• Refine Query
  • Source
  • Publication year
  • to
  • Language
  • 3
  • 2
  • Tagged with
  • 11
  • 11
  • 11
  • 9
  • 8
  • 7
  • 6
  • 6
  • 5
  • 5
  • 5
  • 4
  • 4
  • 3
  • 3
  • About
  • The Global ETD Search service is a free service for researchers to find electronic theses and dissertations. This service is provided by the Networked Digital Library of Theses and Dissertations.
    Our metadata is collected from universities around the world. If you manage a university/consortium/country archive and want to be added, details can be found on the NDLTD website.
1

Aplicação da Espectrometria de Massas Ambiente Por Paper Spray Ionization na Identificação e Quantificação de Cocaína e no Controle de Qualidade de Bebidas

TOSATO, F. 09 December 2016 (has links)
Made available in DSpace on 2018-08-01T21:58:48Z (GMT). No. of bitstreams: 1 tese_10611_Flavia Tosato.pdf: 3350639 bytes, checksum: 70973978751713caf9a8020e18b13280 (MD5) Previous issue date: 2016-12-09 / Análises rápidas, baratas e eficientes são necessárias para as rotinas laboratoriais, principalmente quando aplicada em química forense. As utilizações de fontes ambientes permitem que as análises sejam diretas e rápidas. Assim, são opções inovadoras para melhorar a sensibilidade e seletividade. Neste trabalho, foi desenvolvida uma metodologia utilizando a espectrometria de massas ambiente por paper spray ionization mass spectrometry (PS-MS) para diferentes matrizes de dados: (i) identificar e quantificar cocaína e seus adulterantes a partir da cromatografia em camada delgada acoplada ao PS-MS; (ii) realizar a discriminação ou classificação de dez marcas brasileiras de cervejas em pilsen e lager; e (iii) identificar a falsificação controlada de Uisque com cachaça visando quantificar o volume de cachaça adicionado na mistura. Na análise de cocaína e adulterantes, os padrões foram identificados na CCD e analisados por PS-MS, e uma curva de calibração foi otimizada. A cerveja foi previamente fracionada usando a metodologia de extração em fase sólida (SPE) com água/metanol e os quatro extratos foram caracterizados no modo positivo de ionização, PS(+)MS. Para ambos os casos, foram aplicados de 20 µL do analito sobre a superfície do papel do PS-MS. Na quantificação de cachaça em misturas de whisk-cachaça. Os resultados indicam que, utilização da CCD acoplado ao PS-MS possibilita a identificação de cocaína e seus adulterantes uma ótima linearidade paras as curvas foi encontrada (cocaína (R2 = 0,9989), benzocaína, (R2 = 0,9934), a cafeína (R2 = 0,9988), a fenacetina (R2 = 0,9966), e a lidocaína (R2 = 0,9987)) e LOD inferior ao da técnica de CCD. Para as amostras de cerveja os sinais de açúcares se sobressaem sobre os demais grupos, e após a extração com água/metanol foi possível distinguir os espectros das diferentes marcas de cervejas e classifica-las em pilsen e lager pela técnica de PCA. Utilizando o PS(±)-MS e PLS com seleção de variáveis foi possível estimar quantitativamente o teor de cachaça misturado ao uísque. Com isso, utilização de fontes ambientes, como PS mostra-se eficaz para identificação de diversas matrizes, facilitando as análises de rotina.
2

Paper spray ionization: análise direta de licores do processo de etanol 2G por espectrometria de massas / Paper spray ionization: direct analysis of liquors of 2G ethanol by mass spectrometry

Carvalho, Thays Colletes de 06 March 2015 (has links)
Submitted by Luciana Ferreira (lucgeral@gmail.com) on 2015-11-19T11:42:47Z No. of bitstreams: 2 Dissertação - Thays Colletes de Carvalho - 2015.pdf: 2499571 bytes, checksum: fe876dabf52c3d28675aeb6e1dae2d21 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2015-11-19T11:44:31Z (GMT) No. of bitstreams: 2 Dissertação - Thays Colletes de Carvalho - 2015.pdf: 2499571 bytes, checksum: fe876dabf52c3d28675aeb6e1dae2d21 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) / Made available in DSpace on 2015-11-19T11:44:31Z (GMT). No. of bitstreams: 2 Dissertação - Thays Colletes de Carvalho - 2015.pdf: 2499571 bytes, checksum: fe876dabf52c3d28675aeb6e1dae2d21 (MD5) license_rdf: 23148 bytes, checksum: 9da0b6dfac957114c6a7714714b86306 (MD5) Previous issue date: 2015-03-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / 2G Ethanol production is a laborious process that may result in formation of glucose -fermenting yeasts, which reduces the process yield. The search for new rapid and sensitive methods are required to show the condition with the formation of free sugars and absence of fermentation inhibitors (Hidroximetilfurfural and furfural). The present work proposes utilizing the Paper Spray (PS) Ionization source as a method of detecting and quantifying fermentation yeasts inhibitors and sugars generated in 2G ethanol-acquiring processes. The method was optimized and was obtained as calibration curves for the glucose obtained by enzymatic hydrolysis process. These conditions were used for analysis actual sample of sugarcane bagasse liquors. The best analysis conditions by PS were: distance between 1 and 5 mm, dry spot application mode, Whatman Grade 1 paper, 60º angle, modified paper with paraffin barrier, 10 μL volume and sample application concentration of 0,1mg/mL. The detection of the expected product in the pretreatment and hydrolysis liquors of sugarcane bagasse was performed as expected. The paper with paraffin channel proved to be more effective for the quantification of glucose with improved linearity (0.9952) and limits of detection (2.77 mmol/L) and quantification (9.27 mmol/L) compared to without changing paper and paper cur ends. Applying the PS prototype in determining sugars and inhibitors in sugarcane bagasse liquors has proven to be efficient and quick, opening up a perspective of utilizing this method on monitoring Ethanol 2G production processes. / A produção de etanol 2G é um processo laborioso, que pode resultar na formação de inibidores de leveduras fermentadoras de glicose, o que diminui os rendimentos do processo. A busca de novas metodologias rápidas e sensíveis são necessárias para evidenciar a condição com a formação de açúcares livres e ausência de inibidores da fermentação (Hidroximetilfurfural e furfural). Este trabalho apresenta a proposta de utilizar a fonte de ionização Paper Spray Ionization (PS) como método de detecção e quantificação de inibidores e açúcares gerados nos processos de obtenção de etanol 2G. O método foi otimizado e obteve-se curvas de calibração para a glicose obtida pelo processo de hidrolise enzimática. Essas condições foram usadas para análise de amostras reais de licores de bagaço de cana-de-açúcar. As melhores condições de análise por PS foram: Distância entre 1 e 5 mm, modo de aplicação por aplicação a seco, papel Whatman Grade 1, ângulo de 60°, papel modificado com barreira de parafina, volume de 10 μL e concentração de amostra de 0,1mg/mL. A detecção dos produtos esperados nos licores de pré-tratamento e hidrólise do bagaço de cana-de-açúcar foi realizada como esperado. O papel com canal de parafina mostrou-se ser mais eficaz para a quantificação da glicose com melhor linearidade (0,9952) e limites de detecção (2,77 mmol/L) e quantificação (9,27 mmol/L) em relação ao papel sem modificação e o papel arredondado. A aplicação do PS na determinação de açúcares e inibidores em licores de bagaço de cana-deaçúcar mostrou-se eficiente e rápido abrindo a perspectiva de utilização deste método no acompanhamento de processos de produção de etanol 2G.
3

QUANTITATION OF ANTI-INFECTIOUS DISEASE MOLECULES UTILIZING PAPER SPRAY MASS SPECTROMETRY

Christine L Skaggs (11166399) 06 August 2021 (has links)
<p>Suboptimal dosing of anti-microbial agents increases the likelihood of therapeutic failure and resistance. Dosing optimization, while an attractive approach to combat these issues, is difficult to implement due to the different pharmacokinetics of each individual. These limitations highlight the inadequacies of a “standardized” dosing strategy. Therapeutic drug monitoring (TDM) provides a tailored treatment for individuals while avoiding adverse side effects from compounds with a narrow therapeutic window where elevated concentrations of a drug cause organ toxicity. This strategy involves accurately measuring the concentration of the analyte and interpreting the results based on pharmacokinetic parameters. Clinicians then draw conclusions regarding dose adjustment for their patient. However, TDM is expensive and difficult to perform because measurements occur in biofluids. Rapid and robust methods are necessary to quantify antimicrobial agents at the institutional level to guide patient care toward improved outcomes in serious infection. Paper spray ionization (PS), an emerging ambient ionization technique for clinical settings, demonstrations a wide versatility both in analyte variety and applications. This technique offers a rapid, accurate method to analyze these compounds with low rates of false positives even when multiplexing.</p><p><br></p><p>The work herein explains the method development of assays for TDM of various antimicrobial agents. Chapters two and three describe ways to improve the quantitative capability of paper spray through substrate pre-treatment, modification, and manipulation of key factors. Chapter four describes real-world applications for paper spray utility in clinical settings with the cross-validation of antifungal agents against a “gold standard” method. The final chapter, while not clinical based, describes the method development process for a LC-MS/MS assay to detect urobilinoids in fly guts.</p>
4

Quantitation of Anti-Infectious Disease Molecules Utilizing Paper Spray Mass Spectrometry

Skaggs, Christine Lynn 08 1900 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Suboptimal dosing of anti-microbial agents increases the likelihood of therapeutic failure and resistance. Dosing optimization, while an attractive approach to combat these issues, is difficult to implement due to the different pharmacokinetics of each individual. These limitations highlight the inadequacies of a “standardized” dosing strategy. Therapeutic drug monitoring (TDM) provides a tailored treatment for individuals while avoiding adverse side effects from compounds with a narrow therapeutic window where elevated concentrations of a drug cause organ toxicity. This strategy involves accurately measuring the concentration of the analyte and interpreting the results based on pharmacokinetic parameters. Clinicians then draw conclusions regarding dose adjustment for their patient. However, TDM is expensive and difficult to perform because measurements occur in biofluids. Rapid and robust methods are necessary to quantify antimicrobial agents at the institutional level to guide patient care toward improved outcomes in serious infection. Paper spray ionization (PS), an emerging ambient ionization technique for clinical settings, demonstrations a wide versatility both in analyte variety and applications. This technique offers a rapid, accurate method to analyze these compounds with low rates of false positives even when multiplexing. The work herein explains the method development of assays for TDM of various antimicrobial agents. Chapters two and three describe ways to improve the quantitative capability of paper spray through substrate pre-treatment, modification, and manipulation of key factors. Chapter four describes real-world applications for paper spray utility in clinical settings with the cross-validation of antifungal agents against a “gold standard” method. The final chapter, while not clinical based, describes the method development process for a LC-MS/MS assay to detect urobilinoids in fly guts.
5

Detection and Quantitation of Hazardous Chemicals in Environmental Matrices using Paper Spray Mass Spectrometry

Dowling, Sarah Naciye 08 1900 (has links)
Indiana University-Purdue University Indianapolis (IUPUI) / Paper spray mass spectrometry (PS-MS) is an ambient ionization technique that has been proven useful in many types of investigative analyses. However, the use of this technique with regards to environmental samples has been largely unexplored since the technique’s development. In this work, paper spray mass spectrometry was utilized to detect and quantify compounds for environmental, forensic and chemical defense applications. Due to the sensitive nature of some projects, the work was split into two volumes. Volume 1 focuses on the detection of pharmaceuticals in soil using paper spray (Chapter 2) and the detection of chemical warfare agent (CWA) simulants and CWA hydrolysis products (Chapter 3). Volume 2 focuses on the detection and quantitation of fentanyl analogs in environmental matrices. Chapter 5 focuses on the rapid analysis of fentanyl analogs in soil matrices. The following chapter evaluates the ability of PS-MS to detect low concentrations of fentanyl analogs in water (Chapter 6). Throughout this work, paper spray has proven to be an effective, rapid alternative to chromatography for the analysis of environmental samples.
6

Nova estratégia para análise de contaminantes emergentes em águas residuais industriais por espectrometria de massas ambiente (PSI-MS) / A new strategy for analysis of emerging contaminants in industrial residual waters by ambient mass spectrometry (PSI-MS)

Rodrigues, Marcella Ferreira 28 February 2018 (has links)
Submitted by Franciele Moreira (francielemoreyra@gmail.com) on 2018-04-04T11:53:17Z No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-04-04T13:25:36Z (GMT) No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) / Made available in DSpace on 2018-04-04T13:25:36Z (GMT). No. of bitstreams: 2 Dissertação - Marcella Ferreira Rodrigues - 2018.pdf: 1869503 bytes, checksum: 8b0fc83d8e1366a8a5952aa48164bfd3 (MD5) license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Previous issue date: 2018-02-28 / Conselho Nacional de Pesquisa e Desenvolvimento Científico e Tecnológico - CNPq / Water is an essential natural resource for life that is compromised by the release of emerging contaminants, including synthetic hormones. These compounds can be released directly through industrial effluents and indirectly through domestic sewage. Monitoring emergent contaminants (ECs) in the aquatic environment has become a priority as they pose risks to human health and the environment because of their ability to deregulate the endocrine system. Thus, verification analyzes of the emerging contaminants produced by the pharmaceutical industries are required. The most common analytical methods for analysis of this class of compounds involve the use of liquid or gas chromatography coupled to tandem mass spectrometry (MS / MS) with procedures for the preparation of long samples and long chromatographic runs. In this study, a methodology was developed for the analysis of emerging contaminants in raw and treated industrial wastewater from a local industry's hormone production line by an environmental ionization technique known as Paper Spray Ionization (PSI). Here, we have proposed an analytical approach based on the use of waxed papers. Analyzes of the synthetic hormones levonorgestrel and algestone acetophenide occurred by adding the sample to a triangular paper that was moistened with methanol solution (0.1% formic acid). The paper was fixed at the input of the mass spectrometer through a metal clip which provided a voltage to the paper. The analytical curves presented a linear correlation coefficient above 0.99. For the hormone levonorgestrel the intra-day and inter-day precision ranged from 0.5 to 5.3%, accuracy ranged from -7.0 to 4.2% while recovery ranged from 82.2 to 101.3%. For the hormone algestone acetophenide the intra-day and inter-day precision ranged from 0.9 to 10.7%, accuracy ranged from -7.7 to 8.9% while recovery ranged from 88.4 to 101.6%. The levonorgestrel hormone was also analyzed with the classic LC-MS method, showing consistent results between the two approaches, thus confirming the reliability of the proposed method. / A água é um recurso natural essencial para vida que ultimamente está comprometido pela descarga de contaminantes emergentes, dentre os quais, hormônios sintéticos. Esses compostos podem ser lançados diretamente através de efluentes industriais e indiretamente através de esgoto doméstico. O monitoramento de contaminantes emergentes (ECs) no ambiente aquático tem se tornado uma prioridade, visto que eles apresentam riscos para a saúde humana e para meio ambiente devido a sua capacidade de desregular o sistema endócrino. Dessa forma, é necessário análises de verificação dos contaminantes emergentes produzidos pelas indústrias farmacêuticas. Os métodos analíticos mais comuns para análises dessa classe de compostos envolvem o uso de cromatografia líquida ou gasosa, acoplado a espectrometria de massas tandem (MS/MS) com procedimentos de preparos de amostras demorados e longas corridas cromatográficas. Neste trabalho desenvolveu-se uma metodologia para análise de contaminantes emergentes em água residual industrial bruta e tratada de uma linha de produção de hormônios de uma indústria local, por uma técnica de ionização ambiente conhecida como Paper Spray Ionization (PSI), cuja principal vantagem é o preparo mínimo de amostra. Neste trabalho, a técnica de PSI com papel contendo barreiras de parafinas foi empregada para análise de hormônios em águas residuárias. As análises dos hormônios sintéticos levonorgestrel e algestona acetofenida ocorreram através da adição da amostra sobre um papel triangular que foi umedecido com solução de metanol (0,1% de ácido fórmico). O papel foi fixado na entrada do espectrômetro de massas através de um clipe metálico que forneceu uma voltagem ao papel. As curvas analíticas apresentaram coeficiente de correlação linear acima de 0,99. Para o hormônio levonorgestrel a precisão intra-dias e inter-dias variou de 0,5 a 5,3%, a exatidão variou de -7,0 a 4,2% enquanto a recuperação variou de 82,2 a 101,3%. Para o hormônio algestona acetofenida a precisão intra-dias e inter-dias variou de 0,9 a 10,7%, a exatidão variou de -7,7 a 8,9% enquanto a recuperação variou de 88,4 a 101,6%. O hormônio levonorgestrel também foi analisado com o método clássico LC-MS, mostrando resultados consistentes entre as duas abordagens, confirmando assim a confiabilidade do método proposto.
7

Detection and Quantitation of Hazardous Chemicals in Environmental Matrices using Paper Spray Mass Spectrometry: Volume 2

Sarah Dowling (6944351) 16 October 2019 (has links)
<p>Paper spray mass spectrometry (PS-MS) is an ambient ionization technique that has been proven useful in many types of investigative analyses. However, the use of this technique with regards to environmental samples has been largely unexplored since the technique’s development. In this work, paper spray mass spectrometry was utilized to detect and quantify compounds for environmental, forensic and chemical defense applications. Due to the sensitive nature of some projects, the work was split into two volumes. Volume 1 focuses on the detection of pharmaceuticals in soil using paper spray (Chapter 2) and the detection of chemical warfare agent (CWA) simulants and CWA hydrolysis products (Chapter 3). Volume 2 focuses on the detection and quantitation of fentanyl analogs in environmental matrices. Chapter 5 focuses on the rapid analysis of fentanyl analogs in soil matrices. The following chapter evaluates the ability of PS-MS to detect low concentrations of fentanyl analogs in water (Chapter 6). Throughout this work, paper spray has proven to be an effective, rapid alternative to chromatography for the analysis of environmental samples. </p>
8

Development of Mass Spectrometry-Based Analytical Assays for Environmental and Defense Applications

Sarah Dowling (6944351) 03 January 2024 (has links)
<p dir="ltr">Mass spectrometry (MS) is a powerful and versatile technique that is useful for addressing a wide range of complex analytical challenges. In this work, mass spectrometry-based assays were developed to address issues relating to environmental contamination and for detecting analytes of interest to the defense industry. Chapter one is an overview of the history of mass spectrometry, the fundamental operation of a mass spectrometer, as well as, advancements in chromatographic separation and ionization methods. Chapter two focuses on the development of an assay that uses blow flies as environmental sensors of chemical weapon release. In that work, a liquid chromatography – tandem mass spectrometry (LC-MS/MS) method was developed to detect chemical warfare agent simulants and chemical warfare agent hydrolysis products in flies exposed to the chemicals in controlled feeding experiments. The work in chapter three describes the development of a surface enhanced Raman spectroscopy assay coupled to paper spray mass spectrometry for a more fieldable and environmentally friendly approach to detect organophosphorus compounds. Chapter four describes the development of a paper spray mass spectrometry assay for the detection and semi-quantitation of per- and polyfluoroalkyl substances in whole blood without sample cleanup or chromatographic separations. This method would be useful in detecting high levels of these carcinogenic compounds in individuals highly exposed via their occupations. The final chapter (chapter five) returns to using blow flies as environmental sensors, but this time to detect insensitive munitions in the environment. The work focuses on the development of two different liquid chromatography mass spectrometry methods for the detection of insensitive munitions, which are less shock sensitive explosives, and their transformation products in the environment. Controlled feeding experiments were also performed where flies were exposed to contaminated soil and water sources to show the feasibility of this method in a more realistic scenario. The projects detailed herein show the extensive range with which mass spectrometry can be used for the detection of harmful chemistries of environmental concern.</p>
9

Ambient Ionization Mass Spectrometry: Advances in Monitoring Clandestine Activities, Supporting the Warfighter, and Chemical Laboratory Education Redevelopment

Patrick W. Fedick (5929664) 03 January 2019 (has links)
<p>Ambient ionization mass spectrometry enables rapid <i>in-situ</i> analysis of a plethora of analytes that are relevant to the forensic and defense communities. As the arsenal of ambient ionization techniques, aimed at solving specific targeted problems, continues to expand, the adoption of these techniques into non-academic settings has been relatively slow. At times, although the technique can provide answers in a more rapid and cheaper manner, the technique does not pass all of the required legal rules for a particular analysis when dealing with forensic evidence. This can be demonstrated with the rapid detection of drugs by paper spray ionization mass spectrometry. Paper spray ionization mass spectrometry can have drugs deposited onto the paper substrate, the paper can wipe a surface for trace analytes, and there are commercial and automated ionization sources for this process. While analysis by paper spray is rapid, the Scientific Working Group for the Analysis of Seized Drugs (SWGDRUG) states that a minimum of two instrumental techniques need to be utilized. Utilizing paper substrates that have nanoparticles embedded for surface enhanced Raman spectroscopy, that can also be utilized for paper spray ionization mass spectrometry, makes ambient ionization more appealing as it completes that first legal requirement. </p> <p>Other times, the slow adoption of these new ambient ionization techniques is due to specific communities not being aware of ambient ionization, and specific applications have not yet been demonstrated. Swab touch spray ionization mass spectrometry follows similar processes as paper spray ionization, as the swab acts both as the sampling substrate and the ionization source and can swab for analytes in a manner where the paper substrate may be damaged and unable to perform the ionization for analysis. This can be seen for the swabbing of organic gunshot residues and explosives, both of which current methods already use a swab for sampling but then need lengthy extraction techniques. The applicability of paper spray ionization and swab touch spray ionization for these forensic and defense analyses is only furthered by the fact that they both couple extremely well with portable mass spectrometers for analysis in the field.</p> <p>There are also many fields that ambient ionization is just starting to take its place in the analytical toolbox. Two such defense fields that are just beginning to expand into ambient ionization are the analysis of pyrotechnics and microelectronics. Pyrolysis gas-chromatography mass spectrometry methods have been developed and utilized for environmental tests for pyrotechnic formulation, but they are slow and there is an abundance of cleaning steps between analyses to prevent carry over and contamination. Using paper and swabs as the collection device and ionization source for environmental analysis of these pyrotechnics allow for them to be functioned at ambient conditions at the scale at which will be utilized in the field by the Warfighter. Similarly, authenticating microelectronics by desorption electrospray ionization mass spectrometry removes the subjectivity of the current methods, while rendering the integrated circuit intact enabling future use if deemed as a genuine part. By taking slower or more subjective tests, in a field that has not utilized ambient ionization heavily in the past and adding these new capabilities to their tool chest expands the acceptance and future applications of the technique.</p> <p>As acceptance and utilization of ambient ionization grows, the next generation of scientists need to have hands on training in these techniques. Through the development of new teaching laboratories that couple both the fundamentals of the technique at hand, while also examining an interesting application to better engage the students, a number of laboratory exercises have been developed. The creation of new laboratory exercise utilizing the next generation of instrumentation and analytical techniques is vital for the future and rapid application of these techniques. The work discussed herein chronicles the utilization and demonstration of ambient ionization mass spectrometry in monitoring clandestine activities, supporting the Warfighter, and redeveloping chemical laboratory education. </p>
10

Espectrometria de massas por paper spray Ionization: técnica analítica versátil para os desafios da química forense / Mass spectrometry by paper spray Ionization: versatile analytical technique for the challenges of forensic chemistry

Carvalho, Thays Colletes de 05 October 2018 (has links)
Submitted by Liliane Ferreira (ljuvencia30@gmail.com) on 2018-11-27T10:54:13Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Tese - Thays Colletes de Carvalho - 2018.pdf: 10167238 bytes, checksum: e63cc8b9621f34c961582121789dd84c (MD5) / Approved for entry into archive by Luciana Ferreira (lucgeral@gmail.com) on 2018-11-27T11:56:05Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Tese - Thays Colletes de Carvalho - 2018.pdf: 10167238 bytes, checksum: e63cc8b9621f34c961582121789dd84c (MD5) / Made available in DSpace on 2018-11-27T11:56:05Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Tese - Thays Colletes de Carvalho - 2018.pdf: 10167238 bytes, checksum: e63cc8b9621f34c961582121789dd84c (MD5) Previous issue date: 2018-10-05 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior - CAPES / Ionization is a crucial step in mass spectrometry (MS) and governs the versatility of this important analytical technique. Ionization is responsible for transferring atoms and molecules, in their respective ionized forms, into the high vacuum environment of mass spectrometers, where they are discriminated as a function of their m/z ratio. Among the several techniques of ionization of MS, the technique of ionization by Paper spray (PS) is one of the simplest, versatile and can be implemented easily in MS system. In this work, several PS-MS applications in the forensic area were developed, demonstrating their ability to screen new synthetic drugs as a complementary tool to the thin layer chromatography (TLC) method and as a tool to monitor Date-rape Drugs in blood. In the first application, PS-MS was shown to be an effective and rapid method for the identification of synthetic drugs lysergic acid diethylamide (LSD), 2,5-dimethoxy-4-chloroamphetamine (DOC), 2,5-dimethoxy-4-bromoamphetamine (DOB), 25C-NBOMe, 25B-NBOMe and 25I-NBOMe) in bottles, both by the isotopic profile of the substances and by the fragmentation presented in tandem mass spectrometry. In the second application, the TLC was coupled to the PS-MS in order to achieve greater reliability in the CCD results. In this way, a CCD method for the analysis of cocaine and adulterants (caffeine, benzocaine, lidocaine and phenacetin) was optimized by evaluating its sensitivity and selectivity. In order to improve the Detection and Quantification Limits for cocaine and adulterants, the spots were analyzed by PS-MS, obtaining improvements in the. Finally, in order to solve the low PS-MS selectivity, a new substrate was developed, especially when the analytical target is in complex mixtures, such as blood. It is a membrane coated with a molecularly printed polymer (MIP) with dual function: simultaneous extraction and ionization of targets in the same device. The developed membrane was applied in the determination of benzodiazepines in blood samples from alleged date rape- drugs victims. Blood is a complex sample containing several compounds that can suppress the analyte signal. With this modification, any suppression is avoided, obtaining excellent results, both qualitative and quantitative. In conclusion, PS-MS is a fast and low-cost technique that can replace or complement conventional analyzes in a laboratory of expertise, increasing the productivity of Brazilian justice. / A ionização é uma etapa crucial em espectrometria de massas (MS) e rege a versatilidade desta importante técnica analítica. A ionização é a responsável por transferir átomos e moléculas, em suas respectivas formas ionizadas, para o ambiente de alto vácuo dos espectrômetros de massas, onde são discriminados em função de sua razão massa sobre carga (m/z). Dentre as diversas técnicas de ionização de MS, a técnica de ionização por Paper spray (PS) é uma das mais simples, versátil e pode ser implementada facilmente em sistema de MS. Nesse trabalho diversas aplicações do PS-MS na área forense foram desenvolvidas, demonstrando sua capacidade para screening de novas drogas sintéticas, como ferramenta complementar ao método de cromatografia de camada delgada (TLC) e como ferramenta para monitorar “boa noite cinderela” em sangue. Na primeira aplicação, o PS-MS mostrou ser um método eficaz e rápido para identificação de drogas sintéticas dietilamida do ácido lisérgico (LSD), 2,5-dimetoxi-4-cloroanfetamina (DOC), 2,5-dimetoxi-4- bromoanfetamina (DOB), 25C-NBOMe, 25B- NBOMe e 25I-NBOMe) em selos, tanto pelo perfil isotópico das substâncias, quanto pela fragmentação apresentada na espectrometria de massas tandem. Já na segunda aplicação, acoplou-se TLC ao PS-MS visando alcançar maior confiabilidade nos resultados de TLC. Desta maneira, otimizou-se um método de TLC para análise de cocaína e adulterantes (cafeína, benzocaína, lidocaína e fenacetina) avaliando sua sensibilidade e seletividade. Com intuito de melhorar os Limites de Detecção e Quantificação para a cocaína e adulterantes, os spots foram analisados por PS-MS, obtendo melhorias nos resultados. Por fim, com o intuito de resolver a baixa seletividade do PS-MS, um novo substrato foi desenvolvido, principalmente quando o alvo analítico está em misturas complexas, como sangue. Trata-se de uma membrana recoberta com um polímero molecularmente impresso (MIP) com dupla função: extração e ionização simultânea de alvos em um mesmo dispositivo. A membrana desenvolvida foi aplicada na determinação de benzodiazepínicos em amostras de sangue de supostas vítimas de benzodiazepínicos. O sangue é uma amostra complexa que contém vários compostos que podem suprimir o sinal do analito. Com essa modificação qualquer supressão é evitada, conseguindo-se ótimos resultados, tanto qualitativos quanto quantitativos. Sendo assim, o PS-MS é uma técnica rápida e de baixo custo, que pode substituir ou complementar as análises convencionais em um laboratório de perícia, aumentando a produtividade da justiça brasileira.

Page generated in 0.5089 seconds