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Visible light photoredox catalysis has proven to be a powerful tool for promoting transformations in organic synthesis. Hence this project was carried out to develop tools for predicting reactivity patterns of visible light- promoted redox reactions. Fluorination is of immense importance in organic chemistry, and so is trifluoromethoxylation. The fluorination reaction has been studied for a long time and has been accomplished in milder ways, while the generation of a trifluoromethoxy-radical at room temperature and atmospheric pressure remains a challenge. The design of the reaction in this project is to overcome the instability and take control of the catalytic event under visible- light photocatalytic conditions. The trifluoromethoxylation reaction proceeded at room temperature with the reaction time of 60 min using acetonitrile as the solvent and blue LED (10 W) as the external light source. No yield of the desired product was obtained for any of the substrates. More surprisingly, in all entries, 3,3-diphenylprop-2-en-1-ol was attained as a side product. The same side product was also detected in the entry with ambient light, concluding that the reaction was completed without any external light source. Thus, no photoredox catalysis took place. / Fotoredoxkatalys via ljus inom det synliga spektrat har visat sig vara ett kraftfullt verktyg för att gynna reaktioner inom organisk syntes. Detta projekt genomfördes med syfte att utveckla verktyg avsedda för att förutspå reaktivitetsmönster vid fotoredoxkatalys med synligt ljus. Fluorinering och trifluorometoxylering är viktiga verktyg inom organisk syntes. Fluorineringsreaktionen har studerats länge och har kunnat genomföras under milda reaktionsbetingelser, medan generering av trifluorometoxyradikal vid rumstemperatur och atomsfärstryck fortfarande är en utmaning. Reaktionen i det här projektet är designad för att kringgå instabilitetsproblemet och ta kontroll över katalysmomentet, under fotokatalysförhållanden i synligt ljus. Reaktionen utfördes i rumstemperatur med en reaktionstid på 60 minuter, med acetonitril som lösningsmedel och blå LED (10 W) som extern ljuskälla. Inget av substraten reagerade till den önskade produkten. Mer överraskande var att 3,3-difenylprop-2-en-1-ol erhölls som sidoprodukt vid alla reaktionsstillfällen. Samma sidoprodukt upptäcktes även vid reaktion genomförd i dagsljus, vilket indikerar att reaktionen skedde utan någon extern ljuskälla. Således skedde ingen fotoredoxkatalys.

This thesis has an approved one-year embargo applied to it. Please, refer to the corresponding forms, and please, so not publish immediately until the embargo has been sorted out. The thesis contains two unpublish papers and patents pending. Thank you! / Conventional single-use plastic packaging has contributed significantly to the health and well-being of our society but also negatively impacted our environment due to its persistence after use. Since recycling is not a complete solution, rapidly biodegradable materials like thermoplastic starch (TPS) blends offer a more sustainable alternative. Additionally, to stave off the premature breakdown of starch-containing materials as well as extend the shelf life of enclosed foods, microbial control strategies need to be developed. To overcome the inherent brittleness of TPS, this work explores the potential of xylitol and erythritol as melt plasticizers for waxy corn starch (̴100% amylose). Characterizations revealed that both xylitol and erythritol can gelatinize and plasticize starch under 25% wt. Particularly, xylitol demonstrated superior plasticizing and compatibilizing effects, leading to a ductile TPS packaging film with uncharacteristically high elongation at break (EB, 422% ± 48%). The ductile TPS was blended with up to 70% Ecovio bioplastic without requiring compatibilizers and retaining much of its EB value (298 ± 24%). Using xylitol as a melt plasticizer also enhanced the mechanical and hydrophobic qualities of the TPS/Ecovio film as well as its oxygen permeability and puncture extension. Furthermore, polymerized curcumin copolymer (PCEG) was investigated as a grafted coating onto the developed TPS/Ecovio® blend. The antimicrobial activity of PCEG and PCEG coating film was evaluated against foodborne bacteria. The polymerized curcumin by itself demonstrated antimicrobial activity against the gram-negative bacteria Escherichia coli BL21 and Pseudomonas aeruginosa PA01, as well as the gram-positive bacterium Staphylococcus aureus. Additionally, the PCEG-coated films showed surface inhibition of Glutamicibacter soli (IAI-3), a gram-positive bacterium making polymerized curcumin copolymer coatings a suitable approach to add antimicrobial features in thermoplastic starch composites for biodegradable food packaging. / Thesis / Master of Applied Science (MASc) / Canada's Zero Plastics initiative represents a commitment to the environment while upholding the advancements in food safety and public health that come with single-use food packaging. Achieving this balance demands the creation of novel materials. These materials should mimic the qualities of synthetic polymers but have the added ability to decompose naturally in the environment upon reaching the end of their utility. A significant challenge in this effort is preventing the premature degradation of starch-containing packaging materials. Moreover, extending the shelf life of the food they enclose is equally crucial. To solve this paradox, the development of microbial control strategies becomes imperative. This study highlights the antimicrobial potential of a polymerized curcumin copolymer (PCEG) as a coating on a blend of thermoplastic starch (TPS)/xylitol/Ecovio®, creating an innovative packaging film. The curcumin copolymer coating exhibited antimicrobial properties, suggesting its potential use in thermoplastic starch composites for biodegradable food packaging.

Thesis (PhD (Wine Biotechnology))--University of Stellenbosch, 2011. / Includes bibliography. / ENGLISH ABSTRACT: Alcoholic fermentation, and especially wine fermentation, is one of the most ancient microbiological processes utilized by man. Yeast of the species Saccharomyces cerevisiae are usually responsible for most of the fermentative activity, and many data sets clearly demonstrate the important impact of this species on the quality and character of the final product. However, many aspects of the genetic and metabolic processes that take place during alcoholic fermentation remain poorly understood, including the metabolic processes that impact on aroma and flavour of the fermentation product. To contribute to our understanding of these processes, this study took two approaches: In a first part, the initial aim had been to compare two techniques of transcriptome analysis, DNA oligo-microarrays and Serial Analysis of Gene Expression (SAGE), for their suitability to assess wine fermentation gene expression changes, and in particular to assess their potential to, in combination, provide combined quantitative and qualitative data for mRNA levels. The SAGE methodology however failed to produce conclusive data, and only the results of the microarray data are shown in this dissertation. These results provide a comprehensive overview of the transcriptomic changes during model wine fermentation, and serve as a reference database for the following experiments and for future studies using different fermentation conditions or genetically modified yeast. In a second part of the study, a screen to identify genes that impact on the formation of various important volatile aroma compounds including esters, fatty acids and higher alcohols is presented. Indeed, while the metabolic network that leads to the formation of these compounds is reasonably well mapped, surprisingly little is known about specific enzymes involved in specific reactions, the genetic regulation of the network and the physiological roles of individual pathways within the network. Various factors that directly or indirectly affect and regulate the network have been proposed in the past, but little conclusive evidence has been provided. To gain a better understanding of the regulations and physiological role of this network, we took a functional genomics approach by screening a subset of the EUROSCARF strain deletion library, and in particular genes encoding decarboxylases, dehydrogenases and reductases. Thus, ten genes whose deletion impacted most significantly on the aroma production network and higher alcohol formation were selected. Over-expression and single and multiple deletions of the selected genes were used to genetically assess their contribution to aroma production and to the Ehrlich pathway. The results demonstrate the sensitivity of the pathway to cellular redox homeostasis, strongly suggest direct roles for Thi3p, Aad6p and Hom2p, and highlight the important role of Bat2p in controlling the flux through the pathway. / AFRIKAANSE OPSOMMING: Alkoholiese fermentasie, en veral die maak van wyn, is een van die vroegste mikrobiologiese prosesse wat deur die mensdom ingespan is. Die gisspesie Saccharomyces cerevisiae is gewoonlik grotendeels verantwoordelik vir die fermentasie and verskeie vorige studies het gedemonstreer dat hierdie spesie ‘n baie belangrike rol speel in die uiteindelike kwaliteit en karakter van die voltooide produk. Nieteenstaande die feit is daar steeds baie aspekte van beide die genetiese en metaboliese prosesse wat plaasvind tydens alkoholiese fermentatsie wat nog swak verstaan word, insluitende metaboliese padweë wat ‘n impak het op die smaak en aroma van die fermentasie produk. Om ons kennis van die veld uit te brei het die studie twee aanslae geneem: In die eerste geval is gepoog om twee tegnieke van transkriptoom analiese, nl. DNA oligomikro- arrays en Serial Analysis of Gene Expression (SAGE) te bestudeer vir hul vermoë om geen ekspressie veranderinge tydens wynfermentasie te ondersoek en meer spesifiek om hul potensiaal om ‘n kombinasie van kwantitatiewe sowel as kwalitatiewe data met betreking to mRNA vlakke te produseer. Die SAGE metode kon egter geen betroubare resultate produseer nie en dus word slegs die resultate van die mikro-array eksperimente in die tesis bespreek. Die resultaat is ‘n geheeloorsig oor die geenekspressie veranderinge wat so ‘n wyngis tydens alkoholiese fermentasie ondergaan en dien as ‘n verwysingsraamwerk vir toekomstige studies met geneties gemodifiseerde gis of selfs verskillende fermentasieparameters. Die tweede deel van die studie het gefokus op die identifikasie van gene wat ‘n impak het op die vorming van belangrike, vlugtige aroma komponente, o. a. Esters vetsure en hoër alkohole d.m.v. ‘n siftingseksperiment. Alhoewel daar redelik baie inligting is oor die onderligende metaboliese netwerke wat lei tot die vorming van die verbindings, is daar min kennis van die genetiese regulasie van die netwerk en die fisiologiese rol van individuele padweë wat die netwerk vorm. Verskeie faktore – wat of die netwerk direk of indirek affekteer – is al voorgestel, meer met min konkrete bewyse. Dus het ons gepoog om meer lig op die onderwerp te laat m.b.v. ‘n funksionele genoom aanslag deur ‘n siftingseksperiment te doen op ‘n subgroep (spesifiek gene wat kodeer vir dekarboksilase, dehidrogenase en reduktase ensieme) van die EUROSCARF delesiebiblioteek. Dus is tien gene geïdentifiseer – die delesie waarvan ‘n merkbare effek het op die aroma produksie netwerk en spesifiek die van hoër alkohole. Ooruitdrukkings en enkel en meervoudige delesie rasse van die tien gene is gemaak om d.mv. genetiese analiese, hulle rol in aroma produksie en die Ehrlich padweh uit te pluis. Die resultate toon dat hierdie padweg sensitief is teenoor die sellulêre redoks balans en dui op direkte rolle vir Thi3p, Aad6p en Hom2p, asook dat Bat2p ‘n baie belangrike rol speel in die werking van die padweg.

L’oxydation sélective des alcools en aldéhydes, acides ou cétones est une transformation très importante en chimie. L’emploi d’oxygène moléculaire comme oxydant permet de se placer dans une perspective de chimie verte, avec la production d’eau comme seul sous-produit principal. L’oxydation d’alcools primaires (1-octanol et géraniol) et d’alcools secondaires (2-octanol, 1-phénylethanol et alcools hétéroaromatiques dérivés de la pyridine) a été étudié en présence de catalyseurs au platine supportés sur charbon sous pression d’air, en solvant organique ou mélange à de l’eau. Les résultats ont montré une forte influence du solvant sur l’activité catalytique, avec un effet promoteur très important de l’eau sur la réaction. Cet effet a été discuté sur la base de différentes hypothèses. La promotion des catalyseurs au platine par le bismuth a permis d’observer des modifications de l’activité avec un effet positif en particulier dans l’oxydation des alcools hétéroaromatiques secondaires. La désactivation observée lors de l’oxydation de certains substrats a été analysée et des solutions ont été proposées pour la surmonter. / The selective alcohols oxidation to aldehydes, acids and ketones is an important transformation in chemistry. The use of molecular oxygen as oxidant is in adequation with a green chemistry perspective, since water is the only by-product. The oxidation of primary alcohols (1-octanol and geraniol) and secondary alcohols (2-octanol, 1-phenylethanol and pyridine substituted alcohols) has been studied in the presence of platinum supported carbon catalysts under air pressure in organic or mixed organic/aqueous media. The results have shown a strong influence of the solvent on the catalytic activity, with an important promoting effect of water on the reaction. This effect has been discussed based on several hypotheses. The promotion of platinum supported catalysts by bismuth has shown some modifications of the activity, with a positive effect in particular in the oxidation of secondary heteroaromatic alcohols. The deactivation observed during the oxidation reaction of some substrates has been analyzed and some solutions have been proposed to overcome the problem.

Bumblebees are important pollinators, commercially used in large-scale plant growing in greenhouses. Their males produce marking pheromones for mating, which attract young bumblebee queens. These pheromones are often a complicated mixture of chemicals, which is produced in the male labial gland, and the mixture itself is specific for each bumblebee species. The regulation of bumblebee sexual pheromone biosynthesis is largely unknown, and this Master's thesis is focused on the analysis of the mechanisms which lead to the regulation of the Bombus terrestris male pheromone's fat-acid and terpenes biosynthesis, specifically on stereospecific enzymatic reduction of double bond of farnesol. This thesis studies the influence of potential neurohormones on a specific enzymatic mixture, which is involved in the pheromone biosynthesis. Methods used in this project include biochemical, analytic and molecular-biology methods.

Thesis advisor: Amir H. Hoveyda / Abstract Chapter 1: Development of Efficient and Kinetically E-Selective Cross-Metathesis to Generate Alkenyl Halides We have devised a broadly applicable strategy to achieve kinetically E-selective cross-metathesis to generate a valuable set of E-alkenyl chlorides and fluorides in high efficiency. The synthetic utility was demonstrated through several concise syntheses of E-alkenyl chloride and fluoride precursors to biologically active molecules. The design principles delineated in this study are expected to initiate a wider range of efficient and kinetically controlled E-selective olefin metathesis processes where there is a diminished preference for the E isomer such as macrocyclic ring-closing metathesis. Chapter 2: Development of Efficient and Kinetically E-Selective Macrocyclic Ring-Closing Metathesis We devised a strategy to achieve high E selectivity in ring-closing metathesis to afford E-macrocyclic alkenes of various ring sizes regardless of the associated thermodynamic preferences. The key findings revealed that E-alkenylB(pin), widely recognized for its broad use in catalytic cross-coupling chemistry, possesses the appropriate steric and electronic attributes to serve as a suitable cross-partner in ring-closing metathesis with Mo alkylidenes. Synthetic utility was demonstrated through ring-closing metathesis at a late stage of a multi-step route. The investigation described herein offers a practical solution to a compelling problem in olefin metathesis, further elevating the utility of this widely used transformation. Chapter 3: Stereoselective Synthesis of E- and Z-Trisubstituted Alkenes by Combining Stereoretentive Catalytic Cross-Metathesis and Catalytic Cross-Coupling We introduced a general solution to a longstanding and compelling problem in olefin metathesis: a broadly applicable strategy for the reliable and efficient synthesis of acyclic E- and Z-trisubstituted alkenyl halides. Complications resulted from the formation of an unstable methylidene species or less reactive disubstituted alkylidene complexes can be addressed by utilizing a stereo-defined E- or Z-trisubstituted alkene and a 1,2-disubstituted olefin as substrates. By merging two central catalytic transformations in organic synthesis, cross-coupling and CM, various E- or Z-trisubstituted alkenyl chloride and bromides were readily accessed by the same catalytic system without the need for directing groups. The synthetic utility of the present protocol was demonstrated through several concise and efficient synthesis of biologically active natural products/synthetic precursors. Notably, the E- or Z-trisubstituted alkenyl halides prepared by CM may be readily converted to other trisubstituted olefins with complete retention of stereochemical purity by means of a second cross-coupling reaction. Based on the new findings, we revisited previously unaddressed problems and establish that readily available isoprenoid alkenes can serve as a suitable surrogate for unhindered terminal alkenes in CM. Chapter 4: In situ Protection/Deprotection for Catalytic Olefin Metathesis in the Presence of Polar Protic Functional Groups We demonstrated that protic groups such as alcohols and carboxylic acids that are problematic with high-oxidation-state alkylidenes could be effectively masked in situ prior to CM reactions by an appropriate borane reagent. The commercial sample of alkenes that are usually contaminated with protic impurities could be ‘purified’ in situ by a sub-stoichiometric amount of pinacolborane. Deprotection of the in situ boron-based protecting group proceeded under mild conditions and could be performed in the same vessel. The one-pot protection/cross-metathesis/deprotection of alcohol and carboxylic acid-containing alkenes described herein is likely to have an impact on the diversity of organic molecules that can be prepared in a laboratory setting. / Thesis (PhD) — Boston College, 2018. / Submitted to: Boston College. Graduate School of Arts and Sciences. / Discipline: Chemistry.

Orientador: Carlos Eduardo Jordão Machado / Banca: Célia Reis Camargo / Banca: Eduardo Romero de Oliveira / Banca: Luis Soares de Camargo / Banca: Jaime Rodrigues / Resumo: Esse trabalho trata das relações sociais que permeiam o consumo de bebidas alcoólicas na cidade de São Paulo, no final do século XIX e começo do XX, desvelando gestos e sensibilidades do cotidiano da cidade, captando costumes, modos de vida e sujeitos extintos. O objetivo é explorar uma cultura gestual, material e sensível, historicamente construída, ligada aos alcoóis, seus objetos, suas maneiras de saborear e lugares de consumo / Abstract: This work deals with the social relations that permeate the consumption of alcoholic beverages in the city of São Paulo in the late nineteenth and early twentieth centuries, unfolding daily gestures and sensitivities of the city, capturing customs, lifestyles and extinct subjects. The aim is to explore a gestural, material and sensitive culture, historically constructed, linked to alcohols, their objects, ways of enjoying, and places of consumption / Doutor

Quando aplicada em bebidas alcoólicas, a radiação ionizante pode ser usada para descontaminação de malte ou esterilização de mostos e tem sido proposta sua aplicação na aceleração do envelhecimento. Devido à internacionalização da cachaça, alguma confusão tem surgido sobre a sua identidade e a do rum. Este trabalho teve como propósito identificar, quantificar e comparar as substâncias químicas responsáveis pelo aroma de amostras de cachaça de alambique e de rum comercial, por meio de análises instrumentais e sensoriais. Pode-se afirmar haver forte correlação entre a concentração dos compostos voláteis analisados com a dose de radiação aplicada (0, 150 e 300Gy), em todas as amostras. De acordo com os testes triangulares, apenas para aroma, todos os provadores puderam distinguir nas amostras não irradiadas e irradiadas com 300Gy, a cachaça envelhecida do rum e a cachaça não envelhecida do rum, porém, não foram observadas diferenças entre a cachaça não envelhecida e a envelhecida. Os resultados da Análise Descritiva Quantitativa mostraram que as amostras não irradiadas de cachaça não envelhecida e as do rum diferiram entre si em relação aos atributos de aroma definidos como álcool, vinagre, baunilha, citros, melão, condimento, vegetal e grama, mas não em relação aos atributos caramelo e maçã. As amostras de cachaças não envelhecidas não irradiadas e irradiadas (300Gy) e as de rum não irradiadas e irradiadas (300Gy) diferiram entre si em relação aos atributos de aroma definidos como maçã, caramelo, vinagre, baunilha, citros, melão, condimento, vegetal e grama, mas não em relação ao aroma de álcool. De acordo com os resultados da cromatografia gasosa/olfatometria foi encontrada diferença significativa entre cachaça e rum não irradiados; cachaça não irradiada e cachaça irradiada (300Gy); e rum não irradiado e irradiado (300Gy), quando foram comparados seus aromas. / The irradiation process has being presented as an alternative technique in food preservation. When apply on beverages, radiation is mainly used for malt decontamination or sterilization of musts and had been proposed also to accelerate aging. Some confusion over rum and cachaça identities has arisen due to the internationalization of cachaça. This research aims to identify, quantify and compare the effect of gamma radiation on the aroma of the Brazilian spirit with rum, irradiated and non irradiated, by instrumental and sensory analysis. Results showed that the content of volatile compounds presented strong correlation with the radiation dose (0, 150 and 300Gy) for all the samples. According to Triangle Test for aroma, all the judges could distinguish among non irradiated and irradiated samples (300Gy), aged cachaça from rum and non aged cachaça from rum, but they couldn\'t distinguish aged cachaça from non aged cachaça. Analysis of variance (ANOVA) of the results from the quantitative descriptive analysis showed that non irradiated non aged cachaça and rum were different in their alcohol, vinegar, vanilla, citrus, melon, spice, vegetal and grass except caramel and apple aroma attributes. Non irradiated cachaça and irradiated cachaça (300Gy); and non irradiated rum and irradiated rum (300Gy) were different in their apple, caramel, vinegar, vanilla, citrus, melon, spice, vegetal and grass except alcohol aroma attributes. According to the gas chromatography/olfatometry results, significant difference was found among non irradiated cachaça and rum; non irradiated cachaça and irradiated cachaça (300Gy); and non irradiated rum and irradiated rum (300Gy) when their aromas were compared.

Im Rahmen dieser Dissertation wurden die Herstellung sowie Reaktionen von geminalen Dihydroperoxiden erforscht. Dabei kamen die dargestellten Dihydroperoxide sowohl als Sauerstofftransferreagenz, insbesondere zur enantioselektiven Epoxidation, als auch als Baustein zur Synthese von 1,2,4,5-Tetroxanen zum Einsatz. Es wurde eine in unserem Arbeitskreis gefundene Methode zur Darstellung gem - Dihydroperoxide zunächst hinsichtlich der Reaktionsbedingungen optimiert, um dann eine Vielzahl an Dihydroperoxiden vornehmlich mit dieser Methode zu synthetisieren. Insbesondere gelang es hier erstmals, primäre Dihydroperoxide aus aliphatischen Aldehyden darzustellen. Desweiteren wurde erstmals eine größere Anzahl an enantiomerenreinen DHPs dargestellt. Weitere DHPs konnten durch Ozonolyse von olefinischen Terpenen mit etherischer Wasserstoffperoxidlösung dargestellt werden. Die enantiomerenreinen DHPs wurden verwendet, um enantioselektiv sowohl 2-substituierte Naphthochinone wie auch Allylalkohole, insbesondere tertiäre Allylalkohole, zu epoxidieren. Die Epoxide der letzteren sind nach der normalerweise verwendeten Methode nach Sharpless nicht zugänglich. Außerdem konnten durch Sulfidoxidation Sulfoxide enantiomerenangereichert dargestellt werden. Dies stellt die erste Nutzung von geminalen Dihydroperoxiden zur enantioselektiven Sauerstoffübertragung dar. Die primären aliphatischen gem-DHPs wurden desweiteren zur Darstellung bisher unbekannter 1,2,4,5-Tetroxane genutzt. Insbesondere wurde gefunden, daß durch Kondensation mit Orthoestern verläßlich alkoxysubstituierte Tetroxane erzeugt werden können. Diese wurden in der Literatur bisher nur an sehr wenigen Beispielen beschrieben. / In the course of this dissertation thesis the preparation and reactions of geminal dihydroperoxides were researched. The hereby synthesized dihydroperoxides were used as an oxygen transfer reagent, especially for enantioselective epoxidation, as well as a building block for the synthesis of 1,2,4,5-tetroxanes. A method for synthesis of gem-dihydroperoxides that was found in our workgroup was first optimized concerning reaction conditions, and later utilized to synthesize a large number of dihydroperoxides. It was notably possible to synthesize primary DHPs from aliphatic aldehydes for the first time. Also for the first time, a large number of enantiomerically pure gem-DHP was prepared by this method. Additional enantiomerically pure DHPs were made by ozonolysis of olefinic terpenes using ethereal hydrogen peroxide solution. The enenantiomerically pure DHPs were utilized to both epoxidize 2-substituted naphthoquinones as well as allylic alcohols, especially tertiary allylic alcohols. The latter kind does not react via the normally used Sharpless epoxidation. Additionally, enantioenriched sulfoxides could be prepared from sulfides. This is the first time that geminal dihydroperoxides were used for enantioselective oxygen transfer. Primary aliphatic DHPs were further utilized to prepare previously unknown 1,2,4,5-tetroxanes. Notably it was found that condensation with orthoesters reliably yielded alkoxy-substiuted tetroxanes. These were only described in a very few cases in literature before.