Various α,β-unsaturated carbonyl compounds and derivatives were explored in order to expand the range of substrates for the 1,4-addition of alkenylboronates using 3,3′-disubstituted binaphthols. Enones 2.60 were examined and found to be suitable for conjugate addition under our proposed reaction conditions. The asymmetric 1,4-additions of alkenylboronates to enones 2.60 using catalytic amounts of 3,3′-disubstituted binaphthols was shown to occur with moderate to good yields and high enantioselectivities. The chiral products could serve as enantioenriched substrates for further transformation such as asymmetric reduction, which was performed with good yield and selectivity. The absolute configuration for the alkenylation of enones was also confirmed to be the (R) enantiomer using (S)-3,3′-disubstituted binaphthols via X-ray crystallographic analysis. Investigations into selective Baeyer-Villiger oxidation of 1,4-addition products of enones was also examined. Although the desire ester products were not obtained, intriguing informative findings were still obtained from the investigation.

Various α,β-unsaturated carbonyl compounds and derivatives were explored in order to expand the range of substrates for the 1,4-addition of alkenylboronates using 3,3′-disubstituted binaphthols. Enones 2.60 were examined and found to be suitable for conjugate addition under our proposed reaction conditions. The asymmetric 1,4-additions of alkenylboronates to enones 2.60 using catalytic amounts of 3,3′-disubstituted binaphthols was shown to occur with moderate to good yields and high enantioselectivities. The chiral products could serve as enantioenriched substrates for further transformation such as asymmetric reduction, which was performed with good yield and selectivity. The absolute configuration for the alkenylation of enones was also confirmed to be the (R) enantiomer using (S)-3,3′-disubstituted binaphthols via X-ray crystallographic analysis. Investigations into selective Baeyer-Villiger oxidation of 1,4-addition products of enones was also examined. Although the desire ester products were not obtained, intriguing informative findings were still obtained from the investigation.

The seasonal and diurnal concentrations of atmospheric carbonyls were measured by the LpDNPH-Cartridge and the microcomputer air sampling device at Nan-Chie and Hsiung-Kong sites in Kaohsiung area. Then, factor analysis and absolute principal component analysis were also used to determine the source apportionment in Kaohsiung area. Total concentrations of carbonyls were higher in Summer than in winter at Nan-Chie and Hsiung-Kong sites. Measurements showed that the highest carbonyls were formaldehyde and acetaldehyde, due to the fact that photochemical activities are stronger in summer than in winter. The concentrations of total carbonyls, formaldehyde, acetaldehyde were showed similar diurnal variations, that highest concentrations were found in the morning and noon, then drop down at afternoon and increased at night. Due to the fact that photochemical activities and vehicle exhausts. C1-C3 ratio indicated the local participation of anthropogenic hydrocarbons was important in the production of carbonyls in the Kaohsiung area. C1/C2 was highest in the summer than in the winter, that photochemical activities cause highest concentrations of formaldehyde, especially in the summer noon. The results of factor analysis and absolute principal component analysis showed that the primary pollution sources at Nan-Chie were traffic exhausts (diesel and gasoline vehicle) and stationary sources (petrochemical and food industry) and restaurant emissions, and the primary pollution sources at Hsiung-Kong were traffic exhausts (diesel and gasoline vehicle), stationary emissions (metal assembly and petrochemical industry) and restaurant emissions.

This study investigated the fuel properties, engine performances, and emissions of two biodiesels and diesel. The fuels examined were D100 (ultra-low sulfur diesel), B20 (20% palm biodiesel +80% ultra-low sulfur diesel) and B100 (palm biodiesel). The fuel properties analysis results showed that the benefits of biodiesel were high cetane value, extremely low sulfur and aromatic contents, and good lubricity. While the defects of biodiesel were high pour point. The particulates emitted from the burning of D100, B100, B20 were mainly fine particulates, also known as young aerosols. Particles smaller than 2.5 µm easily enter the trachea and bronchus via the upper respiratory tract, finally deposit on the alveolus, which could cause severe injury to human health. The emission of soluble organic fraction (SOF) from diesel engine using D100, B100 and B20 were 23.2%, 19.9% and 20.2%, respectively. The SOF of D100 is slightly higher than B100 and B20. It suggested that adding biodiesel into diesel can decrease SOF and thus reduce the potential danger to human health. The original total PAHs concentration of tail gas emitted from engines using D100, B100 and B20 were 241, 50.6 and 98.8 µg/m3, respectively. Adding 20% biodiesel into D100 could reduce 59.0% of PAHs emission. Moreover, the original total BaPeq concentration of tail gas emitted from diesel engines using D100, B100 and B20 were 0.714, 0.509 and 0.570 µg/m3, respectively. Adding 20% biodiesel into D100 could also reduce 20.2% of total BaPeq emission. Hence, adding biodiesel into diesel can effectively reduce the emission of PAHs and the potential danger to human health. The emission factors of carbonyl compounds from diesel engines using D100, B100 and B20 were 395, 1,170 and 326 mg/BHP-hr, respectively. carbonyl compounds of B100 were obviously higher than D100 and B20. The results indicated that using pure palm biodiesel in diesel engine can increased the emission of carbonyl compounds. However, adding 20% biodiesel into D100 can effectively reduce 17.5% of carbonyl compounds emission. Keyword: ultra-low sulfur diesel, palm biodiesel, fuel properties¡BThe emission of soluble organic fraction (SOF)¡BPAHs¡Bcarbonyl compounds¡C

Thesis (Ph. D.)--Oregon State University, 2010. / Printout. Includes bibliographical references (leaves 190-208). Also available on the World Wide Web.

published_or_final_version / abstract / toc / Chemistry / Master / Master of Philosophy

Bibliography: leaves 204-208 / 208 leaves : ill ; 30 cm. / Title page, contents and abstract only. The complete thesis in print form is available from the University Library. / Thesis (Ph.D.)--University of Adelaide, 1985

Submitted by Ana Hilda Fonseca (anahilda@ufba.br) on 2016-08-31T13:23:27Z No. of bitstreams: 1 TESE VERSÃO FINAL_completaseg.pdf: 1586143 bytes, checksum: a57cce30857cde7aaf0e0e909a4950aa (MD5) / Approved for entry into archive by Vanessa Reis (vanessa.jamile@ufba.br) on 2016-09-02T16:10:30Z (GMT) No. of bitstreams: 1 TESE VERSÃO FINAL_completaseg.pdf: 1586143 bytes, checksum: a57cce30857cde7aaf0e0e909a4950aa (MD5) / Made available in DSpace on 2016-09-02T16:10:31Z (GMT). No. of bitstreams: 1 TESE VERSÃO FINAL_completaseg.pdf: 1586143 bytes, checksum: a57cce30857cde7aaf0e0e909a4950aa (MD5) / A análise dos compostos carbonílicos (CCs) é um dos procedimentos de rotina em muitos laboratórios de cont role de qualidade de bebidas, no entanto, atualmente são quantificados apenas os CCs totais expressos em teores de acetaldeído, sem que sejam associados outros CCs com a sua qualidade. Esses compostos possuem impacto olfativo no aroma dos vinhos e uma forte afinidade pelo bissulfito, adicio nado na vinificação, podendo formar adutos estáveis que interferirão também no aroma. Os maiores desafios, no entanto, consistem em predizer qu ais CCs têm maior afinidade pelo S(IV), que circunstâncias favorecem es ta interação e como analisá-los em conjunto. Por esse motivo, no presente estudo foi avaliado o perfil de 22 CCs em “solução modelo" e em dez amostras reais de vinhos, empregando uma metodologia desenvolvida e validada para analisá-los de forma simultânea, que utiliza CLAE co m sistema de gradiente binário de eluição. Baseado na Análise de Componentes Principais (ACP) e nas constantes de dissociação (K d ), os resultados revelaram que os aldeídos alifáticos formam adutos com S(IV), enquanto as cetonas, os aldeídos cíclicos e os trans-alcenais interagiram fracamente e são encontrados predominantemente em sua forma livre . Estes resultados revelaram também que a faixa de pH entre 10 e 11 foi definida como a mais apropriada para a dissociação do adu to CC-S(IV), favorecendo a quantificação segura dos CCs na form a total. Nos vinhos e uvas estudados foram identificados o fo rmaldeído, acetaldeído, butanal, hexanal, furfural, benzaldeído, E -penten-2-al, ciclo hexanona e 2-etil hexanal, sendo este último identificado pela primeira vez neste tipo de matriz. Os quatro primeiros aldeídos citados podem ser considerados aromas primários por estarem presentes tanto nos vinhos quanto nas uvas que lhes deram origem. / Carbonyl compounds analysis is one of the routine procedures in several laboratories of control and quality of beverages. However, only total CCs, expressed by the acetald ehyde concentration, are quantified which results in a lack of knowl edge about the beverage’s quality and other CC concentrations. Although present in minute quantity, other CCs have a strong olfactory impact in many fermented beverages. In addition, the CCs found in wines have a strong affinity for bisulfite, added in winemaking process, and can form st able adducts, which will also interfere in the characteristics of ar oma. The greatest challenge, however, is to predict which CCs have the st rongest affinity for S(IV), what conditions favor this interaction and ho w to analyze them jointly. In order to better understand the reaction of CC- bisulfite adduct formation, this study has evaluated the role of 22 CCs in a “model soluction” containing bisulfite and in ten real samples of different wines, using a methodology developed and validated to analyze them simultaneously. This methodology is based on HPLC with binary gradient system of elution. On the basis of Principal Component Analysis (PCA) and dissociation constants (K d ), the results revealed that aliphatic aldehydes form adducts with S(IV), whereas ketones, cyclic aldehydes and trans- alkenes interact weakly and are found predominantly in their free form. These results revealed also that pH 10 and 11 were defined as the most appropriate for CC-S(IV) adduct dissociation and the total CCs were quantified reliably. In the wines and grapes studied were identified formaldehyde, acetaldehyde, butanal, hexanal, furfural, benzaldehyde, cyclo hexanone, E -pent-2-en-1-al, and 2-ethil hexanal, being the last one firstly identified in wines. Formald ehyde, acetaldehyde, butanal, and hexanal can be considered primary aroma since they are present in wines as well in their respective grapes.

Submitted by Edileide Reis (leyde-landy@hotmail.com) on 2013-04-23T12:41:25Z No. of bitstreams: 1 Luciana.pdf: 1586143 bytes, checksum: a57cce30857cde7aaf0e0e909a4950aa (MD5) / Made available in DSpace on 2013-04-23T12:41:25Z (GMT). No. of bitstreams: 1 Luciana.pdf: 1586143 bytes, checksum: a57cce30857cde7aaf0e0e909a4950aa (MD5) Previous issue date: 2007 / A análise dos compostos carbonílicos (CCs) é um dos procedimentos de rotina em muitos laboratórios de controle de qualidade de bebidas, no entanto, atualmente são quantificados apenas os CCs totais expressos em teores de acetaldeído, sem que sejam associados outros CCs com a sua qualidade. Esses compostos possuem impacto olfativo no aroma dos vinhos e uma forte afinidade pelo bissulfito, adicionado na vinificação, podendo formar adutos estáveis que interferirão também no aroma. Os maiores desafios, no entanto, consistem em predizer quais CCs têm maior afinidade pelo S(IV), que circunstâncias favorecem esta interação e como analisá-los em conjunto. Por esse motivo, no presente estudo foi avaliado o perfil de 22 CCs em “solução modelo" e em dez amostras reais de vinhos, empregando uma metodologia desenvolvida e validada para analisá-los de forma simultânea, que utiliza CLAE com sistema de gradiente binário de eluição. Baseado na Análise de Componentes Principais (ACP) e nas constantes de dissociação (Kd), os resultados revelaram que os aldeídos alifáticos formam adutos com S(IV), enquanto as cetonas, os aldeídos cíclicos e os trans-alcenais interagiram fracamente e são encontrados predominantemente em sua forma livre. Estes resultados revelaram também que a faixa de pH entre 10 e 11 foi definida como a mais apropriada para a dissociação do aduto CC-S(IV), favorecendo a quantificação segura dos CCs na forma total. Nos vinhos e uvas estudados foram identificados o formaldeído, acetaldeído, butanal, hexanal, furfural, benzaldeído, E-penten-2-al, ciclo hexanona e 2-etil hexanal, sendo este último identificado pela primeira vez neste tipo de matriz. Os quatro primeiros aldeídos citados podem ser considerados aromas primários por estarem presentes tanto nos vinhos quanto nas uvas que lhes deram origem. / Salvador

Na última década, a utilização de misturas de gasolina e etanol em qualquer proporção como combustível em veículos do tipo “flex” aumentou de forma significativa no Brasil. Compostos Carbonílicos (CC) pertencem a uma importante classe de poluentes emitidos pela frota veicular. A cidade de São Paulo, Brasil, tem 9,2 milhões de veículos, os quais afetam diretamente a qualidade do ar. Neste trabalho, foi determinada a concentração de quatorze CC na atmosfera, em três diferentes sítios de amostragem localizados na zona oeste da cidade de São Paulo, dois nos campus da Cidade Universitária: Instituto de Astronomia, Geofísica e Ciências Atmosféricas (IAG) e Instituto de Ciências Biomédicas (ICB) e um em Cerqueira César, Faculdade de Saúde Pública (FSP), no período de 2008/2009. Os CC foram coletados em cartucho de sílicagel, impregnada com 2,4-dinitrofenilhidrazina e analisados por Cromatografia Líquida de Alta Eficiência (CLAE) com detecção UV-visível. O conjunto de dados gerado foi caracterizado aplicando Análise de Componentes Principais (PCA) e Análise de Agrupamentos Hierárquicos (HCA). Foi utilizado o cromatograma completo, uma abordagem quimiométrica ainda não utilizada para avaliação de CC na atmosfera. Os cromatogramas das amostras foram alinhados utilizando os algoritmos Peakmatch e Optim_COW, deslocamentos de linha base e ruído foram removidos empregando, respectivamente, a primeira derivada e o método de ajuste polinomial de Savitzky- Golay. As amostras coletadas nos três sítios apresentaram contrações significativas de formaldeído (F), acetaldeído (A) e acetona e concentrações menores de butiraldeído, benzaldeído, valeraldeído e propionaldeído. A quantidade de acetaldeído foi superior à de formaldeído para a maioria das amostras, levando a uma razão F/A menor do que 1, fato que tem sido atribuído ao uso de etanol em larga escala como combustível veicular. Na análise univariada, foi observado um perfil semelhante nos gráficos de concentração dos CC em qualquer um dos sítios de amostragem. Na análise multivariada por PCA, a PC1 representou a quase totalidade da variação experimental (97,6%). Estes resultados podem sugerir a presença de uma única fonte de emissão. O gráfico de scores da PCA e o dendograma da HCA indicaram a formação de dois agrupamentos: um formado pelas amostras FSP e IAG e outro pelas amostras ICB. O gráfico de loadings da PCA indicou que as diferenças são devidas à concentração de todos os CC. A separação das amostras ICB das demais pode ser explicada pelas diferentes condições meteorológicas observadas no sítio ICB / In the last decade, the use of ethanol-blended-gasoline in any proportion as fuel in light vehicles (flex fuel) has significantly increased in Brazil. Carbonyl compounds (CC) are an important class of vehicular total hydrocarbons emission. São Paulo City, Brazil, has 9,2 million vehicles that directly affect the air quality. In this work, the concentration of fourteen CCs in the air of three different sites of São Paulo city was determined during 2008/2009. Two sites (IAG and ICB) were located inside São Paulo University whereas a third one was located in Cerqueira César (FSP). Compounds were collected in a silica-gel cartridge coated with 2,4-dinitro-phenylhydrazine and analyzed by CLAE with UV-Vis detection (365 nm). The sites were characterized by Principal Component Analysis (PCA) and Hierarquical Cluster Analysis (HCA). The entire chromatogram was used to multivariate calculations, which represents an innovative approach in CC studies. Chromatograms of the samples were aligned using the Optim_COW and Peakmatch algorithms, the baseline was corrected by the first derivative and instrumental noise was removed by Savitzky-Golay polynomial fit. The samples collected at the three sites presented different amounts of formaldehyde (F), acetaldehyde (A) and ketone and minor concentrations of butiraldehyde, benzaldehyde, valeraldehyde and propionaldehyde. The acetaldehyde content was observed to be superior to the formaldehyde, so that the F/A was lower than 1 for all sites. This fact can be related to the increasing use of ethanol as fuel. It was observed a similar profile of CC concentration in all sites studied. In PCA analysis, only one Principal Component could describe a large amount of experimental variability (97.57 %), indicating that a single emission source (vehicular) might have been present. The PCA scores graph and HCA dendogram pointed out that samples from FSP and IAG were similar whereas samples from ICB presented a different behavior. The loadings graph indicated that those differences were due to concentration of all CC. This fact could be due to different climatic conditions during sampling