Thesis (Ph. D.)--University of Missouri-Columbia, 2000. / Typescript. Vita. Includes bibliographical references (leaves 151-159). Also available on the Internet.

Thesis (MSc Food Sc)--University of Stellenbosch, 2011. / ENGLISH ABSTRACT: Alicyclobacilli are endospore-forming, thermophilic, acidophilic bacteria (TAB) that survive the pasteurisation process and spoil acidic fruit juices through the production of the taint compound guaiacol. Guaiacol causes an undesirable odour with an unpleasant smoky, medicinal or phenolic-like taste. This thesis reports on the precursors, vanillin and vanillic acid metabolised to guaiacol by Alicyclobacillus spp. in fruit juice, the pathway of guaiacol production and the spoilage potential of contaminated fruit juices supplemented with these precursors. A high performance liquid chromatography method with UV-diode array detection (HPLC-DAD) was developed for the simultaneous detection and quantification of guaiacol and its precursors. Alicyclobacillus acidoterrestris FB2 was incubated at 45 °C for 7 d in Bacillus acidoterrestris (BAT) broth supplemented with ferulic acid, vanillin or vanillic acid. The cell concentrations were determined every 24 h and the concentration of the precursors and the production of guaiacol was determined using HPLC-DAD. The guaiacol production was also determined using the peroxidase enzyme colourimetric assay (PECA). Alicyclobacillus acidoterrestris produced guaiacol from vanillin and vanillic acid, confirming both vanillin and vanillic acid as precursors for guaiacol production by A. acidoterrestris FB2. Furthermore, a metabolic pathway directly from vanillin to guaiacol was identified in this study. However, guaiacol was not produced by A. acidoterrestris FB2 in the samples supplemented with ferulic acid and it is, therefore, not considered a direct precursor for guaiacol production by A. acidoterrestris. The spoilage potential of apple juice supplemented with either 10 mg L-1 or 100 mg L-1 vanillin or vanillic acid by A. acidoterrestris FB2 (106 cfu mL-1) was also evaluated. The production of guaiacol increased with the increase in vanillin or vanillic acid concentrations (in BAT broth and apple juice) indicating that the concentration of vanillin and vanillic acid present in fruit juice will influence the spoilage potential of the juice. Guaiacol concentrations in apple juice well above the best estimated threshold value of guaiacol for taste (0.24 – 2.00 μg L-1) and odour (0.50 - 2.32 μg L-1) was produced by A. acidoterrestris FB2 in the apple juice supplemented with 10 mg L-1 vanillin or vanillic acid. This indicates that fruit juice with a vanillin or vanillic acid concentration as low as 10 mg L-1 has the potential to spoil if the juice is contaminated with A. acidoterrestris. The concentrations of vanillin and vanillic acid in different fruit juices can be used to indicate if a specific fruit juice is susceptible to guaiacol spoilage by Alicyclobacillus spp. In the development of juice products and different blends of fruit juices, special care must be taken not to concentrate the amount of vanillin and vanillic acid present in the fruit juices. / AFRIKAANSE OPSOMMING: Alicyclobacilli is endospoor-vormende, termofiliese, asidofiliese bacterie (TAB) wat die pasteurisasie proses oorleef en suur vrugtesappe bederf met die produksie van ‘n taint komponent guaiakol. Guaiakol veroorsaak ‘n ongewensde reuk en onaangename rookagtige, medisinale of fenoliese smaak. Hierdie tesis doen verslag oor die voorloper komponente, vanillien en vanilliensuur in vrugtesappe wat gemetaboliseer word na guaiakol deur Alicyclobacillus spesies, die padweg van guaiakol produksie en die bederfbaarheid van gekontamineerde vrugtesap aangevul met hierdie voorloper komponente. ‘n Hoëprestasie vloeistof chromatografie metode met UV-deteksie (skanderend) (HPVC) is ontwikkel vir die gesamentlike deteksie en kwantifisering van guaiakol en die voorloper komponente. Alicyclobacillus acidoterrestris FB2 is geïnkubeer by 45 °C vir 7 d in Bacillus acidoterrestris (BAT) medium aangevul met feruliensuur, vanillien of vanilliensuur. Die sel konsentrasies is elke 24 h bepaal en die aangevulde komponente en die geproduseerde guaiakol is bepaal deur van HPVC gebruik te maak. Die guaiakol konsentrasies is ook bepaal deur van die peroksidase ensiem kolorimetriese bepaling (PEKB) gebruik te maak. Alicyclobacillus acidoterrestris het guaiakol geproduseer vanaf vanillien en vanilliensuur, dus is beide vanillien en vanilliensuur bevestig as voorlopers van guaiakol produksie deur A. acidoterrestris FB2. A padweg direk van vanillien na guaiakol is in hierdie studie geïdentifiseer. Guaiakol is nie geproduseer deur A. acidoterrestris FB2 in the monsters wat met feruliensuur aangevul is nie en feruliensuur is dus nie ‘n direkte voorloper van guaiakol produksie deur A. acidoterrestris. Die bederf potensiaal van appelsap aangevul met 10 mg L-1 of 100 mg L-1 vanillien of vanilliensuur deur A. acidoterrestris (106 kve mL-1) is ook geëvalueer. Die produksie van guaiakol het toegeneem met die toename in vanillien of vanilliensuur konsentrasies (in beide BAT en appelsap) wat aandui dat die konsentrasie vanillien en vanilliensuur teenwoordig in vrugtesap die bederfbaarheid van die sap sal beïvloed. Guaiakol konsentrasies in appelsap hoog bo die drumpel waardes van guaiacol vir smaak (0.24 – 2.00 μg L-1) en reuk (0.50 - 2.32 μg L-1) is geproduseer deur A. acidoterrestris FB2 in die appelsap monsters aangevul met 10 mg L-1 vanillien of vanilliensuur. Hierdie verskynsel dui aan dat vrugtesap met ‘n vanillien of vanilliensuur konsentrasies van so laag as 10 mg L-1 die potensiaal het om te bederf indien die sap gekontamineer is met A. acidoterrestris. Die konsentrasies van vanillien en vanilliensuur in verskillende vrugtesappe kan gebruik word om aan te dui of ‘n spesifieke vrugtesap ‘n hoë risiko het vir guaiakol bederf deur Alicyclobacillus spesies. Tydens die ontwikkeling van vrugtesap produkte en verskillende mengsels van vrugtesappe moet seker gemaak word dat die hoeveelhede vanillien en vanilliensuur in die sappe nie gekonsentreer word nie.

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No / Background/Aims: The oxidation of xenobiotic-derived aromatic aldehydes with freshly prepared liver slices has not been previously reported. The present investigation compares the relative contribution of aldehyde oxidase, xanthine oxidase and aldehyde dehydrogenase activities in the oxidation of vanillin, isovanillin and protocatechuic aldehyde with freshly prepared liver slices. Methods: Vanillin, isovanillin or protocatechuic aldehyde was incubated with liver slices in the presence/absence of specific inhibitors of each enzyme, followed by HPLC. Results: Vanillin was rapidly converted to vanillic acid. Vanillic acid formation was completely inhibited by isovanillin (aldehyde oxidase inhibitor), whereas disulfiram (aldehyde dehydrogenase inhibitor) inhibited acid formation by 16% and allopurinol (xanthine oxidase inhibitor) had no effect. Isovanillin was rapidly converted to isovanillic acid. The formation of isovanillic acid was not altered by allopurinol, but considerably inhibited by disulfiram. Protocatechuic aldehyde was converted to protocatechuic acid at a lower rate than that of vanillin or isovanillin. Allopurinol only slightly inhibited protocatechuic aldehyde oxidation, isovanillin had little effect, whereas disulfiram inhibited protocatechuic acid formation by 50%. Conclusions: In freshly prepared liver slices, vanillin is rapidly oxidized by aldehyde oxidase with little contribution from xanthine oxidase or aldehyde dehydrogenase. Isovanillin is not a substrate for aldehyde oxidase and therefore it is metabolized to isovanillic acid predominantly by aldehyde dehydrogenase. All three enzymes contribute to the oxidation of protocatechuic aldehyde to its acid.

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Les résines phénoliques de type résole présentent des propriétés applicatives et thermiques adaptées à l'élaboration de matériaux composites pour l'industrie aérospatiale. En particulier, ces résines peuvent être polymérisées en plusieurs étapes et présentent des propriétés de charbonnement très élevées. Seulement, ces résines sont principalement synthétisées à partir de formaldéhyde et de phénol. Ces précurseurs sont classés Cancérigène Mutagène Reprotoxique (CMR) respectivement de catégorie 1B et 2 et sont issus de ressources pétrolières. Du fait de cette classification CMR et de la raréfaction des ressources pétrolières, la société SAFRAN-Herakles souhaite substituer le formaldéhyde par des précurseurs non classés CMR et d'origine renouvelable. Les précurseurs aldéhyde aromatiques issus des lignines, 4-hydroxybenzaldéhyde, vanilline et syringaldéhyde, ne sont pas toxiques et peuvent être issus d'une ressource renouvelable abondante et bon marché, les lignines. Néanmoins, nous avons montré que ces trois précurseurs bio-sourcés ne sont pas réactifs en synthèse de résines résole. Nous avons également montré que le formaldéhyde doit être substitué par des précurseurs dialdéhyde aromatiques réactifs pour synthétiser des résines phénoliques avec d'excellentes propriétés de charbonnement. Ainsi, nous avons mis au point deux méthodes de fonctionnalisation pour transformer ces composés aldéhyde aromatiques bio-sourcés en de tels précurseurs dialdéhyde aromatiques réactifs. Les précurseurs obtenus ont ensuite été utilisés en synthèses de résines résole sans formaldéhyde et bio-sourcées. Après caractérisation de ces résines, nous avons enfin identifié des précurseurs donnant accès à des résines résole bio-sourcées avec des propriétés de charbonnement supérieures aux résines formophénoliques actuelles. En résumé, ces nouveaux précurseurs aldéhyde bio-sourcés représentent des alternatives prometteuses à l'usage de formaldéhyde pour la synthèse de résines résole avec des propriétés cibles pour des applications dans l'industrie aéropatiale. / Resol-type phenolic resins present applicative and thermal properties suitable for applications such as composite manufacture in aeropatial industry. Especially, resols can be polymerized stage-wise and present after curing high char yield properties. However, those resins are typically synthesized from formaldehyde and phenol. Those precursors are both classified as Carcinogenic Mutagenic Reprotoxic (CMR), respectively 1B and 2, and are petrobased. Because of this classification and of the fossil feedstock depletion, SAFRAN-Herakles wants to substitute formaldehyde by non-toxic and biobased aldehyde precursors. Aromatic aldehyde precursors such as 4-hydroxybenzaldehyde, vanillin and syringaldehyde are interestingly non-toxic and can be produced from the cheap and abundant lignins. Nevertheless, we have shown that those precursors are not reactive in resol synthesis conditions. Also, we have shown that difunctional and reactive aromatic aldehyde precursors are suitable for the synthesis of high char yield resins. Then, we have designed two functionalization methods to turn the biobased aldehyde precursors into difunctional and reactive ones. Finally, those precursors have been used for the synthesis of biobased resols without formaldehyde. Those new resins can be polymerized stage-wise and present higher char yield properties than the current formophenolic resins. Hence, those new biobased aldehyde precursors represent promising alternatives to formaldehyde for the synthesis of resols with target properties for aerospatial industry applications.

Orientador: Rogério Lopes Vieites / Banca: Giuseppina Pace Pereira Lima / Banca: Vera Lúcia Mores Rall / Banca: Maria Monteiro Sigrist / Banca: Nelida Lúcia Del Mastro / Resumo: O presente trabalho teve por objetivo verificar os efeitos da radiação gama e de antimicrobianos naturais na conservação de melão minimamente processado, armazenado sob refrigeração. Foram realizados 4 experimentos: 1 e 2 - frutos de melão Cantaloupe e Pele de Sapo provenientes de Baraúna/RN e Juazeiro/BA, respectivamente; 3 e 4 - frutos de melão Cantaloupe e Gália provenientes da região de Cartagena (Espanha). Após a colheita, os frutos dos experimentos 1 e 2 foram transportados ao Laboratório de Frutas e Hortaliças da Faculdade de Ciências Agronômicas - UNESP - Botucatu/SP, e os dos experimentos 3 e 4 transportados para o Laboratório de Postrecolección e Refrigeración da Universidad Politécnica de Cartagena/Espanha. Após o processamento manual (corte em seções trapezoidais) os melões MP (minimamente processados) dos experimentos 1 e 2 foram acondicionados em embalagens de poliestireno expandido recobertas com filme de polietileno e irradiados nas doses: 0,0kGy; 0,1kGy; 0,2kGy; 0,3kGy; 0,4kGy e 0,5kGy. Os melões MP dos experimentos 3 e 4, após o processamento, foram imersos durante 1 minuto a 5ºC em: água (testemunha); vanilina (1000 mg L-1 e 2000 mg L-1); ácido cinâmico (148,16 mg L-1 e 296,32 mg L-1) e outros dois tratamentos consistiram em aplicação de vapor de ácido cinâmico (148,16 mg L-1 e 296,32 mg L-1) nos melões MP dentro da embalagem (bandejas de polipropileno termo seladas com filme de polipropileno). O armazenamento refrigerado foi realizado durante 10 dias 5±1ºC e 85-90% UR (experimentos 1 e 2) e à 5±1ºC e 85-95% UR (experimentos 3 e 4). As alterações na qualidade foram detectadas por meio das análises: perda de massa fresca, conservação pós-colheita, firmeza, pH, acidez titulável, sólidos solúveis, teores de açúcares redutores e redutores totais, ácido ascórbico, vitamina C, taxa respiratória, produção de etileno... (Resumo completo, clicar acesso electrônico abaixo) / Abstract: The aim of this research was to evaluated the effects of the gamma radiation and the natural antimicrobials in the conservation of fresh-cut melon storaged under refrigeration. Four experiments were accomplished: 1 and 2 - the varieties used were 'Cantaloupe' and 'Pele de Sapo' from Baraúna/RN and Juazeiro/BA, respectively; 3 and 4 - the varieties used were 'Cantaloupe' and 'Gália' from Cartagena (Spain). After harvesting, fruits from experiment 1 and 2 were sent to the Laboratory of Fruits and Vegetables at the University of Sao Paulo State (UNESP - Botucatu/SP). Fruits from experiment 3 and 4 were sent to the Postharvest and Refrigeration Group at the Technical University of Cartagena/Spain. After the manual processing (cut in trapezoidal sections) the fresh-cut melons of the experiment 1 and 2 were conditioned in polystyrene trays involved by polyethylene film and irradiated with doses: 0,0kGy; 0,1kGy; 0,2kGy; 0,3kGy; 0,4kGy and 0,5kGy. After processing, fresh-cut melons from experiment 3 and 4 were immersed for 1 min at 5ºC in water (control); vanillin (1000 mg L-1 and 2000 mg L-1); cinnamic acid (148,16 mg L- 1 and 296,32 mg L-1). Two additional treatments consisted on the application of cinnamic acid vapor (148,16 mg L-1 e 296,32 mg L-1) on fresh-cut melons within the packages (polypropylene trays heat-sealed with polypropylene). The storage was realized during 10 days in a cold camera to 5±1ºC and 85-90% HR (experiment 1 and 2) and to 5±1ºC and 85- 95% HR (experiment 3 and 4). The quality alterations were detected through the analyses: loss of fresh mass, postharvest conservation, firmness, pH, acidity titratable, soluble solids, reducing and total reducing sugar content, ascorbic acid, vitamin C, respiration rate, ethylene production, gas composition (CO2 and O2), enzymes activity (peroxidase, polygalacturonase and pectinmethylesterase), antioxidant... (Complete abstract click electronic access below) / Doutor

Ce mémoire présente une exploration des polymères à empreintes moléculaires (MIP) comme outils d’une libération contrôlée de bioactifs olfactifs ou pour le criblage/préselection de composés à activité antivirales ou anti-tumorales sur le site actif d’une enzyme. La première partie est une étude de la complexation de la vanilline sur des billes polymériques sphériques en vue d’une libération contrôlée (pH, salinité, …). Ces études portent sur les caractéristiques de l'absorption et la libération de la molécule d'intérêt dans le milieu aqueux sur les microsphères fonctionnalisées fourni par Merck ESTAPOR® Microsphères. Nous avons ensuite synthétisé divers MIP de vanilline au format monolithique. Plusieurs stratégies d’impression ont été étudiées: non covalente, covalente et semi-covalente. La composition du MIP préparé dans chaque approche a été optimisée pour obtenir les meilleures propriétés et performances. L'affinité, la sélectivité et la capacité du MIP ont été déterminées. Les MIPs ont été évalués par extraction en phase solide (SPE) d'analogues structuraux de la vanilline dans des échantillons naturels (extrait de vanille, vin). La deuxième partie de ce mémoire concerne l’évaluation de MIPs de l’adénosine 5’-monophosphate (AMP) Le polymère a été préparé par une approche non-covalente et son efficacité de recapture a été caractérisée par analyse frontale (FA). L’analyse frontale est une technique qui permet de discriminer des interactions spécifiques des non spécifiques et de comprendre les mécanismes de liaison dans des cavités spécifiques. / This thesis report presents the exploration of molecularly imprinted polymers (MIP) for the application in controlled release and targeting antivirus and anticancer drugs. The first part of this study describes the imprinting of vanillin as a monolith. Several strategies were studied: non-covalent, covalent and semi-covalent. The composition of the MIP prepared in each approach was optimized to obtain the best properties and performance. The affinity, selectivity and capacity of MIP were determined. MIPs were evaluated in solid-phase extraction (SPE) of structural analogues in natural samples (vanilla extract, wine). We also present the study of the exploration of spherical beads as potential tools for the controlled release of vanillin. These studies concern the characteristics of uptake and release of the molecule of interest in the aqueous medium on functionalised microspheres supplied by Merck ESTAPOR Microspheres®. The second part of this thesis is devoted to studies on the evaluation of MIP of adenosine 5'-monophosphate (AMP). The polymer was prepared in non-covalent approach and efficiency of binding was characterised using frontal analysis (FA). FA is a useful technique that allows discriminate specific and nonspecific interactions and to understand the binding mechanisms in specific cavities.

Made available in DSpace on 2014-06-11T19:32:26Z (GMT). No. of bitstreams: 0 Previous issue date: 2009-06-01Bitstream added on 2014-06-13T18:43:52Z : No. of bitstreams: 1 moreira_gc_dr_botfca.pdf: 1778915 bytes, checksum: c6b29f50c1945159f217677f6de1a95a (MD5) / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES) / O presente trabalho teve por objetivo verificar os efeitos da radiação gama e de antimicrobianos naturais na conservação de melão minimamente processado, armazenado sob refrigeração. Foram realizados 4 experimentos: 1 e 2 - frutos de melão Cantaloupe e Pele de Sapo provenientes de Baraúna/RN e Juazeiro/BA, respectivamente; 3 e 4 - frutos de melão Cantaloupe e Gália provenientes da região de Cartagena (Espanha). Após a colheita, os frutos dos experimentos 1 e 2 foram transportados ao Laboratório de Frutas e Hortaliças da Faculdade de Ciências Agronômicas – UNESP – Botucatu/SP, e os dos experimentos 3 e 4 transportados para o Laboratório de Postrecolección e Refrigeración da Universidad Politécnica de Cartagena/Espanha. Após o processamento manual (corte em seções trapezoidais) os melões MP (minimamente processados) dos experimentos 1 e 2 foram acondicionados em embalagens de poliestireno expandido recobertas com filme de polietileno e irradiados nas doses: 0,0kGy; 0,1kGy; 0,2kGy; 0,3kGy; 0,4kGy e 0,5kGy. Os melões MP dos experimentos 3 e 4, após o processamento, foram imersos durante 1 minuto a 5ºC em: água (testemunha); vanilina (1000 mg L-1 e 2000 mg L-1); ácido cinâmico (148,16 mg L-1 e 296,32 mg L-1) e outros dois tratamentos consistiram em aplicação de vapor de ácido cinâmico (148,16 mg L-1 e 296,32 mg L-1) nos melões MP dentro da embalagem (bandejas de polipropileno termo seladas com filme de polipropileno). O armazenamento refrigerado foi realizado durante 10 dias 5±1ºC e 85-90% UR (experimentos 1 e 2) e à 5±1ºC e 85-95% UR (experimentos 3 e 4). As alterações na qualidade foram detectadas por meio das análises: perda de massa fresca, conservação pós-colheita, firmeza, pH, acidez titulável, sólidos solúveis, teores de açúcares redutores e redutores totais, ácido ascórbico, vitamina C, taxa respiratória, produção de etileno... / The aim of this research was to evaluated the effects of the gamma radiation and the natural antimicrobials in the conservation of fresh-cut melon storaged under refrigeration. Four experiments were accomplished: 1 and 2 – the varieties used were ‘Cantaloupe’ and ‘Pele de Sapo’ from Baraúna/RN and Juazeiro/BA, respectively; 3 and 4 - the varieties used were ‘Cantaloupe’ and ‘Gália’ from Cartagena (Spain). After harvesting, fruits from experiment 1 and 2 were sent to the Laboratory of Fruits and Vegetables at the University of Sao Paulo State (UNESP – Botucatu/SP). Fruits from experiment 3 and 4 were sent to the Postharvest and Refrigeration Group at the Technical University of Cartagena/Spain. After the manual processing (cut in trapezoidal sections) the fresh-cut melons of the experiment 1 and 2 were conditioned in polystyrene trays involved by polyethylene film and irradiated with doses: 0,0kGy; 0,1kGy; 0,2kGy; 0,3kGy; 0,4kGy and 0,5kGy. After processing, fresh-cut melons from experiment 3 and 4 were immersed for 1 min at 5ºC in water (control); vanillin (1000 mg L-1 and 2000 mg L-1); cinnamic acid (148,16 mg L- 1 and 296,32 mg L-1). Two additional treatments consisted on the application of cinnamic acid vapor (148,16 mg L-1 e 296,32 mg L-1) on fresh-cut melons within the packages (polypropylene trays heat-sealed with polypropylene). The storage was realized during 10 days in a cold camera to 5±1ºC and 85-90% HR (experiment 1 and 2) and to 5±1ºC and 85- 95% HR (experiment 3 and 4). The quality alterations were detected through the analyses: loss of fresh mass, postharvest conservation, firmness, pH, acidity titratable, soluble solids, reducing and total reducing sugar content, ascorbic acid, vitamin C, respiration rate, ethylene production, gas composition (CO2 and O2), enzymes activity (peroxidase, polygalacturonase and pectinmethylesterase), antioxidant... (Complete abstract click electronic access below)