Dissertations / Theses on the topic 'Aromatic species'

Thesis (Ph. D.)--University of Missouri-Columbia, 2005.
The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file viewed on (May 23, 2006) Vita. Includes bibliographical references.

Mestrado Vinifera Euromaster - Instituto Superior de Agronomia - UL
Wine is an alcoholic beverage obtained from the fermentation of grape juice. Alcoholic fermentation is the main process to obtain the final product but of course other reactions take place during the transformation of grape juice into wine. Yeasts are one of the fundamental microorganisms to realize the alcoholic fermentation, that leads sugars to be transformed in ethanol and to development of other compounds. Yeasts as known are living organisms so they need nutrients for their reproduction and often the lack of some important nutrients can lead to a stuck or slug in their metabolic activity. One of the most important nutrient for yeasts growth is Nitrogen, main component of aminoacids and proteins, that constitute the basic structures of the microorganism.In winemaking, both in the cellar and in the vineyards, the addition of nitrogen under different circumstances is a common practice. Nitrogen seems to influence not only fermentation rate and yeast growth but many of the fermentation product such as ethanol, acetic acid, glycerol, and of course residual sugars and the production of some off flavours,such as hydrogen sulphide. Although each yeast, species and strains,showed different behaviour both in the fermentation rates, growth and production of different metabolites. Not only the quantity and kind of Nitrogen source but also the timing of the addition seem to influence all these aspects in slightly different way between different strain. The nitrogen compounds especially apparently ammino acids showed also a particular relationship with the production of esters of higher alcohols and other compounds but the pattern of ester production is still uncertain. In this study there will be considered the main aspects of nitrogen nutrition, how it affects the yeasts ecology and the different conditions on which it is used and also different strains and species requirements

This study involved the isolation, characterization, quantification and evaluation of the enantiomeric purity of linalool in the essential oil of aromatic species Lippia alba (Mill.) NE Brown (chemotype linalol-1,8-cineole), Ocimum basilicum L., Pelargonium graveolens L'Herit, Cinnamomum camphora Nees and Eberm var. linaloolifera Fujita, Aniba rosaeodora Ducke and Coriandrum sativum L., and carvone and limonene in the essential of Lippia alba (chemotype carvone-limonene). The quantification of monoterpenes was performed by GC-FID method for the internal standard. The analytical curves for quantification were linear in the range 1.0 to 10.0 mg mL-1 and showed appropriate values of correlation coefficients (0.996 to 0.999). The linalool was found with 91.38% (w/w) in essential oil of A. rosaeodora, 84.00% in C. camphora, 79.25% in L. alba, 79.00% in C. sativum, 73.33% in O. basilicum and 13.60% in P. graveolens. The carvone showed 58.13% and limonene showed 31.71% (w/w) of essential oil of L. alba. The enantiomeric purity analysis performed by GC-FID, using a column with enantioselective phase (β-cyclodextrin) and co-injection with commercial patterns, revealed the presence of the enantiomer (S)-(+)-linalool in L. alba and (R)-(-)-linalool in O. basilicum and C. camphora. The two enantiomeric forms of linalool were found in the P. graveolens, A. rosaeodora and C. sativum species. In the L. alba species (chemotype carvone-limonene) was observed a single enantiomeric form (R)-(-)-carvone and limonene showed the enantiomeric forms (S)-(-)-limonene and (R)-(+)-limonene, with predominance of the latter. The linalool was isolated from the essential oil of L. alba by TLC and subjected to analysis of GC-MS, GC-FID, 1H and 13C NMR and [α]D, which elucidated its structure and stereochemistry. The (S)-(+)-linalool isolated from L. alba (> 99%) was used to obtain the analytical curve. This isolation was necessary due to unavailability of acquire the (S)-(+)-linalool commercially pure.
Este estudo envolveu isolamento, caracterização, quantificação e avaliação da pureza enantiomérica do linalol nos óleos essenciais das espécies aromáticas Lippia alba (Mill.) N. E. Brown (quimiotipo linalol-1,8-cineol), Ocimum basilicum L, Pelargonium graveolens L Herit, Cinnamomum camphora Nees e Eberm var. linaloolifera Fujita, Aniba rosaeodora Ducke e Coriandrum sativum L. e da carvona e do limoneno no óleo essencial de Lippia alba (Mill.) N. E. Brown (quimiotipo carvona-limoneno). A quantificação dos monoterpenos foi realizada por CG-DIC pelo método do padrão interno. As curvas analíticas para a quantificação foram lineares no intervalo de 1,0 a 10,0 mg mL-1 e apresentaram valores adequados de coeficientes de correlação (0,996 a 0,999). O linalol foi encontrado com 91,38% (m/m) no óleo essencial de A. rosaeodora, 84,00% em C. camphora, 79,25% em L. alba, 79,00% em C. sativum, 73,33% em O. basilicum e 13,60% em P. graveolens. A carvona apresentou 58,13% e o limoneno 31,71% (m/m) no óleo essencial de L. alba (quimiotipo carvona-limoneno). As análises de purezas enantioméricas realizadas por CG-DIC, utilizando uma coluna com fase enantiosseletiva (β-ciclodextrina) e a co-injeção com padrões comerciais, revelaram a presença do enantiômero (S)-(+)-linalol em L. alba e do (R)-(-)-linalol em O. basilicum e em C. camphora. As duas formas enantioméricas do linalol foram encontradas nas espécies P. graveolens, A. rosaeodora e C. sativum. Na espécie L. alba (quimiotipo carvona-limoneno) foi observada uma única forma enantiomérica (R)-(-)-carvona e o limoneno apresentou as formas enantioméricas (S)-(-)-limoneno e (R)-(+)-limoneno com predominância desta última. O linalol foi isolado do óleo essencial de L. alba por CCD e submetido à análise por CG-EM, CG-DIC, RMN de 1H e 13C e [α]D, as quais elucidaram sua estrutura e estereoquímica. O (S)-(+)-linalol isolado de L. alba (> 99%) foi utilizado na obtenção da curva analítica. Esse isolamento foi necessário devido à indisponibilidade em adquirir o (S)-(+)-linalol comercialmente puro.

Doutoramento em Ciências do Mar e do Ambiente
Os incêndios florestais tornaram-se, nas últimas décadas, uma grande preocupação social e ambiental nas regiões de clima tipo-Mediterrâneo em todo o mundo, incluindo Portugal, devido ao aumento da sua frequência, severidade e extensão de áreas ardidas. Estas preocupações são ainda mais agravadas pelos cenários de alterações climáticas que preveem um aumento das condições propícias à ocorrência de incêndios. Enquanto que os efeitos dos incêndios na vegetação e processos hidrológicos do solo estão bem documentados, o seu impacto na produção e mobilização temporal de contaminantes em cinzas e solos queimados e dos seus efeitos nos sistemas aquáticos a jusante, tem sido pouco estudado. Em particular, a libertação pós-incêndio de metais e hidrocarbonetos aromáticos policíclicos (HAPs) para o meio ambiente, a qual assume particular preocupação devido à sua toxicidade, persistência e tendência para a bioacumulação, com impactos potencialmente nocivos no ambiente assim como na saúde humana, permanecem uma lacuna importante da investigação. Neste contexto, este trabalho pretende ser um contributo para compreender e avaliar o papel dos incêndios florestais na mobilização temporal de metais e HAPs, assim como dos seus efeitos a jusante. Deste modo, foi adotada uma abordagem integrativa para atingir estes objectivos. Primeiramente, quantificaram-se os níveis de vários metais (V, Mn, Co, Ni, Cu, Cd, Hg e Pb) e de quinze HAPs prioritários, em cinzas e solos não queimados e queimados recolhidos em plantações florestais no Centro-Norte de Portugal. Estas cinzas e solos foram recolhidos imediatamente após o incêndio, assim como quatro (após o primeiro evento de chuva pós-incêndio), oito e quinze meses após o incêndio. Foi também avaliado em que medida o tipo de floresta (plantações de eucalipto versus pinho) refletia os teores de contaminantes nas amostras analisadas. Por fim, foi realizada uma avaliação ecotoxicológica para investigar os efeitos tóxicos das escorrências superficiais recolhidas imediatamente e um ano após o incêndio. Esta avaliação foi efectuada com quatro espécies standard, representando diferentes grupos funcionais e níveis tróficos. De um modo geral, os resultados deste estudo indicaram um aumento consistente dos níveis de metais e HAPs em solos queimados de eucalipto em comparação com os solos de eucalipto não queimados. Estes incrementos apontaram para uma incorporação destes elementos nos solos queimados durante ou após o incêndio. Contrariamente, os resultados mostraram que 30 % do Hg retido nos solos de eucalipto foi libertado pelo incêndio, correspondendo a uma perda de 1.0 - 1.1 g Hg ha-1. Além disso, as cinzas apresentaram-se sempre enriquecidas em metais e HAPs em relação aos solos subjacentes, sugerindo que as concentrações de metais e HAPs na camada superficial do solo foram influenciadas pela deposição das cinzas resultantes do incêndio florestal. Adicionalmente, as cinzas e os solos queimados caracterizaram-se por elevados níveis de HAPs com três e quatro anéis, no entanto, o perfil de composição diferiu entre os solos queimados e não queimados. A distribuição dos HAPs pelo número de anéis e as razões de diagnóstico apontaram para que o incremento de HAPs nos solos queimados tenham sido maioritariamente originados pela queima de biomassa. As cinzas e os solos das encostas de eucalipto apresentaram níveis mais elevados de Hg relativamente às áreas de pinho, enquanto que o oposto se verificou para os teores de Co, Ni e HAPs. O tempo decorrido após o incêndio influenciou o comportamento dos metais e HAPs totais de três modos distintos: diminuição abrupta nas concentrações de Mn, Cd e HAPs após os primeiros eventos de chuva pós-incêndio (quatro meses após o incêndio); aumento dos níveis de V, Ni e Co durante os primeiros oito meses após o incêndio; e os níveis de Cu, Hg e Pb mantiveram-se praticamente inalterados durante todo o período de estudo. Além sido, as cinzas apresentaram picos de concentração em metais e HAPs imediatamente após o incêndio, registando-se uma diminuição brusca quatro meses depois. Esta diminuição poderá estar relacionada com a precipitação intensa ocorrida e a geração de escorrência superficial que terá promovido a lavagem e a lixiviação destes elementos das cinzas e dos solos. As escorrências superficiais apresentaram valores de HAPs significativamente mais elevados (quatro vezes) após o primeiro evento de chuva pós-incêndio do que um ano mais tarde. Do mesmo modo, verificaram-se diferenças na composição em termos de anéis e em termos de HAPs individuais. Ambas as amostras de escorrências superficiais induziram uma redução no crescimento dos dois produtores primários - Pseudokirchneriella subcapitata e Lemna minor – e inibiram a luminescência da bactéria Vibrio fischeri. Contrariamente, o invertebrado - Daphnia magna, não foi significativamente afetado nos respetivos ensaios. Surpreendentemente, a amostra de escorrência superficial recolhida um ano após o incêndio revelou ser a mais tóxica para as espécies estudadas. No geral, o presente trabalho contribui com uma nova perspetiva sobre o papel dos incêndios e as chuvas subsequentes na mobilização de metais e HAPs de solos e cinzas de áreas florestais ardidas, os quais constituem uma importante fonte difusa de poluição. Adicionalmente, este trabalho também enfatiza os riscos apresentados por estes contaminantes para os sistemas aquáticos a jusante, com consequências deletérias em ambas as suas condições química e biológica. Tendo isto em consideração, este estudo poderá ser um ponto de partida para a conceção e implementação de futuros programas de monitorização de áreas ardidas como parte dos planos de gestão pós-incêndio.
The increased frequency, severity and extent of wildfires over the past decades have become a major societal and environmental concern in Mediterranean-type climate regions across the world, including Portugal. These concerns are further aggravated by the likely future climate conditions, increasingly propitious to wildfire ignition and spreading. Whilst the impacts of wildfires on vegetation and soil hydrological processes have received considerable research attention, little is known about contaminants in ashes and burnt soils, their production and mobilization with time-since-fire and their off-site effects on aquatic systems. In particular, the fire-induced release of major and trace elements (metals) and polycyclic aromatic hydrocarbons (PAHs) into the environment, which assumes a singular concern due do their toxicity, persistence and tendency to bio-accumulate, with potentially harmful impacts on the environment as well as human health, has been neglected. Hence, the present work aims to be a contribution to understand and evaluate the role of wildfire and time-since-fire in the mobilisation of metals and PAHs and their off-site effects. As a way to fulfil these proposes an integrative approach was adopted. First, the levels of metals (V, Mn, Co, Ni, Cu, Cd, Hg and Pb) and the fifteen priority PAHs were surveyed in ashes and burnt and unburnt soils collected immediately after a wildfire in forest plantations in north-central Portugal, as well as four (after the first post-fire rainfall events), eight and fifteen months later. It was also investigated in what extent the forest type (eucalypt versus pine plantations) constrain the levels of the contaminants. Then, to assess the toxic effects of the surface runoff collected immediately after fire and one year later, an ecotoxicological assessment was performed using four standard species representing different functional groups and trophic levels. In general, results of this study showed a consistent increase in the levels of metals and PAHs in burnt eucalypt soils compared to unburnt eucalypt soils. The inputs of these contaminants point to an incorporation of these elements in burnt soils during or after the fire. However, results showed that 30 % of the Hg retained in the eucalypt soils were released by the wildfire, corresponding to a loss of 1.0-1.1 g Hg ha-1. Moreover, ashes were consistently enriched in metals and in PAHs relatively to the underlying topsoil, suggesting that concentrations of metals and PAHs in topsoil were influenced by the deposition of ash resulting from the wildfire. Additionally, ashes and burnt soils were characterized by higher levels of PAHs with three to four rings, however the homologue profile differed between the unburnt and burnt soils. The PAHs’ composition profile and the isomeric diagnostic ratios indicates that PAHs in forest soils were mainly originated from biomass burning. Ashes and soils from eucalypt hillslopes were consistently enriched in Hg relatively to pine areas, and the opposite was true for Co, Ni and PAHs levels. Time-since-fire has shown to influence metals and PAHs in three different ways: concentrations of Mn, Cd and PAHs declined abruptly after the first rainfall event (four months after the fire); concentrations of V, Ni and Co increased during the first eight months after the fire; and levels of Cu, Hg and Pb hardly changed during the study period. Additionally, ashes also revealed peak concentrations of metals and PAHs immediately after the fire, with a sharply decline four months later. These decreases could be related to the heavy rainfall and subsequent overland flow that have promoted the washout and leaching of these elements from soils and ashes. The total PAHs loads in the runoff samples were markedly higher (four times) following the first rainfall event after the wildfire than one year later and also had noticeably different compositions in terms of ring-based as well as individuals PAHs. Both runoff samples was found to induce significant decreases in the growth of the two primary producers- Pseudokirchneriella subcapitata and Lemna minor- and inhibited the luminescence of the bacteria Vibrio fischeri. Conversely, the invertebrate - Daphnia magna, was not significant affected. Surprisingly, the runoff collected one year after the wildfire has shown to be the most toxic to the tested species. Overall, findings of this study brings a new insight on the role of wildfire and subsequent rainfall in the mobilisation of metals and PAHs in ashes and soils from burnt forest plantations, which constitutes an important source of diffuse pollution. In addition, this study also emphasize the risks posed by these contaminants to downstream water bodies, with deleterious consequences for both chemical and biological conditions. In view of that, this study may be a starting point for design and implement future monitoring programs in burnt areas as part of post-fire management plans.

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Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior (CAPES)
Este trabalho teve como objetivo desenvolver procedimentos de germina??o, estaquia e micropropaga??o de Xylopia aromatica. Os experimentos foram conduzidos na Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM), em diamantina ? MG, cujos trabalhos foram divididos em dois cap?tulos. No primeiro cap?tulo foram realizados oito experimentos. A germina??o foi avaliada em quatro experimentos, onde sementes de Xylopia aromatica, separadas em lotes distintos quanto ? densidade, foram submetidas ? quebra de dorm?ncia utilizando GA3 em diferentes concentra??es (0; 25; 50; 100; 250; 500; e 1000 mg L-1), nos tempos de imers?o 24 e 48 horas. N?o ocorreu germina??o durante os 210 dias de avalia??o. Foram realizados quatro experimentos de estaquia, onde segmentos caulinares (com e sem folhas) e radiculares com classes de di?metros distintas, foram imersos por 30 segundos em solu??o de AIB (0; 2000; 4000; 6000; 8000 e 10.000 mg L-1) a fim de induzir o enraizamento advent?cio. Foi avaliado o percentual de enraizamento durante 140 dias. N?o houve enraizamento em nenhum dos experimentos, porem ocorreu brota??es nas estacas caulinares que foram imersas nas concentra??es de 2000, 4000 e 6000 mg L-1 de AIB. No segundo cap?tulo, foram realizados seis experimentos, que envolveram etapas de multiplica??o, alongamento e enraizamento in vitro. Explantes foram submetidos a diferentes meios de cultura (MS e WPM), e concentra??es de BAP (0,5 e 0,8 mg L-1), objetivando determinar o melhor meio de cultura e concentra??o de BAP para a multiplica??o da esp?cie. Avaliou-se tamb?m, o alongamento em explantes com o uso de combina??es de ANA e BAP e GA3, e enraizamento com o uso de AIB e ANA. O meio MS acrescido de 0,8 mg L-1 de BAP foi o que apresentou melhores resultados para a multiplica??o de Xylopia aromatica. Na fase de alongamento, o GA3 na concentra??o de 5,0 mg L-1 foi o regulador de crescimento que apresentou melhor resultado em altura e n?mero de folhas. No enraizamento, o AIB e o ANA n?o foram eficazes na indu??o de ra?zes, necessitando mais estudos relacionados ? etapa de enraizamento para a esp?cie.
Disserta??o (Mestrado) ? Programa de P?s-Gradua??o em Ci?ncia Florestal, Universidade Federal dos Vales do Jequitinhonha e Mucuri, 2016.
This study aimed to develop germination procedures, cutting and micropropagation Xylopia aromatica. The experiments were conducted in Universidade Federal dos Vales do Jequitinhonha e Mucuri (UFVJM) in Diamantina - MG, whose works were divided into two chapters. In the first chapter were carried out eight experiments. Germination was evaluated in four experiments where aromatica Xylopia seeds, separated into separate lots for density, were submitted to dormancy breaking using GA3 at different concentrations (0, 25, 50, 100, 250, 500, and 1000 mg L-1) under immersion for 24 and 48 hours. Not germinated during the 210 days of evaluation. Four cutting experiments were carried out where segments shoot (with and without leaves) and root with different diameter classes were immersed for 30 seconds in AIB solution (0; 2000; 4000; 6000; 8000 and 10,000 mg L-1) to induce adventitious roots. Rooting percentage was evaluated during 140 days. There was no rooting experiments, however sprouting occurred in the cuttings were dipped in concentrations of 2000, 4000 and 6000 mg L-1 AIB. In the second chapter, we were conducted six experiments, involving multiplication steps, stretching and in vitro rooting. Explants were subjected to different culture medium (MS and WPM) and BAP (0,5and 0,8mg L-1), in order to determine the best medium and concentration of BAP for the multiplication of the species. It also evaluated the elongation explants using combinations of ANA and BAP and GA3 and rooting using AIB and ANA. The MS medium plus 0.8 mg L-1 BAP showed the best results for the multiplication of Xylopia aromatica. In the stretching step, the concentration of GA3 at 5,0 mg L-1 was the growth regulator showed better results in height and leaf number. Rooting, AIB and ANA were not effective in inducing roots, requiring more studies related to the rooting stage for the species.

Le calvados est une eau-de-vie obtenue par distillation du cidre. Le cidre de distillation résulte d’une fermentation naturelle spontanée non maîtrisée, qui permet toutes les interactions possibles entre les différentes communautés microbiennes. En fin de fermentation alcoolique, le glycérol produit peut être dégradé et converti en 3-hydroxypropionaldehyde (3-HPA) par Lactobacillus collinoides via l’enzyme glycérol déshydratase codée par l’opéron pdu. Lors de la distillation, la déshydratation du 3-HPA en acroléine entraîne des désordres organoleptiques connus sous le nom de piqûre acroléique en développant un goût d’amertume dans les calvados. Ces travaux de thèse ont eu pour premier objectif d’apporter une réelle nouveauté dans l’étude de la diversité de dix cidres de distillation normands lors de la fermentation par une approche de métagénomique et d’établir des liens entre la composition microbienne et la qualité aromatique. Cette approche a permis de mettre en évidence plus de 40 genres bactériens et fongiques et des différences significatives ont été constatées au sein de ces populations entre les cidres des différents producteurs au cours du processus de fermentation, suggérant que les pratiques d’élaboration mènent à une typicité du cidre et donc à celle du calvados. L’étude de la composition des communautés microbiennes en lien avec la composition aromatique des cidres de distillation et celle des micro- distillats a été effectuée. Trois groupes de dynamiques et compositions microbiennes, directement liées aux producteurs, émergent conduisant à des compositions aromatiques différentes. L’analyse comparative de huit génomes de souches de Lactobacillus collinoides isolées à partir de cidres de distillation portant sur les métabolismes associés à la fermentation et sur la capacité des souches à métaboliser le glycérol a été effectuée. Deux types d’opéron pdu se profilent et cette variabilité génétique observée entre les souches de L. collinoides suggère des capacités différentes de dégradation du glycérol. Un plan expérimental (D-optimal) faisant varier 6 facteurs (glucose, fructose, azote, éthanol, acide malique, pH) a été élaboré pour étudier le métabolisme du glycérol chez ces souches. Trois profils génétiques et métaboliques ont pu être mis en évidence. Les souches de L. collinoides possédant l’opéron de type I sont toujours capables de dégrader le glycérol, contrairement à celles porteuses de l’opéron de type II. Ces travaux ouvrent des perspectives intéressantes quant à la présence et la physiologie de L. collinoides lors de l’élaboration du cidre et son implication dans la piqûre acroléique
Calvados is a Normandy brandy made by the distillation of cider. Ciders destined for distillation resultfrom spontaneous fermentation without any human intervention, leading to various interactions between thedifferent microbial communities. At the end of alcoholic fermentation, glycerol produced can be degraded andconverted to 3-hydroxypropionaldehyde (3-HPA) by Lactobacillus collinoides via the glycerol dehydrataseenzyme encoded by the pdu operon. During distillation, dehydration of 3-HPA to acrolein leads to organolepticdisorders, developing a bitterness taste in calvados known as “piqûre acroléique”. The first objective of this thesiswas to unveil the diversity of ten ciders for distillation during fermentation using a high throughput sequencing(16S, ITS1) approach and to establish links between microbial composition and aromatic quality. This approachallowed us to identify more than 40 bacterial and fungal and significant differences were found among fungal andbacterial populations between producers during the fermentation process, suggesting that the practices lead to thetypicity of cider, and therefore to the typicity of calvados. The study of the microbial composition was correlatedwith the aromatic composition of ciders for distillation during the fermentation process and of the micro-distillates.Three groups of microbial dynamics and compositions, directly related to the producers, were observed leading todifferent aromatic compositions. A comparative analysis of eight genomes of Lactobacillus collinoides strainsisolated from the ciders according to the different metabolisms associated with fermentation as well as on theability of the strains to metabolize glycerol was performed. Two types of operon pdu were highlighted and thisgenetic variability between L. collinoides strains suggests different abilities for glycerol degradation. Anexperimental design (D-optimal) by varying 6 factors (glucose, fructose, nitrogen, ethanol, malic acid, pH) wasdeveloped to study the metabolism of glycerol in these strains. 3 genetic and metabolic profiles were identified. L.collinoides strains with operon type I are always able to degrade glycerol, contrarily to those harbouring the operonof type II. This work opens up interesting perspectives regarding the presence and physiology of L. collinoidesduring the development of cider and its involvement in the “piqûre acroléique”

A three part study involving aspects of radical properties of various aromatic species was accomplished. Experiments to ascertain the importance of geometric and electronic effects on the intramolecular transfer of a pi-complexed radical to a terminal double bond was performed. Several 4-aryl-1-butenes were reacted in competition with 1-undecene with a variety of radical precursors at 70��C. The reactions were studied in both complexing and noncomplexing solvents. Most of the relative rates varied little from unity and no dependence on solvent was observed. A series of 21 phenacylarenes was subjected to mass spectrometry. The fragmentation process leading to arylmethyl radicals and benzoyl cations was measured by calculating the ratios of parent ion to benzoyl cation signal strength. In the case of the eleven homoaromatic compounds little overall correlation of these values to traditionally accepted arylmethyl radical stabilities was found. The degree of fragmentation for isomers of the same compound were found to be explicable in term of arylmethyl radical stabilities. Degrees of fragmentation of some compounds could be rationalized in terms of the bond order of the bond being broken, as calculated by AM1 methods. The ten heteroaromatic compounds showed little correlation of fragmentation with bond order. The degree of fragmentation was found to be dependent on many different variables of the individual molecules. No correlation with any one factor could be found. The relative rates of benzylic hydrogen atom abstraction from a series of substituted toluenes and cumenes under conditions of bromination by diethyl bromomalonate were determined at 70��C. A range of reactivity of 21.7 and 10.5 was found for the toluenes and cumenes respectively. The relative rates were found to correlate best with Hammett sigma plus constants. Hammett values of -0.89 and -0.73 were calculated for the substituted toluenes and cumenes. Reactivities for several alkyl benzenes having different steric requirements at the reaction site were also studied. The relative rates for these compounds indicate a relatively large radical to be the atom abstracting agent. The results of the Hammett correlations combined with the studies involving the steric properties of the abstracting radical suggest that diethyl malonyl radical is the hydrogen atom abstracting species.
Graduation date: 1997

碩士
國立成功大學
環境工程學系碩博士班
101
Worshipping ancestors and gods by burning incense sticks has been one of the important traditions in many Asian nations. However, burning incense can produce a great amount air particulates. In addition, the surface of the particulates adsorbes many organic (e.g., polycyclic aromatic hydrocarbons, PAHs) and inorganic chemicals, (e.g., heavy metals).These adsorbed chemicals, once enter the human respiratory system, can stimulate human lungs, and possibly induce cancer. According research, people spend approximate 80% of day in the indoors space, and many Chinese burn incenses daily, so incenses smoke has long time been an indoor pollution in Tawan. Our research use a combustion chamber to simulate the indoor environment. After collecting the combustion products, a traditional extract method was used to extract PAHs and heavy metals of incense particulate, and to investigate the toxicological characteristics of incense particulates. Our Considering that the first target organ is the lungs when human are exposed to air pollution, we utilized normal human bronchial epithelial cell (the BEAS-2B cell line) as the target cell for biological toxicity tests, along with the MTT assay and the Comet assay. Hope chemical analysis result and biological toxicity result can help us to understand incense particulates toxicity characteristic. Our results show that, in terms of particulate emission, Xin Shan incense, Chen incense, and Liao incense are respectively 41.3, 19.02, and 16.05 mg/g-incense. The emission from the Xin Shan incense stick is higher than both Chen incense and Liao incense. In the heavy metal part, all incense particulates mainly contain K, Na, Ca, which are harmless to human. The heavy metals found in the extract did not exhibit toxicity respond in cell tests. However, PAHs extract of incenses particulate clearly showed toxicity. The respond (average of cell viability is 50.33±15.2%), Chen incense is 8.90±1.11 µg/g-incense, Xin Shan incense is 8.17±0.78 µg/g-incense Liao incense is 4.51±0.43 µg/g-incense. Among the three incences Chen incense was the highest, and PAHs toxicity equivalency had a highly negative correlation with the cell viability (r= -0.87). In addition, genotoxicity test results show PAHs in the incenses particulate can cause DNA damage. This result was also consistent with the cell viability test result. It is therefore concluded that the particulate toxicity of the incense smoke is mainly contributed by PAHs. It is suggested that we should be more concerned about the PAHs emission in the incense smoke.

As plantas têm sido usadas como remédios pelo homem desde há milhares de anos e várias culturas incluem um amplo conhecimento sobre suas virtudes medicinais. Práticas tradicionais, apoiadas por conhecimentos empíricos, crenças e procedimentos, desempenham um papel importante, primeiramente nos cuidados de saúde das populações e, secundariamente, como evidências etnofarmacológicas disponíveis para o desenvolvimento de fármacos. As plantas aromáticas são associadas a muitas aplicações biológicas e médicas. Elas biossintetizam uma grande variedade de metabolitos secundários voláteis que desempenham importantes papéis eco-fisiológicos, tais como, proteção contra organismos prejudiciais, predadores, patogénicos microbianos, stresse abiótico, calor, desidratação, etc ..., desempenhando também um papel importante na interação com outras plantas e organismos. Os metabolitos voláteis, distintivos das plantas aromáticas, são agentes naturalmente seleccionados para interagir com alvos biológicos. Este trabalho está focado em plantas medicinais e aromáticas de Cabo Verde. Teve por base informação etnofarmacológica recolhida por inquéritos diretos à população, e que conduziu ao estudo dos metabolitos voláteis das espécies aromáticas endémicas e nativas utilizadas na medicina tradicional de Cabo Verde. Reportamos a composição dos isolados voláteis das quatro plantas medicinais aromáticas, Artemisia gorgonum, Satureja forbesii, Hytis pectinata e Cymbopogon citratus, colhidas na ilha de Santiago. Os óleos essenciais foram obtidos por hidrodestilação foram analisados por combinação de técnicas de cromatografia de fase gasosa e espectrometria de massa. A informação sobre a composição química dos recursos naturais de Cabo Verde é especialmente relevante, considerando a validação das práticas da medicina tradicional, bem como, a valorização da biomassa vegetal como fonte de compostos úteis para pesquisas, incluindo desenvolvimento de fármacos e outros fins. Este trabalho também é uma homenagem aos terapeutas tradicionais de Cabo Verde e uma contribuição para o conhecimento da cultura e do património vegetal deste arquipélago Verde.
Plants have been used as remedies by man for thousands of years and various cultures have an extensive knowledge about their medicinal properties. Traditional healing practices, supported by empirical knowledge, beliefs and procedures, play important roles, immediately, in health care of populations, secondarily, as ethnopharmacological starting evidence for Drug Discovery. Aromatic plants are very often associated with many biological and medical applications. They produce a wide range of volatile secondary metabolites with important ecophysiological roles, such as, protection against harmful organisms, predators, microbial pathogens, abiotic stress, heat, dehydration, etc..., or playing important interaction with other plants and organisms. Thus, volatile metabolites, distinctive of aromatic plants, are naturally skilled to interact with biological targets. This work is focused on medicinal and aromatic plants from Cape Verde. Ethnopharmacological information, collected by direct inquires to locals, was in the base of a prospective chemical study on volatile metabolites of endemic and native aromatic species from Cape Verde used in traditional medicine. We report on the composition of the volatile isolates of four aromatic medicinal plants, Artemisia gorgonum, Satureja forbesii, Hytis pectinata and Cymbopogon citratus, collected at Santiago Island. The essential oils were prepared at laboratory by hydrodistillation and analyzed by combination of gas chromatography and mass spectroscopy techniques. Chemical information on these natural resources of Cape Verde is useful data in regard to the validation of traditional medicinal practices, as well as, in regard to the valorization of plant biomass as sources of compounds useful for research, including the development of drugs, and other industrial purposes. This work is also homage to the traditional therapists of Cape Verde and contribution for the knowledge of the culture and the vegetal patrimony of this archipelago Verde.

Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous environmental contaminants that can be modified to oxygenated PAH (oxyPAHs) derivatives. It is well known that oxyPAHs tend to be much more reactive than their parent compounds. Toxicity can be attributed to direct interaction with target molecules or generation of reactive oxygen species (ROS). Metals are another class of contaminant found ubiquitously throughout the environment. Some metals are toxic at levels below the 1:1 ratio predicted by the biotic ligand model and are thought to manifest toxicity through ROS generation. Often metals and PAHs occur as co-contaminants in industrialized environments, yet little is known about their potential co-toxicity or mechanisms of action in mammalian reproductive function. Previously, we described that a PAH, 9, 10-phenanthrenequinone (PHEQ), inhibited LH-stimulated progesterone secretion in dispersed rat corpus luteal (CL) cells (Nykamp et al., 2001). Viability was decreased in CL cells exposed to PHEQ and 1,2-dihydroxy-anthraquinone (1,2-dhATQ), but not their parent compounds phenanthrene (PHE) or anthracene (ANT). Similarly, LH-stimulated progesterone production in CL cells was inhibited by PHEQ and 1,2-dhATQ, but not PHE. Further investigation revealed that PHEQ, but not PHE, ANT nor 1,2-dhATQ generated ROS in CL cells. Viability experiments were repeated using the choriocarcinoma cell line JEG-3 with similar results. Various metals were assessed for their toxicity to both CL and JEG-3 cells. The endpoints used to measure viability were metabolic activity and membrane integrity. In general, metabolic activity was a more sensitive indicator of toxicity than membrane integrity. The order of toxicity for metals in CL cells was Hg2+ > Cd2+ > Zn2+ > Ni2+ > Cu2+ for metabolic activity and Hg2+ ≈ Zn2+ > Cd2+ > Cu2+ > Ni2+ for membrane integrity. Only Hg2+ and Cu2+ were tested in JEG-3 cells. While Cu2+ was non-toxic, EC50s for Hg2+ metabolic activity and membrane integrity were 20 mM and 23 mM, respectively. Experiments were designed to study the mixtures of metals and PAHs on viability, ROS production, and LH-stimulated progesterone production in CL cells. Mixtures of each metal with either PHEQ or 1,2-dhATQ were incubated with CL cells and their effect on metabolic activity and membrane integrity assessed. Generally, most metal/oxyPAH mixtures displayed only additive toxicity. However, mixtures of Cu2+ and PHEQ showed synergistic toxicity to both metabolic activity and membrane integrity. Mixture studies in JEG-3 cells used only combinations of Cu2+ or Hg2+ with PHEQ or 1,2-dhATQ. Similar results to metabolic activity and membrane integrity in CL cells were observed. Mixtures of Cu2+ and PHEQ or 1,2-dhATQ were tested in CL cells for their effect on LH-stimulated progesterone secretion and ROS production. Additive effects were observed in both LH-stimulated progesterone secretion and ROS production for Cu2+/1,2-dhATQ mixtures while synergistic effects for both parameters were seen with Cu2+/PHEQ. Efforts to determine the site of action for mixtures of Cu2+/PHEQ involved adding the cholesterol analogue, 22-OH cholesterol (22-OHC) to CL cells in the absence of LH. Cytochrome P450 side-chain cleavage (CYP450scc) enzyme operates constitutively and the addition of 22-OHC to CL cells resulting in a 5-fold increase in progesterone production without added LH. Kinetic assays with 22-OHC show that while progesterone secretion was inhibited with PHEQ addition alone, a further significant reduction with both Cu2+ and PHEQ was not observed. The use of forskolin, an activator of adenylate cyclase, did not show any significant enhancement of progesterone secretion with the addition of Cu2+/PHEQ compared to PHEQ alone. The potential targets of Cu2+/PHEQ mixture include any step in the steroidogenic cascade from activation of protein kinase A onward with the proteins of the mitochondria, cytochrome P450 side chain cleavage enzyme and steroidogenic acute regulatory protein, being the most likely. Differential display polymerase chain reaction (ddPCR) was a molecular approach taken to determine the effect of PHEQ on JEG-3 gene expression. The genes whose expression appeared to be up-regulated with PHEQ exposure were serine protease inhibitor, Alu repeat sequence, heterogeneous ribonuclear ribonucleoprotein C (hnRNP C), eukaryotic translation initiation factor 3 (eIF3), nucleoporin-like protein, eukaryotic translation elongation factor 1a1 (eEF1 a 1), autophagy-linked FYVE domain (Alfy), spectrin, and proteasome. Apparent down-regulated genes in JEG-3 cells after PHEQ exposure included poly(ADP-ribose) polymerase 10 (PARP10), polyglutamine binding protein-1 (PQBP-1), heterogeneous ribonuclear ribonucleoprotein C (hnRNP C), eukaryotic translation initiation factor 5A (eIF5A), and keratin. In both cell types, oxyPAHs were more toxic than their parent compounds. Metals showed greater toxicity to metabolic activity than to membrane integrity. Of the combinations tested, only PHEQ and Cu2+ exhibited synergistic toxicity. ROS generation was the likely mechanism behind PHEQ/Cu2+ toxicity. Both cell types used represent critical roles in human reproductive health. The proper production of progesterone, a critical hormone for the maintenance of pregnancy in mammals, represents a unique endpoint for the assessment of toxicity. These results illustrate the need to study modified oxyPAHs, metals and metal/oxyPAH mixtures for their potential impact on human reproductive health.

碩士
國立成功大學
環境醫學研究所
97
Metalworking fluids (MWFs) are used recycling in fastener manufacturing industries. Oil mists found in the workplace are formed via the impaction of MWFs and heating- evaporation- condensation process caused by the frictions of machines. MWFs are made of the hydrocarbons, containing polycyclic aromatic hydrocarbons (PAHs), organic compounds, and metal elements. Recycling of MWFs lead to the accumulation of their PAH and metal contents. Workers exposed to oil mists could cause adverse health effects. Studies have indicated that adverse health effects may derive from not only PAHs and metals but also oxidative stress, initiated by the formation of reactive oxygen species (ROS). The formation mechanism of ROS on particles may relate to PAHs and metals. The objective of this study is to determine the impact associated with the change of MWFs on oil mists, PAHs, metals and ROS concentration in the workplace at the different period of metalworking fluids in the threading process. The eight-stage cascade impacter (Marple 298) was used in static sampling to collect particle and segregate particles in sizes. The collected particles were pretreated for analyzing their chemical compositions including metals, PAHs, and ROS. The results show particle size distributions of oil mists occurred in the workplace were dominated by the fine mode (86.0-88.6%) for samples collected at the different of metalworking fluids. And particle size distributions weren’t influenced by the production rate. PAHs concentrations of coarse particles in the workplace were dominated by the HMW-PAHs at the different period of metalworking fluids; PAHs concentrations of fine particles were dominated by the LMW-PAHs; Total PAHs concentrations were dominated by the fine particles. The longer MWFs were used, more amounts of PAHs concentration were found. The longer MWFs were used, the less the amounts of LMW-PAHs concentration could be found. The longer MWFs were used, more amounts of MMW-PAHs and HMW-PAHs concentration were found. The results show the same trend with the different molecular weight PAHs in MWFs. The longer MWFs were used, more amounts of metals concentration were produced. The results have the same trend with metals concentration in MWFs. The longer MWFs were used, higher ROS concentration were produced. The relationship between the different molecular weight PAHs and metals concentrations and ROS concentrations was determined. The result found that the combination of both coarse particles and fine particles of total PAHs could explain the variations of ROS concentrations up to 51%. The combination of both coarse particles of Fe and Na could explain the variations of ROS concentrations up to 92%. By conducting regression analyses, this study found that the production rate would be able to explain the variations of LMW-, MMW-, HMW-PAHs, and metals concentrations up to 70.0%, 78.0%, and 85.0%. The above result clearly indicates that the predicable model was a useful method for assessing LMW-, MMW-, HMW-PAHs, metals and ROS concentration in the workplace. In conclusion, the longer MWFs was used, more LMW-, MMW-, HMW-PAHs, metals and ROS concentrations were produced suggesting that appropriate air pollution control devices should be used in this industry immediatedly.

碩士
國立中興大學
農業企業經營管理碩士在職專班
105
Rice is the core industry in Taiwan''s agricultural sector, and it is also the industry that inputs the most agricultural resources. Facing the global climate change and other environmental issues, WTO’s agriculture agreements, economic growth, changes in eating habits and domestic agricultural policy changes and other issues, Taiwan''s rice industry has encountered the important issues of how to promote agricultural transformation and sustain the use of agricultural land. Through the literature review and the SWOT model, this study analyzes the important strategies of successful agricultural transformation for "Wufeng Aromatic Rice". The strengths of "Wufeng Aromatic Rice" include having good irrigation water resource, establishing the multi-year agreement of contract farming, building brand value of "Wufeng Aromatic Rice", mastering food safety requirements, and developing the sightseeing cluster of agricultural tourism. The weaknesses include price competition and product differentiation among many brands of aromatic rice in the market. The threats include insufficient stability of the rice quality, the old- fashioned marketing channels, and the risk of pesticide residues. The opportunities include establishing the database of production and marketing traceability and combining the innovation of rice culture with local leisure tourism. It is suggested that the government may borrow from the relevant experience of Wufeng Aromatic Rice to assist the farmers'' association to continue to promote the special rice production and marketing areas.