Espectrometria de massas de alta resolução acoplada a espectrometria mobilidade iônica para análise de matrizes complexas

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dc.contributor.advisor1Romão, Wanderson
dc.contributor.authorTose, Lilian Valadares
dc.contributor.referee1Cunha Neto, Álvaro
dc.contributor.referee2Kuster, Ricardo Machado
dc.contributor.referee3Aquije, Gloria Maria de Farias Viégas
dc.contributor.referee4Lima, Francisco Alberto Fernandez
dc.date.accessioned2019-03-11T12:44:20Z
dc.date.available2019-03-11
dc.date.available2019-03-11T12:44:20Z
dc.date.issued2018-08-16
dc.description.abstractMass spectrometry (MS) is a technique able to ionize simple molecules until complex structures, performing efficiently and dynamically with a wide application using high sensitivity and speed of analysis. Although MS hasconsiderable interest in the scientific society, the application of new technologies in the field of complex matrix analysis still is little explored.Inanalyzes of crude oil, paraffin and condensed aromatic standards, the atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful ionization sourceforcharacterization of samples in original form. Initially, two methodologies were used to determine the chemical composition of the samples: (1) using a temperature gradient ranging from 150 to 600 °C at a heating rate of 150 °C.min-1(parafina) or 50 °C.min-1; (2) with a constant temperaturearound350 °C. ASAP(+)-MS ionized crude oil and paraffin, showing a typical petroleum profile in the range of m/z200 -1400 for both samples. This performancecould relateASAP sourceto detection of compounds of high molecular weight (> 1000 Da). In addition, the AC standardswere identifiedin two ionicforms: radicals, [M]+•and protonated cations, [M+H]+, with minimal fragmentation. Therefore, ASAP was efficient for accessing the chemical composition of polar and non-polar compounds.Analysis of the Cannabis sativaL. plant, were doing by ultra-high performance liquid chromatography coupled to travelingwave ionic mass spectrometry (UPLC-TWIMS MS) using electrospray ionization source in both modes, ESI (±). Hashish, marijuana, and parts of the plant Cannabis sativaL. (flower and leaf) were analyzed. Isomeric compounds were identified inacomplex mixture of cannabinoids, mainly ?9-THC, cannabidiol (CBN-C5and Mw= 310 Da), ?9-tetrahydrocannabinolic acid A and B (?9-THCA-C5A/B and Mw= 358 Da) and their isomers. Analizes by ESI-TWIMSMS were identified three isomers, m/z315/313, 311, and 357, while a high selectivity was observedin UPLC-ESI-TOF MS data, identifying more thanfour isomeric compounds in the single ion acquisition mode (SIM).In other study, we evaluated the use of a high resolution mobility analyzer coupled to ultra high resolution mass spectrometry for molecular characterization of dissolved organic matter. The main goal wastovalidate the reproducibility of trapped ion mobility spectrometry (TIMS), the range of applicability and possible challenges during routine analysis.TIMS coupledto TOF MS and FT-ICR MS showed similar 18performance and high reproducibility. For the analysis of complex mixtures, both platforms were able to aquiriedthe main characteristics. However, the increase ofchemical complexity at nominal mass level (m/z> 300-350), only TIMS-FT-ICR MS was able to solve the compositional tendencies of lower Mass spectrometry (MS) is a technique able to ionize simple molecules until complex structures, performing efficiently and dynamically with a wide application using high sensitivity and speed of analysis. Although MS hasconsiderable interest in the scientific society, the application of new technologies in the field of complex matrix analysis still is little explored.Inanalyzes of crude oil, paraffin and condensed aromatic standards, the atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful ionization sourceforcharacterization of samples in original form. Initially, two methodologies were used to determine the chemical composition of the samples: (1) using a temperature gradient ranging from 150 to 600 °C at a heating rate of 150 °C.min-1(parafina) or 50 °C.min-1; (2) with a constant temperaturearound350 °C. ASAP(+)-MS ionized crude oil and paraffin, showing a typical petroleum profile in the range of m/z200 -1400 for both samples. This performancecould relateASAP sourceto detection of compounds of high molecular weight (> 1000 Da). In addition, the AC standardswere identifiedin two ionicforms: radicals, [M]+•and protonated cations, [M+H]+, with minimal fragmentation. Therefore, ASAP was efficient for accessing the chemical composition of polar and non-polar compounds.Analysis of the Cannabis sativaL. plant, were doing by ultra-high performance liquid chromatography coupled to travelingwave ionic mass spectrometry (UPLC-TWIMS MS) using electrospray ionization source in both modes, ESI (±). Hashish, marijuana, and parts of the plant Cannabis sativaL. (flower and leaf) were analyzed. Isomeric compounds were identified inacomplex mixture of cannabinoids, mainly ?9-THC, cannabidiol (CBN-C5and Mw= 310 Da), ?9-tetrahydrocannabinolic acid A and B (?9-THCA-C5A/B and Mw= 358 Da) and their isomers. Analizes by ESI-TWIMSMS were identified three isomers, m/z315/313, 311, and 357, while a high selectivity was observedin UPLC-ESI-TOF MS data, identifying more thanfour isomeric compounds in the single ion acquisition mode (SIM).In other study, we evaluated the use of a high resolution mobility analyzer coupled to ultra high resolution mass spectrometry for molecular characterization of dissolved organic matter. The main goal wastovalidate the reproducibility of trapped ion mobility spectrometry (TIMS), the range of applicability and possible challenges during routine analysis.TIMS coupledto TOF MS and FT-ICR MS showed similar 18performance and high reproducibility. For the analysis of complex mixtures, both platforms were able to aquiriedthe main characteristics. However, the increase ofchemical complexity at nominal mass level (m/z> 300-350), only TIMS-FT-ICR MS was able to solve the compositional tendencies of lower aMass spectrometry (MS) is a technique able to ionize simple molecules until complex structures, performing efficiently and dynamically with a wide application using high sensitivity and speed of analysis. Although MS hasconsiderable interest in the scientific society, the application of new technologies in the field of complex matrix analysis still is little explored.Inanalyzes of crude oil, paraffin and condensed aromatic standards, the atmospheric solids analysis probe mass spectrometry (ASAP-MS) is a powerful ionization sourceforcharacterization of samples in original form. Initially, two methodologies were used to determine the chemical composition of the samples: (1) using a temperature gradient ranging from 150 to 600 °C at a heating rate of 150 °C.min-1(parafina) or 50 °C.min-1; (2) with a constant temperaturearound350 °C. ASAP(+)-MS ionized crude oil and paraffin, showing a typical petroleum profile in the range of m/z200 -1400 for both samples. This performancecould relateASAP sourceto detection of compounds of high molecular weight (> 1000 Da). In addition, the AC standardswere identifiedin two ionicforms: radicals, [M]+•and protonated cations, [M+H]+, with minimal fragmentation. Therefore, ASAP was efficient for accessing the chemical composition of polar and non-polar compounds.Analysis of the Cannabis sativaL. plant, were doing by ultra-high performance liquid chromatography coupled to travelingwave ionic mass spectrometry (UPLC-TWIMS MS) using electrospray ionization source in both modes, ESI (±). Hashish, marijuana, and parts of the plant Cannabis sativaL. (flower and leaf) were analyzed. Isomeric compounds were identified inacomplex mixture of cannabinoids, mainly ?9-THC, cannabidiol (CBN-C5and Mw= 310 Da), ?9-tetrahydrocannabinolic acid A and B (?9-THCA-C5A/B and Mw= 358 Da) and their isomers. Analizes by ESI-TWIMSMS were identified three isomers, m/z315/313, 311, and 357, while a high selectivity was observedin UPLC-ESI-TOF MS data, identifying more thanfour isomeric compounds in the single ion acquisition mode (SIM).In other study, we evaluated the use of a high resolution mobility analyzer coupled to ultra high resolution mass spectrometry for molecular characterization of dissolved organic matter. The main goal wastovalidate the reproducibility of trapped ion mobility spectrometry (TIMS), the range of applicability and possible challenges during routine analysis.TIMS coupledto TOF MS and FT-ICR MS showed similar 18performance and high reproducibility. For the analysis of complex mixtures, both platforms were able to aquiriedthe main characteristics. However, the increase ofchemical complexity at nominal mass level (m/z> 300-350), only TIMS-FT-ICR MS was able to solve the compositional tendencies of lower abundance
dc.description.resumoA espectrometria de massas (MS) é uma técnica que consiste na ionização de moléculas simples até estruturas complexas, realizando de forma eficiente e dinâmica com ampla aplicação devido a sua sensibilidade e velocidade de análise. Embora seja um tema que desperte bastante interesse perante a sociedade científica, a aplicação de novas tecnologias da MS no campo das analises de matrizes complexas ainda constitui uma linha de pesquisa pouco explorada. Para analises de óleo bruto, parafina e padrões de aromáticos condensados, a atmospheric solids analysis probe mass spectrometry (ASAP-MS) é uma poderosa ferramenta na carcaterização de amostras na sua forma original. Inicialmente, duas metodologias foram usadas para determinar a composição química das amostras: (1) usando gradiente de temperatura variando de 150 a 600 ºC a uma taxa de aquecimento de 150 ºC.min-1 (Parafina) ou 50 ºC.min-1 (Óleo bruto); (2) com temperatura constate de aproximadamente de 350 ºC. O ASAP(+)-MS ionizou o óleo bruto e a parafina, mostrando um perfil de petróleo típico na faixa de m/z 200 - 1400 para ambas amostras. Esse desempenho, principalmente relacionado à detecção de compostos de alto peso molecular (> 1000 Da), é superior ao de outras fontes de ionização tradicionais, como ESI, APCI, DART e DESI. Além disso, os padrões de AC foram identificados em ambas as formas: radicais, [M]+ e cátions protonados, [M+H]+, com mínima fragmentação. Portanto, o ASAP foi eficiente por acessar a composição química de compostos polares e não polares. Para analises da planta Cannabis sativa L. foi empregada a cromatografia líquida de ultra eficiência acoplado a espectrometria de massas de mobilidade iônica por traveling wave (ultra-high performance liquid chromatography coupled to traveling wave ionic mass spectrometry - UPLC-TWIMS MS) usando a fonte de ionização por electrospray em ambos modos, ESI(±). Foram realizadas analises de haxixe, maconha e partes da planta Cannabis sativa L., flor e folha. A presença de uma mistura isomérica complexa dos canabinóides foram identificadas, principalmente Δ9-THC, canabidiol (CBN-C5 e Mw = 310 Da), ácido Δ9-tetrahidrocanabinólico A e B (Δ9-THCA-C5 A/B e Mw= 358 Da) e seus isômeros. Foram identificados três isômeros, m/z 315/313, 311, e 357 usando infusão direta por ESI-TWIMS MS, enquanto uma alta seletividade foi observada nos dados por UPLC-ESI-TOF MS, com separação isomérica de quatro a cinco compostos obtidos no modo único de aquisição de íons (SIM). Em outro estudo, avaliamos o uso de um analisador de mobilidade de alta resolução com acoplado a espectrometria de massa de ultra-alta resolução para caracterização molecular de matéria orgânica dissolvida. Os objetivos incluem o estudo da reprodutibilidade da trapped ion mobility spectrometry (TIMS), faixa de aplicabilidade e possíveis desafios durante a análise de rotina. O TIMS acoplado ao TOF MS e FTICR MS apresentou desempenho semelhante e alta reprodutibilidade. Para a análise de misturas complexas, ambos analisadores foram capazes de capturar as principais características. No entanto, à medida que a complexidade química aumenta a nível da massa nominal (m/z > 300-350), apenas o TIMS-FT-ICR MS foi capaz de resolver as tendências composicionais de menor abundância.
dc.formatText
dc.identifier.urihttp://repositorio.ufes.br/handle/10/10789
dc.languagepor
dc.publisherUniversidade Federal do Espírito Santo
dc.publisher.countryBR
dc.publisher.courseDoutorado em Química
dc.publisher.departmentCentro de Ciências Exatas
dc.publisher.initialsUFES
dc.publisher.programPrograma de Pós-Graduação em Química
dc.rightsopen access
dc.subject.br-rjbnespectrometria de massa
dc.subject.br-rjbnmobilidade iônica
dc.subject.br-rjbncanabinóides
dc.subject.br-rjbnPetróleo
dc.subject.br-rjbnMatéria orgânica
dc.subject.cnpqQuímica
dc.subject.udc54
dc.titleEspectrometria de massas de alta resolução acoplada a espectrometria mobilidade iônica para análise de matrizes complexas
dc.title.alternativeHigh resolution mass spectrometry coupled to ion mobility spectrometry for the analysis of complex matrix
dc.typedoctoralThesis
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