Orientadores: Roy Edward Bruns, Ieda Spacino Scarminio / Tese (doutorado) - Universidade Estadual de Campinas, Instituto de Química / Made available in DSpace on 2018-08-26T07:44:37Z (GMT). No. of bitstreams: 1 Soares_DanielyXavier_D.pdf: 3162068 bytes, checksum: 54251cdb5d5253a933e10b93e4732324 (MD5) Previous issue date: 2014 / Resumo: "Planejamento e otimização de processos multirespostas: tratamento quimiométrico" Foram estudados três parâmetros cromatográficos: tempo de retenção, resolução e largura dos picos, em cromatogramas obtidos para uma mistura de onze agrotóxicos. Ajustes de modelos de regressão foram construídos e validados por ANOVA. Devido a sua simplicidade, os resultados obtidos para tempo de retenção foram usados em um programa interativo para estudar as separações como função de todo domínio experimental do planejamento simplex centróide. Um planejamento de misturas envolvendo três solventes (etanol, diclorometano e hexano) foi usado para avaliar a extração de alcalóides em Erythrina speciosa. Resultados diferentes foram observados para os extratos da flor, caule e folha, evidenciando que perfis de alcalóides distintos podem ser obtidos a partir de diferentes partes da planta. Modelos de regressão foram construídos e validados por ANOVA para dois alcalóides (tentativamente identificados por espectrometria de massas como eritrartina e 11-metoxi-erisodina, isóbaros em m/z 330, e erisotrina em m/z 314, com base em literatura prévia).A análise das componentes principais foi aplicada ao um conjunto de dados de absorbância de folhas de quatro cultivares de café (IPR-59, CAT, 027 e 083) obtidos entre 350-1100 nm por um espectroradiômetro portátil LI_COR 1800. Esta análise somente conseguiu discriminar espectros obtidos na face adaxial e abaxial das folhas. Como estes dados seguem um planejamento fatorial para quatro fatores (irrigação, estratos extremos, pontos cardeais e face) valores de efeitos foram determinados para absorbância em três comprimentos de onda estratégicos, 520, 554 e 650 nm, que são importantes para a quantificação de conteúdos de clorofilas e antocianinas / Abstract: "Design and multiresponse optimization of processes: chemometric treatment" Three chromatographic separation criteria were evaluated: retention time, resolution and peak width, in chromatograms obtained from a mixture of eleven pesticides. Regression models were constructed and validated by ANOVA. The use of the interactive program proved to be a valuable tool for studying peak separation behavior for the entire experimental domain of the simplex centroid design. Three solvents (ethanol, dichloromethane and hexane) and their binary and ternary mixtures were evaluated as extraction media for alkaloids in Erythrina speciosa. Different results were obtained between extracts of flowers, stems and leaves, showing that distinct alkaloid profiles can be obtained from different sources within the plant. Regression models were constructed and validated by ANOVA for two alkaloids (tentatively identified by MS as erytrartine and 11-methoxy-erisodine, isobaric ions of m/z 330, and erysothrine of m/z 314, based on previous literature). Principal component analysis was applied to data sets of absorbance values for leaves of four coffee cultivars (IPR-59, CAT, 027 and 083) obtained between 350 ¿ 1100 nm by a LI_COR 1800 portable radioespectrometer. This analysis was only able to discriminate between spectra of the abaxial and adaxial faces of the leaves. Since the spectral data were consistent with a factorial design for four factors (irrigated/field water, superior/inferior strata, cardinal points and face) effect values for absorbance were calculated at four strategic wavelengths, 520, 554 and 650 nm that are important for quantifying chlorophyll and anthocyanin contents of coffee / Doutorado / Quimica Analitica / Doutora em Ciências

Le film hydrolipidique est « l’ultime frontière entre l’organisme et l’environnement ». Ainsi, il offre à la peau une bonne protection et contribue largement à ses propriétés. Cependant, il peut être impliqué dans plusieurs perturbations cutanées. Le but de ce travail était d’obtenir un profil global de l’ensemble des lipides cutanés de surface, riche en informations structurales et capable de décrire l’organisation de ces molécules, permettant de suivre l’évolution physiologique du film hydrolipidique au niveau moléculaire. Plusieurs approches analytiques ont été développées et des outils statistiques et chimiométriques ont été utilisés pour exploiter les résultats.La caractérisation des lipides cutanés de surface (LCS) a été réalisée en chromatographie en phase gazeuse à haute température couplée à la spectrométrie de masse (HT-GC/MS). Le protocole analytique a été développé en conservant les structures lipidiques dans leur état intact. Plus de 200 composés ont été identifiés et répartis en 5 classes : acides gras libres, hydrocarbures, cires, stérols et glycérides. L’acide palmitique (C16:0) et l’acide sapiénique (C16:16) sont prépondérants et entrent dans la structure de très nombreux composés. Plusieurs approches quantitatives ont été mises en place : calcul des descripteurs chromatographiques, normalisation interne pour l’analyse par classe et exploitation chimiométrique des composés considérés individuellement.Trois problématiques ont été explorées par ces techniques et ont conduit aux résultats suivants :La répartition des LCS sur différentes zones corporelles se traduit par un ratio squalène/cholestérol plus élevé dans les zones riches en glandes sébacées que dans les zones pauvres. Ce descripteur est ainsi un bon critère d’évaluation de la balance sécrétion sébacée/desquamation. L’évolution des LCS en fonction de la localisation géographique et/ou la couleur de la peau a été étudiée en cherchant les variations de la composition par HT-GC/MS et de l’organisation par spectroscopie Raman. Une différence de composition a été mise en évidence entre les volontaires en fonction de la localisation géographique : le composé le plus impliqué est l’acide sapiénique (C16:1Δ6). Une différence de conformation (trans/gauche) au niveau des chaînes alkyles a été détectée.Enfin, l’adaptation de la barrière cutanée après la naissance a été déjà signalée mais sa traduction au plan moléculaire a pu être étudiée par le protocole analytique développé, chez les nourrissons dès les premiers jours après la naissance jusqu’à l’âge de 6 mois. Une diminution de la quantité globale de sécrétion sébacée a été observée, avec en parallèle, une augmentation sélective du cholestérol estérifié par des acides gras d’origine épidermique. Ceci indique un accroissement de la participation relative des lipides épidermiques dans le film hydrolipidique comme résultat d’une diminution de la sécrétion sébacée.Les approches analytiques développées dans ce travail de thèse permettent une caractérisation moléculaire fine des LCS en vue d’étudier l’évolution physiologique du film hydrolipidique. Les outils statistiques et chimiométriques ont permis une exploitation plus poussée des résultats pour extraire des informations inaccessibles par les approches classiques. Ce travail d’investigation offre de nombreuses perspectives, très prometteuses dans le domaine médical et dans le domaine cosmétique. / Skin hydrolipidic film is "the final frontier between the organism and the environment." Thus, it provides skin protection and contributes to its properties. However, it may be involved in several skin disturbances. The aim of this study was to obtain an overall profile of skin surface lipids (SSLs), rich in structural information and able to describe the organization of these molecules. This information allows monitoring the physiological evolution of hydrolipidic film at the molecular level. Several analytical approaches have been developed and chemometric and statistical tools were used to improve the interpretation of the results.SSL characterization was performed using high-temperature gas chromatography coupled with mass spectrometry (HT-GC/MS). The analytical protocol has been developed keeping the lipids in their intact structures. Over than 200 compounds were identified in the same run. These compounds have been classified in five lipid classes: free fatty acids, hydrocarbons, waxes, sterols and glycerides. The palmitic acid (C16:0) and sapienic acid (C16:16) are predominant and participate in the structure of many compounds. Several quantitative approaches have been implemented: calculation of chromatographic descriptors, normalization of the peak area for analysis by class and chemometric exploitation of individual compounds data.Three issues were explored by these techniques and lead to have the following results:The SSL distribution on different areas of the body, expressed as a squalene / cholesterol ratio, is higher in body areas rich in sebaceous glands than in poor areas. This descriptor is thus a good criterion for sebum secretion / desquamation balance measurement.The SSL evolution based on the geographical location and / or color of skin has been investigated by studying the variations in the composition and organization using HT-GC/MS and Raman spectroscopy. A difference in composition has been demonstrated between the volunteers according to geographical location: the most involved compound is the sapienic acid (C16: 1Δ6). A difference in conformation (trans / gauche) of at the alkyl chains was detected. Skin barrier adaptation after birth has already been reported. In this study, its evolution at the molecular level has been studied in infants from the first days after birth until the age of 6 months. A decrease in the total amount of sebaceous secretion was observed with, in parallel, an increase of cholesterol esterified with fatty acids of epidermal origin. This indicates an increase in the relative participation of epidermal lipids in the hydrolipidic film as the result of a decrease in sebaceous secretion. The analytical approaches developed in this thesis provide a detailed molecular characterization of SSLs in order to study the physiological evolution of the skin hydrolipidic film. Statistical and chemometric tools have allowed further exploitation of the results to extract information not accessible by conventional approaches. This investigative work offers many opportunities, promising in medicine and in cosmetics.