Caracterização de amostras de cocaína por ressonância magnética nuclear de 1H

Tese (doutorado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2018.Neste trabalho, um método de referência externa de RMNq-1H foi desenvolvido e validado para determinação de alcaloides (benzoilmetilecgonina, benzoilecgonina, cis-cinamoilcocaína e trans-cinamoilcocaína) presentes em amostras de cocaína nas formas de base livre e de cloridrato de cocaína. O método foi aplicado a um conjunto de 26 amostras apreendidas pela Polícia Federal, permitindo a determinação destes alcaloides com um tempo de análise de aproximadamente 15 minutos. Os teores de cocaína e de cinamoilcocaínas nas amostras variaram de aproximadamente 63% a 94% (m/m) e de 0,33% a 5,82% (m/m), respectivamente. O método permitiu a determinação destes alcaloides com excelente exatidão (erro relativo < 5% comparado ao material de referência certificado) e precisão (CV < 3%). Algumas figuras de mérito são apresentadas: exatidão, recuperação, repetitividade, precisão intermediária, estabilidade, robustez, incerteza e limites de detecção e quantificação. O grau de oxidação das amostras também foi determinado. Os resultados mostraram uma excelente correlação quando comparados ao método de referência (CG-DIC) e o método pode ser facilmente adaptado para aplicação a outros analitos. Posteriormente, o potencial da técnica de RMN de 1H aliada a ferramentas de análise multivariada para a análise exploratória das amostras de cocaína apreendidas foi avaliado. Analisaram-se 77 amostras de cloridrato de cocaína apreendidas pela Polícia Federal. Os espectros de 1H das amostras foram processados e submetidos a Análise de Componentes Principais e a Análise Hierárquica de Agrupamentos, numa tentativa de estabelecer correlações entre conjuntos de amostras. O método apontou algumas possíveis correlações entre amostras, no entanto, a confirmação destas correlações por outras técnicas seria necessária para uma conclusão definitiva. Alguns dos sinais que apresentaram os maiores pesos foram identificados, dentre eles sinais relativos as moléculas de cis e trans-cinamoilcocaína, bezoilecgonina e acetato de etila. No entanto, uma investigação mais aprofundada tanto acerca de quais sinais podem ser relevantes para classificação, bem como suas identidades, são necessários para aprimoramento do método.Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq), Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) e Financiadora de Estudos e Projetos (FINEP).In this work, an external reference 1H qNMR method is developed and validated for the determination of alkaloids (benzoylmethylecgonine, benzoylecgonine, cis-cinnamoylcocaine and trans-cinnamoylcocaine) in free base cocaine and cocaine hydrochloride samples. The method was applied to a set of 26 cocaine samples seized by Brazilian Federal Police, enabling the determination of these alkaloids with an analysis time of approximately 15 minutes. Cocaine and cinnamoylcocaine content in samples ranged from approximately 63% to 94% (w/w) and from 0,33% to 5,82% (w/w), respectively. The method allowed determination of these alkaloids with excellent accuracy (relative error < 5% compared to the reference material certificate) and precision (RSD < 3%). Some figures of merit are presented, including accuracy, recovery, repeatability, intermediate precision, stability, robustness, uncertainty and limits of detection and quantification. Degree of oxidation of the samples was also determined. The results showed excellent correlation compared to the reference GC-FID methodology. The method can be readily adapted to other analytes. Secondly, the potential of 1H NMR combined with multivariate analysis to exploratory data analysis of cocaine seizures was assessed. Seventy-seven samples of cocaine hydrochloride samples apprehended by Brazilian Federal Police were analyzed. The 1H NMR spectra of samples were processed and submitted to Principal Component Analysis and Hierarchical Cluster Analysis, in an attempt to establish correlations between groups of samples. Method pointed to possible correlations between some samples, however, confirmation of these correlations by other techniques would be necessary to achieve a definitive conclusion. Some of the signals that presented higher loading values were identified, namely signals related to cis and trans-cinnamoylcocaine, benzoylecgonine and ethyl acetate. However, more investigation towards signals that might be relevant to establish these correlations, as well as their identities, are necessary to a reliable application

A validated NMR approach for MDMA quantification in Ecstasy tablets

In recent years, ecstasy trafficking has grown in complexity and tablets has been commonly sold containing different contents of 3,4-methylenedioxymethamphetamine (MDMA) or even other psychoactive substances. In contrast, identification and quantification of drugs of abuse is still a challenge, once the access to drug standards is very restricted in Brazil. In this work, ecstasy tablets seized by the Brazilian Federal Police have their chemical composition identified and quantified by gas chromatography and quantitative 1H nuclear magnetic resonance based on an internal standard approach (IS-1H-qNMR). Both methods were validated and showed suitable results for the figures of merit. IS-1H-qNMR shows excellent results of accuracy (relative error < 5%) and precision (relative standard deviation (RSD) < 2%). Comparatively, IS-1H-qNMR is more efficient and versatile than gas chromatography to accomplish in a single analysis the identification and quantification of target analytes. Since the method does not require a specific reference material, it is cost effective and provides agility to routine forensic analysis

Elaboração, caracterização físico-química e condutividade AC de colóides magnéticos do tipo EDL-MF à base de ferrita de cobalto

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, 2010.Fluidos magnéticos do tipo EDL-MF (Electric Double Layered Magnetic Fluids) são dispersões coloidais de nanopartículas do tipo ferritas espinélio peptizadas em meio aquoso ácido ou básico. Como sendo um material impar, magnético e fluido ao mesmo tempo, vem sendo empregado em nanotecnologia na indústria e mais recentemente na medicina e áreas afins. Avanços na caracterização deste tipo de material têm sido primordial neste sentido. O fato de serem amostras muito absorventes limita o emprego de técnicas espectroscópicas convencionais de análise na região do UV-VIS. Por outro lado, o recente emprego de técnicas eletroquímicas que, diferentemente, exploram as propriedades elétricas do meio, se torna neste caso uma ferramenta poderosa. Neste trabalho procuramos investigar a condução elétrica de um EDL-MF a base de ferrita de cobalto. As amostras investigadas foram sintetizadas quimicamente utilizando-se o método “bottom-up” e caracterizadas à luz de um modelo “core-shell” onde um background teóricoexperimental é apresentado. Em seguida, exploramos questões de estabilidade coloidal das mesmas segundo um modelo do tipo DLVO a partir de medidas experimentais de titulações condutimétricas e potenciométricas simultâneas, com a determinação da densidade superficial de carga elétrica e as constantes de equilíbrio dos sítios ácidos superficiais que lhe dão origem. Finalmente, através de medidas condutimétricas AC procuramos investigar a contribuição das nanopartículas para a condução elétrica de um EDL-MF. Num primeiro experimento as nanopartículas foram floculadas e a condutividade AC do sobrenadante comparada àquela do colóide original. Em um segundo experimento a condutividade AC da amostra foi medida em função do aumento da viscosidade pela adição de glicerol no sentido de reduzir uma possível contribuição das nanopartículas para a condução elétrica do meio pela redução drástica de sua mobilidade em relação àquela dos íons do meio carreador. A partir da análise destes resultados nenhuma evidência foi encontrada no sentido de uma contribuição das partículas para a condutividade AC global do meio. ______________________________________________________________________________ ABSTRACTElectric Double Layered Magnetic Fluids (EDL-MF) are colloidal dispersions of spinel ferrites nanoparticles peptized in aqueous acid or base medium. As being an odd material, magnetic and fluid at the same time, it has been used in industrial nanotechnology and more recently in medicine and related areas. In this regard, advances in characterization have been of paramount importance. The fact that they are highly absorbent samples limits the use of conventional spectroscopic analysis in the UV-VIS range. However, the recent use of electrochemical techniques that, unlike spectroscopic ones, explore the electrical properties of the medium, becomes a powerful tool. In this work we investigate the electrical conduction of an EDL-MF based on cobalt ferrite. The investigated samples were chemically synthesized using a bottom-up method and characterized by a core-shell model. In this context, a theoretical and experimental background is first presented. Then, we explore the colloidal stability using a DLVO approach using experimental measurements of simultaneous conductimetric and potentiometric titration. It allows the determination of the equilibrium constants of surface acid sites and the consequent surface density of electric charge. Finally, by using AC conductivity measurements, we investigated the contribution of nanoparticles to the electric conduction of EDL-MF. In a first experiment, the dispersion has been flocculated and the AC conductivity of the supernatant was compared to that of the original colloid. In a second experiment, AC conductivity has been measured as a function of the sample viscosity which has been tuned by adding glycerol. Indeed, the decrease of the nanoparticles mobility would drastically reduce the nanoparticles contribution to the electrical conduction of the medium when compared to that of ions. The analysis of these results have shown no evidence towards a contribution of particles to the total AC conductivity of the medium

Elaboração, caracterização físico-química e condutividade AC de colóides magnéticos do tipo EDL-MF à base de ferrita de cobalto

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, 2010.Fluidos magnéticos do tipo EDL-MF (Electric Double Layered Magnetic Fluids) são dispersões coloidais de nanopartículas do tipo ferritas espinélio peptizadas em meio aquoso ácido ou básico. Como sendo um material impar, magnético e fluido ao mesmo tempo, vem sendo empregado em nanotecnologia na indústria e mais recentemente na medicina e áreas afins. Avanços na caracterização deste tipo de material têm sido primordial neste sentido. O fato de serem amostras muito absorventes limita o emprego de técnicas espectroscópicas convencionais de análise na região do UV-VIS. Por outro lado, o recente emprego de técnicas eletroquímicas que, diferentemente, exploram as propriedades elétricas do meio, se torna neste caso uma ferramenta poderosa. Neste trabalho procuramos investigar a condução elétrica de um EDL-MF a base de ferrita de cobalto. As amostras investigadas foram sintetizadas quimicamente utilizando-se o método “bottom-up” e caracterizadas à luz de um modelo “core-shell” onde um background teóricoexperimental é apresentado. Em seguida, exploramos questões de estabilidade coloidal das mesmas segundo um modelo do tipo DLVO a partir de medidas experimentais de titulações condutimétricas e potenciométricas simultâneas, com a determinação da densidade superficial de carga elétrica e as constantes de equilíbrio dos sítios ácidos superficiais que lhe dão origem. Finalmente, através de medidas condutimétricas AC procuramos investigar a contribuição das nanopartículas para a condução elétrica de um EDL-MF. Num primeiro experimento as nanopartículas foram floculadas e a condutividade AC do sobrenadante comparada àquela do colóide original. Em um segundo experimento a condutividade AC da amostra foi medida em função do aumento da viscosidade pela adição de glicerol no sentido de reduzir uma possível contribuição das nanopartículas para a condução elétrica do meio pela redução drástica de sua mobilidade em relação àquela dos íons do meio carreador. A partir da análise destes resultados nenhuma evidência foi encontrada no sentido de uma contribuição das partículas para a condutividade AC global do meio. ______________________________________________________________________________ ABSTRACTElectric Double Layered Magnetic Fluids (EDL-MF) are colloidal dispersions of spinel ferrites nanoparticles peptized in aqueous acid or base medium. As being an odd material, magnetic and fluid at the same time, it has been used in industrial nanotechnology and more recently in medicine and related areas. In this regard, advances in characterization have been of paramount importance. The fact that they are highly absorbent samples limits the use of conventional spectroscopic analysis in the UV-VIS range. However, the recent use of electrochemical techniques that, unlike spectroscopic ones, explore the electrical properties of the medium, becomes a powerful tool. In this work we investigate the electrical conduction of an EDL-MF based on cobalt ferrite. The investigated samples were chemically synthesized using a bottom-up method and characterized by a core-shell model. In this context, a theoretical and experimental background is first presented. Then, we explore the colloidal stability using a DLVO approach using experimental measurements of simultaneous conductimetric and potentiometric titration. It allows the determination of the equilibrium constants of surface acid sites and the consequent surface density of electric charge. Finally, by using AC conductivity measurements, we investigated the contribution of nanoparticles to the electric conduction of EDL-MF. In a first experiment, the dispersion has been flocculated and the AC conductivity of the supernatant was compared to that of the original colloid. In a second experiment, AC conductivity has been measured as a function of the sample viscosity which has been tuned by adding glycerol. Indeed, the decrease of the nanoparticles mobility would drastically reduce the nanoparticles contribution to the electrical conduction of the medium when compared to that of ions. The analysis of these results have shown no evidence towards a contribution of particles to the total AC conductivity of the medium

Quantitative NMR as a tool for analysis of new psychoactive substances

Several New Psychoactive Substances (NPS) have appeared on the drug market, following a new trend of drug consumption. Nuclear Magnetic Resonance (NMR) has been used, especially in the case of forensic analysis, as a tool for unambiguous structure determination of unknown NPS. The quantification of NPS in complex mixtures is, however, a very challenging task, especially in the absence of certified reference materials (CRM). In this work, we applied a quantitative 1H NMR (1H-qNMR) methodology performed without certified analytes for quantification of twelve NPS samples seized by the Brazilian Federal Police. The molecular structure of NPS samples were first confirmed by mono and bidimensional 1H and 13C NMR with unequivocally assigned signals, which allowed for the discrimination of constitutional isomers. A detailed compilation of NMR spectroscopic data showed that these NPS samples belong to cathinones, phenethylamines, and tryptamines groups. The quantitative analyses showed high precision (RSD = 2.67%) and low uncertainty (from 0.44% to 0.37%, with k = 2, 95% confidence). The NPS samples exhibited sufficient stability for a period of 48 h, which is longer than the experimental time frame and, therefore, assures the reliability and validity of the obtained results. Evaluation of some other figures of merit (selectivity, limits of quantification and detection) was also performed and confirmed the proposed method presents suitable and reproducible results. These achievements suggest the present methodology is highly adequate for forensic purposes, attaining excellent precision and accuracy, even in the absence of CRM

Essential Oil Constituents and Yields from Leaves of Blepharocalyx salicifolius (Kunt) O. Berg and Myracrodruon urundeuva (Allemão) Collected during Daytime

The purpose of this study was to evaluate the essential oil composition and yield from leaves of two Brazilian species (Myracrodruon urundeuva and Blepharocalyx salicifolius) harvested during daytime. Essential oils were obtained by steam distillation and had their yield determined. Blepharocalyx salicifolius presented yields of 0.049% (9 a.m.), 0.045% (1 p.m.), and 0.069% (5 p.m.). For Myracrodruon urundeuva, we found 0.13% (9 a.m.), 0.11% (1 p.m.), and 0.08% (5 p.m.). Finally, compound identification and quantification were carried out by GC-MS and GC-FID techniques, respectively. Thirteen major compounds were identified for Blepharocalyx salicifolius, representing 91.6% of the EOs, of which p-cymene (25.9%) was detected as amajor component. Nine major compounds were identified for Myracrodruon urundeuva, representing 90.3% of the EOs, whereas β-myrcene showed the greatest concentration (66.4%)

Methods of soil organic carbon determination in Brazilian savannah soils

Several methods exist for determining soil organic carbon, and each one has its own advantages and limitations. Consequently, a comparison of the experimental results obtained when these methods are employed is hampered, causing problems in the comparison of carbon stocks in soils. This study aimed at evaluating the analytical procedures used in the determination of carbon and their relationships with soil mineralogy and texture. Wet combustion methods, including Walkley-Black, Mebius and Colorimetric determination as well as dry combustion methods, such as Elemental and Gravimetric Analysis were used. Quantitative textural and mineralogical (kaolinite, goethite and gibbsite) analyses were also carried out. The wet digestion methods underestimated the concentration of organic carbon, while the gravimetric method overestimated. Soil mineralogy interfered with the determination of carbon, with emphasis on the gravimetric method that was greatly influenced by gibbsite