Orientador: Francisco de Assis Machado Reis / Dissertação (mestrado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-25T12:23:58Z (GMT). No. of bitstreams: 1 Sampaio_FelipeRibeiro_M.pdf: 2993184 bytes, checksum: 76574cddb68ff72787da04d789b1d24d (MD5) Previous issue date: 2013 / Resumo: Nesse trabalho, foram sintetizados 5 padrões 3n-propil-noresgostanos. Esses compostos são os hidrocarbonetos correspondentes a uma série homóloga de biomarcadores ácidos 3n-propil-ergostanóicos encontrados em óleos de Pampo Sul, Bacia de Campos, os quais estão associados a processos de biodegradação (LIMA, 2010). Considerando-se que a estrutura tridimensional dos biomarcadores é crucial, utilizou-se como material de partida o estigmasterol. A rota sintética consistiu em uma série de reações estereo e regiosseletiva que levaram à formação de compostos com diferentes cadeias laterais ligadas ao C-17. As análises por RMN de 13C e espectrometria de massas confirmaram a estereoquímica 3?-propil, 5?(H), 14?(H), 17?(H) e 20R. A amostra de óleo foi extraída, obtendo-se a fração ácida. Esta foi derivatizada a hidrocarbonetos para que fosse possível a co-injeção com os padrões sintéticos. A co-injeção dos padrões com a amostra de óleo derivatizada confirmou a presença desses compostos, porém para picos menos abundantes. Além disso, foi confirmada a presença de um novo biomarcador / Abstract: In this work, 5 standards 3n(propryl)-norergostanes were synthesized. The compounds are the corresponding hydrocarbons of homologous series of acid biomarkers 3n-propyl-ergostanoics found in Pampo Sul, oils, Campos basin, which are associated with biodegradation processes (LIMA, 2010). Considering that the three-dimensional structure of biomarkers is crucial, stigmasterol was chosen as starting material. The synthetic route consisted in a series of stereo and regioselective reactions leading to the formation of compounds with different side chains attached to C-17. Analysis by 13C NMR and mass spectrometry confirmed the stereochemistry 3?-propil, 5?(H), 14?(H), 17?(H) e 20R. The oil sample was extracted, obtaining the acidic fraction which was submitted to a derivatization process, obtaining the hydrocarbons derivatives that were used in co-injection with the synthetic standards. The co-injection of the standards with the oil sample confirmed the presence of these compounds, however for the less abundant peaks. In addition, a new biomarker was confirmed / Mestrado / Quimica Organica / Mestre em Química

Orientador: Francisco de Assis Machado Reis / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-04T13:37:26Z (GMT). No. of bitstreams: 1 Lima_SidneyGoncalode_D.pdf: 16917910 bytes, checksum: 1d80d092bf3733ca0630c99fa60e08b5 (MD5) Previous issue date: 2005 / Doutorado / Quimica Organica / Doutor em Quimica

When and how life first emerged on the Earth is an area of intense research. Signs of the first life on Earth, including morphological fossils, are scarce and hard to interpret. An alternative approach is to study organic biomarkers, which are molecular fossils commonly considered as bona fide biosignatures. The main objective of the project is to develop an approach for analysis of single oil-bearing fluid inclusions and most importantly the detection of organic biomarkers in these inclusions. Analysis of oil-bearing fluid inclusions is advantageous since the inclusions may provide an uncontaminated sample source of Precambrian hopanes and steranes, which are key biomarkers for tracing the early evolution of life on Earth. Due to the presence of several inclusion generations, single inclusion analysis is desired in order to constrain biomarkers to specific inclusions. Time-of-flight secondary ion mass spectrometry (ToF-SIMS) could be an excellent tool for analysis of these types of samples. The development of the approach for analysis of single oil-bearing inclusions was done in a two-step process; i) a number of crude oils were analysed with ToF-SIMS and gas chromatography mass-spectrometry (GC-MS) to facilitate interpretation of ToF-SIMS spectra of these types of samples and, ii) a procedure that combines micrographs with ion etching and ToF-SIMS analysis was developed for analysis of inclusions. The feasibility of the technique was demonstrated for oil inclusions from the Siljan impact crater in which hopanes and steranes where detected. Single oil-bearing fluid inclusions trapped in mid-Proterozoic sandstones from Northern Australia were subsequently analyzed, and steranes and hopanes were detected in these inclusions. If applied on older inclusions this approach may help answer some of the questions regarding the emergence and evolution of life on Earth, and if applied on extraterrestrial samples, also the possibility of life on other planets and moons. / Livets uppkomst och tidiga utveckling på jorden är ett hett forskningsfält. Hur och när livet och dess olika domäner (arkéer, bakterier och eukaryoter) uppstod på jorden är fortfarande oklart vilket beror på att de första tecknen på liv, vilka inkluderar morfologiska fossil, spårfossil och isotoper, är få och svåra att tolka. Ett alternativt sätt att studera det tidiga livet är att studera organiska biomarkörer som är organiska molekyler som anses unika för liv. Huvudmålet med projektet är att utveckla en metod som kan detektera organiska biomarkörer i enskilda oljebärande vätskeinneslutningar. Vätskeinneslutningar, som är små mängder vätska (picoliter) infångad in en sten, är intressanta då de är en potentiell provkälla för prekambriska (äldre än 500 miljoner år) biomarkörer, som hopaner och steraner, vilka används för att utforska livets tidiga utveckling på jorden. Analys av enskilda inneslutningar är emellertid oftast nödvändigt för att kunna tidsavgränsa biomarkörer. På grund av att de flesta inneslutningar är små (10 µm i diameter) är det inte möjligt att analysera en enskild vätskeinneslutning med standardtekniken gaskromatografi-masspektrometri (GC-MS). Time-of-flight secondary ion mass spektrometri (ToF-SIMS) med sin höga känslighet, höga massupplösning och kapacitet för 2D-representation av analysdata och djupprofilering av prover är en utmärkt teknik för analys av enskilda inneslutningar. Metoden för analys av enskilda inneslutningar utvecklades i två steg. Först analyserades ett antal råoljor med ToF-SIMS och GC-MS för att underlätta förståelsen av ToF-SIMS-spektra från dessa typer av prover. Därefter utvecklades en metod som bestod av mikroskopering för att lokalisera inneslutningen, jonetsning för att öppna inneslutningen och ToF-SIMS analys av det exponerade innehållet. Metoden testades framgångsrikt på enskilda inneslutningar i hydrotermala vener av flusspat och kalcit i ordovicisk (488-443 miljoner år sedan) kalksten. Därefter användes den utvecklade metoden för att analysera enskilda vätskeinneslutningar i 1,43 miljarder år gammal sandsten från norra Australien, i vilka hopaner och steraner detekterades. De detekterade steranerna visar att trots att havet under denna tid var syrefritt existerade det lokala syrerika miljöer där eukaryoter kunde överleva. Om den utvecklade metoden används på ännu äldre inneslutningar, vilka har daterats till 3,2 miljarder år, kan den komma att svara på några de mest fundamentala frågorna kring livets uppkomst och tidiga utveckling. Om metoden används på utomjordiska prover kan den svara på frågan om det finns liv på andra planeter eller månar. / At the time of the doctoral defense, the following papers were unpublished and had a status as follows: Paper 3: Manuscript. Paper 4: Submitted.

Orientador: Luzia Koike / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Quimica / Made available in DSpace on 2018-08-11T12:01:09Z (GMT). No. of bitstreams: 1 Silva_AlexsandroAraujoda_D.pdf: 4763363 bytes, checksum: 94ec1b6053e2229aa4f384bbb4fc49d7 (MD5) Previous issue date: 2008 / Resumo: Neste trabalho, serão apresentados os resultados geoquímicos orgânicos de um estudo com amostras de óleos, sendo duas lacustres de água doce (LAD) e duas mistas (M), ambas de campos próximo da costa terrestre, e dois óleos marinho-evaporiticos (ME) de campos localizados à aproximadamente 55 km da costa litorânea, todos ao longo do trend estrutural do Estreito-Guamaré, Bacia Potiguar, RN (Mello et al.79; Santos Neto et al.75) de duas formações: Pendência e Alagamar. Os principais objetivos deste estudo são: caracterizar as amostras de acordo com os componentes biomarcadores neutros e ácidos presentes; e sintetizar componentes padrões derivados do ergosterol e estigmasterol. O protocolo analítico utilizado foi publicado anteriormente por Lopes et al.185 and Koike et al.188. Como resultado, o presente trabalho relata a identificação de onze alquilesteranos [quatro com configuração 5b(H)] e dezesseis carboxialquilesteranos [oito com configuração 5b(H)], distribuídos nas amostras coletadas ao longo do Estreito-Guamare e que evidenciam que estes compostos não são somente de origem salina como salientado na literatura (Peters et al.1) mas também estão presentes em ambientes Lacustres de Água Doce, sendo estes resultados importante na área paleoambiental. Nove alquilesteranos e dez carboxialquilesteranos também foram detectados, além da identificação de 2-metil- e 4-metil-estigmastanos nas amostras ME. Os resultados mostram uma elevada concentração destes compostos nos óleos ME e a presença embora em baixa concentração em óleos LAD, sendo que pela primeira vez foram identificados neste tipo de óleo e em óleos brasileiros. Foram sintetizados três biomarcadores para análise de identificação e que podem também serem utilizados na fortificação de amostras e quantificação de esteranos e alquilesteranos / Abstract: In this work, will be presented the results of the organic geochemistry study oils of the samples with oils, and two lacustrine freshwater (LAD) and two mixed (M), both of fields near the terrestian cost, and two marine evaporitic oils (ME) of fields located approximately 55 km from the litoral coast. All samples collected from over Estreito-Guamare, Potiguar Basin, RN (Mello et al.79; Santos Neto et al.75) this field have two formation Pendencia and Alagamar. The main subject of the this work is the biomakers organic geochemistry characterization from hydrocarbons and acids components in the samples using the analytical protocol from our group (Koike et al.188 and Lopes et al.185) and to synthetise standards biomaker from commercial stigmasterol and ergosterol. As the results in this thesis show the identifications of the eleven alkylsteranes [four with 5b(H)] configuration] and sixteen carboxyalkylsteranes [eigh with 5b(H)] configuration], distribuited in the all samples collected over Estreito-Guamare, Potiguar basin. These results revealed the important scientific information, also in the Lacustrine Fresh Water oils detected the alkylsteranes biomarkers components. In the literature (Peters et al.1) until this moment it has been published that these biomarkers indicate saline enviromental and this result is one important paleoambiental information. Nine alkylsteranes and ten carboxyalkylsteranes were also detected, in addition to the identification of 2-methyl- and 4-methyl-stigmastanes in ME samples. The results show a high concentration of these compounds in the ME oils and presence but in low concentration in LAD oils, which were identified for the first time in this type of oil and oil Brazilians. Were synthesized three biomarkers for analysis of identification and can also be used in the fortification of samples and quantification of steranes and alkyl-steranes / Doutorado / Quimica Organica / Doutor em Ciências