Characterization of vegetable oils and petroleum by mass spectrometry in ambient conditions and with high-accuracy and resolution

Orientador: Marcos Nogueira EberlinTese (doutorado) - Universidade Estadual de Campinas, Instituto de QuímicaResumo: A caracterização química de óleos de forma rápida, eficiente e com mínimo preparo de amostras é um desafio para a química analítica moderna. Este estudo abrangeu a caracterização química de 15 amostras de óleos vegetais e 6 amostras de petróleo, e demonstrou a versatilidade da técnica de espectrometria de massas (MS) nesta área. A caracterização de óleos vegetais foi feita por uma técnica de ionização ambiente desenvolvida no Brasil, denominada Easy Ambient Sonic-Spray Ionization (EASI) e utilizando como analisador de massas um equipamento monoquadrupolar, que possui resolução unitária. Foi obtido, para os óleos vegetais, a sua composição de triacilglicerídeos (TAG), ácidos graxos livres e hidroperóxidos utilizando apenas uma gota de óleo e nenhum preparo de amostra. A análise direta de óleos vegetais possibilitou ainda propor um método quantitativo por EASI-MS para determinação do teor de triacilglicerídeos, que demonstrou concordância com os métodos de referência. Já a caracterização do petróleo empregou a altíssima exatidão e resolução da espectrometria de massas por ressonância ciclotrônica de íons com transformada de Fourier, Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS) com as técnicas de ionização EASI e Electrospray (ESI). O presente trabalho representou ainda a primeira tese de doutorado no Brasil em petroleômica, descrevendo um método de análise que dispensa uma série de procedimentos analíticos dispendiosos e demorados, de maneira a conferir um alto grau de refinamento e desempenho à análise de petróleo. Foram estudados os compostos polares do petróleo que contêm os heteroátomos nitrogênio (N), enxofre (S) e oxigênio (O) na sua composição, sendo possível caracterizá-los por distribuição em porcentagem de classes de heteroátomos, número de carbonos e insaturações por double bond equivalents (DBE). Foi apresentada uma proposta de estudo de precisão para a metodologia de petroleômica-MS por meio da estimativa de repetitividade e reprodutibilidade, além do estudo comparativo de eficiência das técnicas de ionização ESI e EASIAbstract: The chemical characterization of oils in a fast way and with minimal sample preparation is a challenge for modern analytical chemistry. The present study comprised the chemistry characterization of 15 vegetal oil samples and 6 samples of petroleum, demonstrating the versatility of the mass spectrometry (MS) technique in this area. Vegetal oils characterization was performed by an ambient ionization technique developed in Brazil, named Easy Ambient Sonic-Spray Ionization (EASI), and using a monoquadrupole mass analyzer with unitary resolution. EASI-MS detected for vegetable oils the composition of triacylglycerols (TAG), free fat acids and hydroperoxides using only one drop of oil and without sample preparation. The direct analysis provided by EASI-MS allowed us to propose also a quantitative method based on EASI MS data to determine the level of triacylglycerols of the vegetal oils. This method was in agreement with reference methods. For petroleum characterization, we used ultra-high accuracy and resolution of the Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with EASI and electrospray (ESI) ionization. The present work describes results from the first doctorate thesis in Brazil dealing with petroleomic MS, a method of analysis that precludes a series of expensive and time-consuming analytical procedures and that can confer a high degree of refinement and performance to petroleum analysis. We have studied polar components of the petroleum containing nitrogen (N), sulphur (S) and oxygen (O) as heteroatoms in their composition. These components were classified according to the percentage distribution of heteroatoms, carbon number and unsaturations, as well as double bond equivalent (DBE). The study also evaluated precision for petroleomic MS via estimations of repeatability and reproducibility. The efficiencies of ESI and EASI for the petroleum analysis were also comparedDoutoradoQuimica AnaliticaDoutor em Ciência

Determination of crude protein and amino acids in soybean mealby Near Infrared Spectroscopy

Orientador: Ronei Jesus PoppiDissertação (mestrado) - Universidade Estadual de Campinas, Instituto de QuimicaMestradoMestre em Ciência

Electromembrane extraction (EME): Fundamentals and applications

Conventional sample preparation methods are commonly used to ensure the best analytical response of the method. However, these methods still include large solvent and sample consumption, and lengthy operation time, among other drawbacks, contributing to the unfriendly environmental status of such approaches. On the other hand, the miniaturization of such conventional methods can lead to procedures that use less or no volume of organic solvents as well as the automation of such methods resulting in less environmentally harmful methodologies. Electromembrane extraction (EME) is a miniaturized liquid phase extraction, that uses an electrical field to drive the analytes from the sample (donor phase) to an acceptor phase through a hydrophobic membrane containing a supported organic solvent on its porous membrane. Since its introduction, the technique has shown great potential in the preconcentration and clean-up of complex matrices, such as biological fluids and environmental analyses. However, the performance of the method includes many parameters and theoretical understanding to improve the analytical performance of the method. With the increasing number of studies reporting EME application for different matrices, this review has as its main goals to bring an overview of the fundamentals involved during the EME extraction, from the theoretical point-of-view to the current applications of these methods for the evaluation of different complex matrices. We believe that this overview of the fundamentals and current application of EME extraction can be used as a guide to inspire the development of new and advanced EME methods

Analysis of fuels via easy ambient sonic-spray ionization mass spectrometry

8 p. : il.The desorption and ionization of analytes directly from surfaces or natural matrices under ambient conditions has greatly simplified chemical analysis by mass spectrometry. Among the currently available set of such techniques, easy ambient sonicspray ionization (EASI) is one of the simplest and most easily implemented. Fuels are among the most important and most complex classes of chemical mixtures and a challenge for fast and comprehensive chemical analysis. This review summarizes the applications of EASIMS for fast, simple and nearly sample preparation free analysis of various fuels, focusing in typification, adulteration and quality control

Brazil nut oil: Quality control via triacylglycerol profiles provided by easy ambient sonic-spray ionization mass spectrometry

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 samples of Amazonian Brazil nut oil (authentic oils of different geographic origins, commercial oils, 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 ions 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. © 2012 American Chemical Society

Mass spectrometric plasma lipid fingerprinting kynetics after birth in calves as a tool to track metabolic changes in the extra uterine life adaptation

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)17th International Congress on Animal Reproduction (ICAR)47440440Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq

Mass spectrometric plasma lipid fingerprinting kynetics after birth in calves as a tool to track metabolic changes in the extra uterine life adaptation

Sem informação4744044

Influence of package, type of apple juice and temperature on the production of patulin by byssochlamys nivea and byssochlamys fulva

Although the production of patulin in apple fruits is mainly by Penicillium expansum, there is no information on the ability of heat resistant moulds that may survive pasteurization to produce this mycotoxin in juice packages during storage and distribution. In this study, the production of patulin by Byssochlamys spp (Byssochlamys nivea FRR 4421, B. nivea ATCC 24008 and Byssochlamys fulva IOC 4518) in cloudy and clarified apple juices packaged in laminated paperboard packages or in polyethylene terephthalate bottles (PET) and stored at both 21 °C and 30 °C, was investigated. The three Byssochlamys strains were able to produce patulin in both cloudy and clarified apple juices. Overall, the lower the storage temperature, the lower the patulin levels and mycelium dry weight in the apple juices (p < 0.05). The greatest variations in pH and °Brix were observed in the juices from which the greatest mycelium dry weights were recovered. The maximum levels of patulin recovered from the juices were ca. 150 μg/kg at 21 °C and 220 μg/kg at 30 °C. HPLC-UV, HPCL-DAD and mass spectrometry analyses confirmed the ability of B. fulva IOC 4518 to produce patulin. Due to the heat resistance of B. nivea and B. fulva and their ability to produce patulin either in PET bottles or in laminated paperboard packages, the control of contamination and the incidence of these fungi should be a matter of concern for food safety. Control measures taken by juice industries must also focus on controlling the ascospores of heat resistant moulds1421/2156163CONSELHO NACIONAL DE DESENVOLVIMENTO CIENTÍFICO E TECNOLÓGICO - CNPQCOORDENAÇÃO DE APERFEIÇOAMENTO DE PESSOAL DE NÍVEL SUPERIOR - CAPESFUNDAÇÃO DE AMPARO À PESQUISA DO ESTADO DE SÃO PAULO - FAPESPSem informaçãoSem informaçãoSem informaçã

Influence of package, type of apple juice and temperature on the production of patulin by Byssochlamys nivea and Byssochlamys fulva

Although the production of patulin in apple fruits is mainly by Penicillium expansum, there is no information on the ability of heat resistant moulds that may survive pasteurization to produce this mycotoxin in juice packages during storage and distribution. In this study, the production of patulin by Byssochlamys spp (Byssochlamys nivea FRR 4421, B. nivea ATCC 24008 and Byssochlamys fulva IOC 4518) in cloudy and clarified apple juices packaged in laminated paperboard packages or in polyethylene terephthalate bottles (PET) and stored at both 21 degrees C and 30 degrees C, was investigated. The three Byssochlamys strains were able to produce patulin in both cloudy and clarified apple juices. Overall, the lower the storage temperature, the lower the patulin levels and mycelium dry weight in the apple juices (p<0.05). The greatest variations in pH and degrees Brix were observed in the juices from which the greatest mycelium dry weights were recovered. The maximum levels of patulin recovered from the juices were ca. 150 mu g/kg at 21 degrees C and 220 mu g/kg at 30 degrees C. HPLC-UV, HPCL-DAD and mass spectrometry analyses confirmed the ability of B. fulva IOC 4518 to produce patulin. Due to the heat resistance of B. nivea and B. fulva and their ability to produce patulin either in PET bottles or in laminated paperboard packages, the control of contamination and the incidence of these fungi should be a matter of concern for food safety. Control measures taken by juice industries must also focus on controlling the ascospores of heat resistant moulds. (C) 2010 Elsevier B.V. All rights reserved.Conselho Nacional de Desenvolvimento Cientifico e Tecnologico (CNPQ)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundacao de Amparo a Pesquisa do Estado de Sao Paulo (FAPESP)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenacao de Aperfeicoamento de Pessoal de Nivel de Superior (CAPES)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)[282/06]Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)[129/07]Prodetab (Embrapa)Prodetab (Embrapa

Influence of package, type of apple juice and temperature on the production of patulin by Byssochlamys nivea and Byssochlamys fulva

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Although the production of patulin in apple fruits is mainly by Penicillium expansum, there is no information on the ability of heat resistant moulds that may survive pasteurization to produce this mycotoxin in juice packages during storage and distribution. In this study, the production of patulin by Byssochlamys spp (Byssochlamys nivea FRR 4421, B. nivea ATCC 24008 and Byssochlamys fulva IOC 4518) in cloudy and clarified apple juices packaged in laminated paperboard packages or in polyethylene terephthalate bottles (PET) and stored at both 21 degrees C and 30 degrees C, was investigated. The three Byssochlamys strains were able to produce patulin in both cloudy and clarified apple juices. Overall, the lower the storage temperature, the lower the patulin levels and mycelium dry weight in the apple juices (p<0.05). The greatest variations in pH and degrees Brix were observed in the juices from which the greatest mycelium dry weights were recovered. The maximum levels of patulin recovered from the juices were ca. 150 mu g/kg at 21 degrees C and 220 mu g/kg at 30 degrees C. HPLC-UV, HPCL-DAD and mass spectrometry analyses confirmed the ability of B. fulva IOC 4518 to produce patulin. Due to the heat resistance of B. nivea and B. fulva and their ability to produce patulin either in PET bottles or in laminated paperboard packages, the control of contamination and the incidence of these fungi should be a matter of concern for food safety. Control measures taken by juice industries must also focus on controlling the ascospores of heat resistant moulds. (C) 2010 Elsevier B.V. All rights reserved.1421/Fev156163Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)[282/06]Fundo de Apoio Ao Ensino, a Pesquisa e a Extensao (FAEPEX-UNICAMP)[129/07]Prodetab (Embrapa)Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq