological fluid and culture medium by liquid chromatography electrospray ionization tandem mass spectrometry (LC-ESI-MS/MS)

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)The introduction of precise analytical technologies in the biological area is needed to increase the knowledge of the fundamental processes occurring in the animal and human domain. The objective of this study was to develop a highly sensitive and selective method based on liquid chromatography coupled with tandem mass spectrometry (LC-MS/MS) using electrospray ionization for the simultaneous detection and quantification of melatonin (MEL) and its metabolites, 6-hydroxymelatonin (6-HMEL), N-2-acetyl-N-1-formyl-5-methoxykynuramine (AFMK) and N-1-acetyl-5-metoxykynuramine (AMK). Using this methodology, we have studied the role of melatonin and its metabolites in the mammalian embryo in vitro production system, which is fundamental due to the antioxidant and signaling roles of these compounds. Samples comprised of bovine follicular fluid (FF) and tissue culture medium (TCM 199). The optimized procedure uses liquid-liquid extraction with MS monitoring via selective reaction monitoring (SRM). Low limits of detection/quantification were obtained, 3/10 pg mL(-1) for MEL, AFMK and AMK and 30/100 pg mL(-1) for 6-HMEL, respectively using deuterated melatonin (MEL-d(4)) as the internal standard (IS). Validation and correlation coefficients were higher than 0.999 and recoveries were 80-108%. Precision was evaluated as repeatability and intermediate precision with relative standard deviation values <3.55%. The method has been successfully applied to the analysis of pooled FF and TCM 199 samples and results suggest that MEL and its metabolites are involved in oocyte maturation and that their proper quantitation is essential to monitor and study their role in such a process.52469116918Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)FAPESP [2012/20843-0, 2010/51677-2, 2010/18023-9