This project was the very beginning of research into the chemistry of eastern Australian banksia flowers. Using dynamic headspace sampling (DHS) analysis, differences in volatile components, consistent with detection of differences in odour, were detected among three different species and one commercial cultivar. Infraspecific variation was also observed between two known subspecies of Banksia ericifolia and between differently coloured forms of Banksia spinulosa var. collina. The cultivar, Banksia 'Giant Candles', was shown to have some of the chemical components of each of its supposed ancestors. The absence of known wound-response chemicals indicated that this DHS method was successful in leaving the inflorescences undamaged throughout the sampling procedure. The Likens-Nickerson modification of classical hydrodistillation methods was useful. The static headspace method (SHS) was easily automated and was shown to be chemically robust and sufficiently sensitive to detect volatile compounds from only a few flowers. The milder DHS method, which minimised mechanical and heat damage to the plant tissue, produced a different set of results. From the results of this project, a suite of volatile compounds has been proposed that may be useful in future behavioural studies to help determine whether animals are attracted to components of banksia odours. These candidates include some compounds that have been reported in animal secretions, wound-response chemicals that may be produced by the plant to aid its communication with other organisms, and a compound (suggested to be sulfanylmethyl acetate) not previously reported from natural sources. The mildest of the three analytical methods used, dynamic headspace sampling, was shown to be suitable for the potential chemotaxonomic evaluation of some members of the Banksia genus. / Doctor of Philosophy (PhD)

Improvised explosive devices (IEDs) continue to be a national threat to the safety and security of the public. Research in explosives analysis for intact and post-blast samples continue to be a topic in which practitioners are constantly improving and searching for faster methods and techniques to analyze these sample types. The key role crime laboratories play in analyzing these sample types can have limitations, such as increasing turnaround times and backlogs. This concern additionally plays a role in the safety of the public if an unknown individual has not been discovered. Current analytical instrumentation in which explosives are analyzed includes Gas Chromatography – Mass Spectrometry (GC-MS), Liquid Chromatography – Mass Spectrometry (LC-MS), and Ion Mobility Spectrometry (IMS). Each instrument has benefits in the analytical results obtained. Direct Analysis in Real Time - Mass Spectrometry (DART-MS) has shown a significant promise as an analytical approach that can help remedy the time an explosive sample is analyzed, while additionally providing discriminating analytical results. Previous research has shown that DART-MS is capable of analyzing explosives, including smokeless powder. A limitation currently in the area of smokeless powder analysis with DART-MS is the application of utilizing this method and technology to realistic casework that may be encountered in forensic laboratories. Intact and post-blast explosive samples encountered in forensic laboratories arrive in various states and conditions. For example, the severity of the blast and environmental factors may play a role in the detection of smokeless powder on these sample types. To provide objective information and additional research, studies were conducted with mixture samples of smokeless powder and potential matrices that may be encountered in real world case samples. Faster processing time, in addition to the discrimination of smokeless powder, was the ultimate goal of this research. Due to the complexity of the mass spectra that may be generated from sample mixtures, an extraction technique coupled with DART-MS was investigated. A liquid-liquid extraction (LLE) method and dynamic headspace concentration using Carbopack™ X coated wire mesh were tested for the effectiveness of separating the analytes of interest of smokeless powder from various matrix interferences. Hodgdon Hornady LEVERevolution (HHL) smokeless powder, Pennzoil 10W-40 (P10W40) motor oil, and residue from metal end caps (China SLK brand) and black steel pipe nipples (Schedule 40) were used during the course of the matrix interference study. The method of applying dynamic headspace concentration using Carbopack™ X coated wire mesh and analysis by DART-MS provides an effective alternative to obtaining mass spectral data in a shorter amount of time, compared to techniques currently used in forensic laboratories. Effective separation was not achieved using the various LLE methods tested. Further testing would be required in order to evaluate the feasibility of implementing the technique as a sample preparation approach prior to analysis by DART-MS.

Orientador: Fabio Augusto / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T15:09:26Z (GMT). No. of bitstreams: 1 Silva_RogerioCesarda_D.pdf: 4524361 bytes, checksum: 24333539b89a414df416bbcf9e0ee5bd (MD5) Previous issue date: 2005 / Doutorado / Quimica Analitica / Doutor em Quimica

Improvised explosive devices (IEDs) are charged devices often used by terrorists and criminals to create public panic. When the general public is targeted by an act of terrorism, people who are not injured or killed in the explosion remain in fear until the perpetrator(s) has been apprehended. Methods that can provide investigators and first responders with prompt investigative information are required in such cases. However, information is generally not provided quickly, in part because of time-consuming techniques employed in many forensic laboratories. As a result, case report turnaround time is longer. Direct analysis in real time - mass spectrometry (DART-MS) is a promising analytical technique that can address this challenge in the Forensic Science community by permitting rapid trace analysis of energetic materials. The builder of an IED will often charge the device with materials that are readily available. The most common materials employed in the construction of IEDs are black and smokeless powder. However, other materials may include ammonia- or peroxide-based materials such as common household detergents. Smokeless powder is a propellant that is readily available to civilians. They are typically used for reloading ammunition and are sold in large quantities each year in the United States. Some states have stricter regulations than others but typically a firearms license is all that’s required to possess smokeless powder. Smokeless powder is considered a low explosive which is capable of causing an explosion if a sufficient quantity is deflagrated inside a confined container. The most commonly employed confirmatory techniques for the analysis of smokeless powder are gas chromatography-mass spectrometry (GC-MS) or liquid chromatography-mass spectrometry (LC-MS). These methods often require extensive and time-consuming sample preparation procedures to prepare the powders for analysis. In addition to lengthy sample preparation procedures, GC-MS and LC-MS often require chromatographic separations that can range anywhere from 5 to 30 minutes or longer per sample. Ion mobility spectrometry (IMS) is widely used for the field analysis of smokeless powder and can provide faster results in comparison to GC-MS or LC-MS. However, identification is limited to drift time and no structural information is provided unless coupled to a mass spectrometer. In an effort to accelerate the speed of collection and characterization of smokeless powder, an analytical approach that utilizes novel wire mesh coated with CarbopackTM X, dynamic headspace concentration and DART-MS was evaluated to determine if the approach could generate information rich chemical attribute signatures (CAS) for smokeless powder. CarbopackTM X is a graphitized carbon material that has been employed for the collection of various volatile and semi-volatile organic compounds. The goal of using CarbopackTM X coated wire mesh was to increase the collection efficiency of smokeless powder in comparison to traditional swabbing and swiping methods. DART is an ambient ionization technique that permits analysis of a variety of samples in seconds with minimal to no sample preparation and offers several advantages over conventional methods. Heating time, heating temperature and flow rate for dynamic headspace concentration were optimized using Hodgdon Lil’ Gun smokeless powder. DART-MS was compared to GC-MS and validated using the National Institute of Standards and Technology reference material 8107 (NIST RM 8107) smokeless powder standard. Additives and energetic materials from unburnt and burnt smokeless powders were rapidly and efficiently captured by the CarbopackTM X coated wire mesh and successfully detected and identified using DART-MS. The DART source temperature was evaluated with the goal of providing the most efficient desorption of the analytes adsorbed onto the wire mesh. For this to be a robust approach in forensic analysis, chemometric analysis employing predictive models was used to simplify the data and increase the confidence of assigning a mass spectrum to a particular powder. Predictive models were constructed using the machine learning techniques available in Analyze IQ Lab and evaluated for their performance in classifying three smokeless powders: Alliant Reloder 19, Hodgdon LEVERevolution and Winchester Ball 296. The models were able to accurately predict the presence or absence of these three powders from burnt residues with error rates that were less than 4%. This approach has demonstrated the capability of generating comparable data and sensitivity in a significantly shorter amount of time in comparison to GC-MS. In addition, DART-MS also permits the detection of targeted analytes that are not amenable to GC-MS. The speed and efficiency associated with both the sample preparation technique and DART-MS, and the ability to employ chemometric analysis to the generated data demonstrate an attractive and viable alternative to conventional techniques for smokeless powder analysis.

Males of South American fruit fly Anastrepha fraterculus form leks and release sex pheromone to attract females during the reproductive behavior. The aim of my diploma thesis was to collect samples of volatiles released by variously old males, subsequently to analyze and to determine the changes in the quantitative composition of the sex pheromone depending on age. The volatiles were trapped on adsorbent, eluted with hexane containing internal standard and analyzed by gas chromatography with mass detection. Males release twenty volatiles, including fourteen terpenes: α-pinene, camphene, -pinene, myrcene, Δ3-carene, limonene, (Z)--ocimene, (E)--ocimene, aromadendrene, trans-α-bergamotene, (Z)-β-farnesene, (Z,E)-α-farnesene, germacrene D, (E,E)-α-farnesene; one aldehyde: nonanal; two alcohols: (3Z)-non-3-en-1-ol, (3Z,6Z)-nona-3,6-dien-1-ol and three lactones: suspensolide, anastrephin a epianastrephin. From the list of named compounds there were proved antenal activity of six compounds in previous work, namely trans-α-bergamotene, (Z,E)-α-farnesene, (E,E)-α-farnesene, (3Z)-non-3-en-1-ol, (3Z,6Z)-nona-3,6-dien-1-ol and epianastrephin.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work was divided into three parts focusing two main topics: the study of volatiles compouds of P. graveolens and the study of the essential oil of L. alba and its evaluation of insecticidal activity against Spodoptera frugiperda. The chapter 2 approuch the study of the volatile compounds of the leaves of P. graveolens extracted by dynamic headspace using Porapak Q® as adsorbent and in nature peat, a novel adsorbent in the extraction of plant volatiles, and the results were compared with those obtained by hidrodestilation. The results showed that hydrodistilation (HD) was more efficient for extracting linalool and citronellyl formate. While citroneol, geraniol and geranyl tiglate were obtained in greater quantity by dynamic headspace using in nature peat (HSD-T), isomenthone, 6,9- guaiadiene and - muurolene by headspace using Porapak Q® (HSD-P). The study of conversion proved that geraniol converts in linalool when geraniol is subjected to water vapor and high temperature, nevertheless a small ratio. This also prove, in parts, the high percentage of linalool obtained by HD compared to HSD-T and HSD-P. The chapter 3 approuch the study of the essential oils of 9 accessions of L. alba collected in 4 states of Brazil using statistical methods and checking the accessions with the best essential oil content. The statistical methods of hierarchical cluster analysis (HCA) and Principal component analysis (PCA) were used to prove the experimental data and confirmation of training groups. Three groups representatives of the three chemotypes were formed: Group I was characterized by linalool and 1,8-cineole; group II, by limonene and carvone; and group III by neral and geranial. In chapter 4 was approached the evaluation of insecticidal activity of the essential oils of P. graveolens (PEL-001) and L. alba (accessions LA-10, LA-22 and LA-57) and also of the main compounds (geraniol, linalool, 1,8-cineole, limonene, carvone) against S. frugiperda via topical aplication. The test of topical application showed that the essential oils of P. graveolens (PEL-001) and L. alba (accessions LA-10, LA-22, LA-57) showed acute toxicity against larvae of S. frugiperda, causing mortality of up to 100% at a dose 192 μg/larvae. / O presente trabalho foi dividido em 3 partes os quais abordam 2 temas centrais: estudo dos compostos voláteis de Pelargonium graveolens e do óleo essencial de Lippia alba e avaliação de atividade inseticida frente à Spodoptera frugiperda. O capítulo 2 abordou o estudo dos voláteis das folhas de P. graveolens extraídos por headspace dinâmico utlizando Porapak Q® como adsorvente e turfa in natura, um adsorvente inédito empregado na extração de voláteis de plantas, sendo os resultados comparados com àqueles obtidos por hidrodestilação. Os resultados mostraram que a hidrodestilação (HD) foi mais eficiente na extração de linalol e formiato de citronelila. Enquanto citronelol, geraniol e tiglato de citronelila foram obtidos em maior proporção por headspace dinâmico utilizando turfa in natura como adsorvente (HSD-T), isomentona, 6,9- guaiadieno e -muuroleno foram identificados em maior proporção por headspace dinâmico utilizando Porapak Q® (HSD-P). O estudo de conversão comprovou que geraniol se converte em linalol, quando o geraniol é submetido a vapor d água e altas temperaturas, porém a um pequeno percentual. Isso também comprova, em partes, o alto percentual de linalol obtido por HD em relação à HSD-T e HSD-P. A extração do hidrolato revelou variações na composição volátil em comparação com os outros métodos de extração. O Capítulo 3 abordou o estudo dos óleos essenciais de 9 acessos de L. alba coletados em 4 estados do Brasil empregando métodos estatísticos e verificando os acessos com melhores teor de óleo essencial. Os métodos estatísticos de análise hierárquica de agrupamentos (HCA) e análise de componentes principais (PCA) foram empregados para comprovar os dados experimentais e confirmar a formação dos grupos. Três grupos, representando os três quimiotipos, foram formados, dos quais o grupo I foi caracterizado por linalol e 1,8-cineol, grupo II por limoneno e carvona e grupo III por neral e geranial. No capítulo 4 foi abordado a avaliação de atividade inseticida dos óleos essenciais de P. graveolens (PEL-001) e L. alba (acessos LA-10, LA-22 e LA-57), bem como dos seus principais compostos majoritários (geraniol, linalol, 1,8-cineol, limoneno e carvona) frente à S. VII frugiperda. O ensaio de aplicação tópica mostrou que óleos essenciais de P. graveolens (PEL-001) e L. alba (acessos LA-10, LA-22, LA-57) apresentaram toxicidade aguda nas lagartas S. frugiperda, ocasionando mortalidade de até 100% na dose 192 μg/lagarta.

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Among the products of the hive, honey is considered the principal, standing out as natural food and for having multiple pharmacological applications. Honey can be produced by honey bees (Apis mellifera, L.) from the nectar, fruit, plant secretions and excretions of aphids or other sweetened solutions.Their nutritive power, pharmacologic and commercial value depends on its botanical origin, which can be obtained through classical methods as sensory evaluation, physicochemical analyses or melissopalynology. Although, these methods require much experience of the analyst and are costly.In view of the current difficulties in conducting these analyses, methods based on the study of volatile constituents have emerged as an alternative in the search for the source of compound markers of floral honeys. For the identification of these compounds, techniques such as solid in solid phase (SPME) and dynamic headspace (HSD) followed by analysis on gas chromatography coupled to mass spectrometer (GC-MS) are suggested. In this work, different honeyproducing regions in the State of Sergipe were studied, as well as samples of honey originated from other states of Brazil, purchased in local supermarkets. Analyses of volatile components were obtained by dynamic headspace using Porapak Q® and Peat in natura as adsorbent materials. For both, parameters such as amount of sample, salt addition, time and temperature of extractionhave been optimized. Optimization, made possible the identification of 112 different compounds belonging to classes of aliphatic alcohols, aliphatic aldehydes, benzene derivatives, monoterpene hydrocarbons, oxygenated hydrocarbons, norisoprenoids, sesquiterpenes, oxygenated sesquiterpenes, carboxylic acids and others. Among these, a group of senior compounds were studied by principal components analysis and hierarchical cluster analysis. With these analyses was likely to identify the components with biggest weights in the samples and cluster them into five groups with a similarity of 48% based on Euclidean distance. Among the weighty compounds are furfuraldehyde, benzaldehyde, cis-linalool oxide (furanoid), trans-linalool oxide (furanoid), linalool, hotrienol, 4-ketoisoforone, aldehyde lilac (isomer I), cis-linalool oxide (pyranoid) and -terpineol. / Dentre os produtos apícolas o mel é considerado o principal por se destacar como alimento natural e ter várias aplicações farmacológicas, podendo ser produzido por abelhas Apis mellifera a partir do néctar, secreções das plantas e frutos, excreções de afídeos e outras soluções adocicadas. Seu poder nutritivo, farmacológico e valor comercial dependem de sua origem botânica, a qual pode ser obtida através de métodos clássicos como a avaliação sensorial, a melissopalinologia ou análises físico-químicas, porém estes métodos exigem muita experiência do analista e são dispendiosas. Em virtude das dificuldades atuais em realizar essas análises os métodos baseados no estudo dos constituintes voláteis têm surgido como uma alternativa na procura de compostos marcadores da origem floral de méis. Para a identificação destes compostos, técnicas como a microextração em fase sólida (SPME) e headspace dinâmico (HSD) seguido de análise em cromatógrafo em fase gasosa/espectrômetro de massas (CG/EM) são sugeridas. Neste trabalho foram estudados méis de diferentes regiões produtoras do estado de Sergipe, bem como amostras de méis adquiridos em supermercado de Aracaju oriundas de outros estados do Brasil através da análise dos componentes voláteis obtidos por headspace dinâmico utilizando Porapak Q® e Turfa in natura como materiais adsorventes. Para tanto foram otimizados parâmetros como quantidade de amostra, adição de sal, tempo e temperatura de extração. Nas condições otimizadas foi possível identificar 112 diferentes compostos pertencentes às classes dos álcoois alifáticos, benzenóides, aldeídos alifáticos, hidrocarbonetos lineares, monoterpenos, monoterpenos oxigenados, sesquiterpenos, sesquiterpenos oxigenados, norisoprenóides, ácidos carboxílicos e outros. Dentre estes, um grupo de compostos majoritários foram estudados por análise de componentes principais e análise de agrupamento hierárquico. Com estas análises foi possível identificar os componentes de maiores pesos das amostras e agrupá-las em cinco grupos com uma similaridade de 48%, tendo como base a distância Euclidiana. Dentre os compostos de maiores pesos estão o furfural, benzaldeído, cis-óxido de linalol (furanóide), trans-óxido de linalol (furanóide), linalol, hotrienol, 4-ceto-isoforona, lilac aldeído (isômero I), cis-óxido de linalol (piranóide) e o -terpineol.