Over the past decade, bioorthogonal chemistry has emerged as powerful tools used for tracking biomolecules within living systems. Despite the vast number of organic transformations in the literature, only select few reactions meet the stringent requirements of bioorthogonality. There is increasing demands to develop biocompatible reactions that display high specificity and exquisitely fast kinetics under physiological conditions. With the goal of increasing reaction rates as a means for reducing the concentrations of labelling reagents used for bioconjugation, we have developed metal-catalyzed and metal-free alkyne-nitrone cycloadditions as alternatives to azide-alkyne cycloadditions and demonstrate their applications for imaging cell surface proteins. The copper(I)-catalyzed alkyne-nitrone cycloaddition, also known as the Kinugasa reaction, is typically conducted with a Cu(I) catalyst in the absence of air. We have developed highly efficient micelle promoted multicomponent Kinugasa reactions in aqueous media to make the reaction faster and more efficient. Despite good product yields, the slow kinetics, limited substrate scope and competing side-reaction pathways precludes its practical applicability for biological labelling. We have designed and synthesized β-lactam alkyne probes obtained from these reactions for activity-based protein profiling of the activities of membrane proteins. Additionally, we report that alkyne tethered β-lactams serve as surface enhanced Raman spectroscopy (SERS) reporters bound to silver nanoparticles, and demonstrated that alkyne bound silver nanoparticles can be used for SERS imaging cell surface proteins. The strain-promoted alkyne-nitrone cycloaddition (SPANC) was also explored as a rapid alternative bioorthogonal reaction. We found that the reaction proceeded in high yield within aqueous media, and displayed rate enhancements that were 1-2 orders of magnitude faster than analogous reactions involving azides. The scope and kinetics of SPANC was evaluated in model reactions of various nitrones (acyclic and cyclic) with cyclooctynes, with the purpose of identifying stable nitrones that displayed intrinsically faster kinetics than azides in strain-promoted cycloadditions with cyclooctynes. Cyclic nitrones displayed good stability and exceptionally fast reactivity in these reactions. The SPANC reaction exhibited high selectivity in the presence of biological nucleophilic amino acid side chains and the presence of biological media did not adversely affect the reaction. We have utilized SPANC for highly specific labelling of proteins in vitro and for imaging ligand-receptor interactions on the surfaces of live cancer cells. The high selectivity, fast reaction rate, and aqueous compatibility of SPANC makes the reaction suitable for a variety of in vivo biological imaging applications.

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The aim of my thesis was the synthesis of the modified 2'-deoxyribonucleoside triphosphates (dNTPs) bearing electrochemically oxidizable labels and their incorporation into DNA for the application in bioanalysis. In the first part of my thesis, I developed the synthesis of modified dNTPs bearing 2,3- dihydrobenzofuran (DHB) or 2-methoxyphenol (MOP) labels at 5-position of 2'- deoxycytidine 5'-O-triphosphate and at the 7-position of 7-deaza-2'-deoxyadenosine 5'-O- triphosphate by Suzuki-Miyaura cross-coupling reactions. Then modified dNTPs were used as substrates for DNA polymerases in enzymatic synthesis of modified DNA by PCR and primer extension. Electrochemical properties of the DHB and MOP-labeled nucleosides, dNTPs and DNA were studied by using of a square-wave voltammetry (SWV) at the pyrolytic graphite electrode (PGE) giving signals of MOP oxidation around 0.5 V and DHB oxidation around 0.85 V. The use of DHB group in combination with other electrochemical active labels was limited by close position of its oxidation peak to the signals of oxidation of natural nucleobases, whereas MOP moiety was successfully used for redox coding of nucleobases in combination with aminophenyl or benzofurazane label giving two independently readable redox signals in each case. In the second part of this...

A new class of fluorous materials was developed to create a hybrid solid-solution phase strategy for the expedient preparation of 125I-labelled compounds, without the need of HPLC purification. The system is referred to as a hybrid platform in that it combines solution phase labelling and fluorous solid-phase purification in one step as opposed to two separate individual processes. Initial success was achieved by treating fluorous stannanes, coated on fluorous silica, with [125I]NaI and chloramine-T (CAT) as the oxidant, where the desired nonfluorous radiolabelled products were isolated in minutes in biocompatible solutions in high purity (>98%) free from excess starting material and unreacted radioiodine. This platform was initially developed through a model system based on a fluorous benzoic acid derivative. The platform was then validated with simple aryl and heterocyclic derivatives, known radiopharmaceuticals including meta-iodobenzylguanidine (MIBG) and iododeoxyuridine (IUdR), and a new agent with high affinity for prostate-specific membrane antigen (PSMA). The limitation of the platform was the presence of non-radioactive UV impurities which came from the oxidants employed. To resolve this issue a new class of fluorous oxidants based on chloramine-T (CAT, F-CAT) were prepared. F-CAT, was prepared in 87% overall synthesis yield from commercially available starting materials and found to be effective in labelling arylstannanes and proteins with [125I]NaI. The utility of the oxidant was further demonstrated in successfully preparing a radioiodinated tetrazine (125I-Tz) through a concomitant oxidation-halodemetallation reaction. 125I-Tz can be used to label biomolecules through bioorthogonal coupling reactions with prosthetic groups containing strained alkenes including norbornene and trans-cyclooctene (TCO). The reported hybrid platform labelling approach is readily accessible and requires minimal radiochemistry expertise and should therefore find widespread use. It is also noteworthy that a second generation of the fluorous oxidant, F-CAT2, was also prepared with the aim of obtaining an oxidant which has a higher solubility in perfluorinated solvents. Application of F-CAT2 for oxidation of hydrogen sulfide to elemental sulphur in a fluorous-aqueous biphasic system was demonstrated. This approach offers a new metal-free approach to scrubbing sour gas wells and demonstrates that the fluorous oxidants developed here have utility beyond radiochemistry. / Thesis / Doctor of Philosophy (PhD)

Yes / Whilst many studies consider labelling as means of aggregated communication of environmental product features, the presentation of detailed product information seems a promising alternative. However, the mechanisms through which detailed product information takes effect on consumers requires better understanding. This study empirically develops a framework that focuses on consumers’ perceived usefulness of, and trust in, detailed product information, whilst also considering the role of environmental self-identity. This understanding will help businesses to further stimulate eco-friendly consumption. Structural equation modelling and conditional process analysis are utilised to test hypotheses based on a sample of 279 respondents to a German online survey. Findings: Results show that the perceived usefulness of product information has a positive effect on purchase intention, and this effect is intensified by an individual’s environmental self-identity. Furthermore, for consumers with high environmental self-identity, the effect of perceived usefulness of product information on purchase intention is mediated in turn by trust in detailed product information and resistance to negative information. This study contributes to the debate on the role of product information in ethical consumption by showing how detailed product information gives rise to favourable behavioural outcomes. When detailed information is perceived as being useful, it can affect purchase intention through greater trust and an increased resistance to negative information. Further, detailed product information appears beneficial for both, the mass market and specific segments with high environmental self-identity. Hence, this study empirically establishes the effects of detailed product information on consumer decision-making, thus informing sustainability-related marketing theory and practice.

No / During the last decades of nanoparticles research, many nanomaterials have been developed for applications in the field of bio-labelling. For the visualization of transport processes in the body, organs and cells, luminescent quantum dots (QDs) make for highly useful diagnostic tools. However, intercellular routes, bio-distribution, metabolism during degradation or quantification of the excretion of nanoparticles, and the study of the biological response to the QDs themselves are areas which to date have not been fully investigated. In order to aid in addressing those issues, CdSe/CdS/ZnS QDs were radioactively labelled, which allows quantification of the QD concentration in the whole body or in ex vivo samples by gamma-counting. However, the synthesis of radioactively labelled QDs is not trivial since the coating process must be completely adapted, and material availability, security and avoidance of radioactive waste must be considered. In this contribution, the coating of CdSe/CdS QDs with a radioactive (65)ZnS shell using a modified, operator-safe, SILAR procedure is presented. Under UV illumination, no difference in the photoluminescence of the radioactive and non-radioactive CdSe/CdS/ZnS colloidal solutions was observed. Furthermore, a down-scaled synthesis for the production of very small batches of 5 nmol QDs without loss in the fluorescence quality was developed. Subsequently, the radio-labelled QDs were phase transferred by encapsulation into an amphiphilic polymer. gamma-counting of the radioactivity provided confirmation of the successful labelling and phase transfer of the QDs.

Cette thèse s’intéresse à un problème de bin-packing en deux dimensions avec des défauts sur les bins rencontré dans l’industrie verrière. Les plans de découpe sont guillotine 4-stage exact, les objets à couper sans défauts.Une possible résolution utilise la décomposition de Dantzig-Wolfe puis une génération de colonnes et un branch-and-price. Cela est impossible dans notre cas du fait d’instances de trop grande taille. Nous résolvons d’abord le problème de pricing sans défauts par un algorithme incrémental de labelling basé sur un programme dynamique (DP), représenté par un problème de flot dans un hypergraphe. Notre méthode est générique pour les problèmes de sac-à-dos guillotine mais ne résout pas de larges instances en un temps de calcul raisonnable. Nous résolvons alors le problème de bin-packing sans défauts grâce à un DP et une heuristique de diving. Le DP génère des colonnes “non propres”,ne pouvant pas participer à une solution entière. Nous adaptons le diving pour ce cas sans perte d’efficacité. Nous l’étendons alors au cas avec défauts. Nous réparons d’abord heuristiquement une solution du problème sans défauts. La fixation des colonnes dans le diving sans-défaut est ensuite modifiée pour gérer les défauts. Les résultats industriels valident nos méthodes. / This thesis deals with a two-dimensional bin-packing problem with defects on bins from the glass industry. Cutting patterns have to be exact 4-stage guillotine and items defect-free. A standard way to solve it isto use Dantzig-Wolfe reformulation with column generation and branch-and price.This is impossible in our case due to large instance size. We first study and solve the defect-free pricing problem with an incremental labelling algorithm based on a dynamic program (DP), represented as a flow problem in a hypergraph. Our method is generic for guillotine knapsack problems but fails to solve large instance in a short amount of time. Instead we solve the defect freebin-packing problem with a DP and a diving heuristic. This DP generatesnon-proper columns, cutting patterns that cannot be in an integer solution.We adapt standard diving heuristic to this “non-proper” case while keeping itseffectiveness. We then extend the diving heuristic to deal with defects. Ourfirst proposal heuristically repairs a given defect-free solution. Secondly the defect-free diving heuristic is adjusted to handle defects during column fixing.Our industrial results outline the effectiveness of our methods.

Silicone release liners are silicone coatings on top of papers or films that are used in the adhesives industry to prevent adhesion before the final use of the adhesive e.g. labels. The process of production of release liners involves the casting of molten polysiloxanes on top of the substrates that crosslink by hydrosilylation reaction forming silicone networks. The quality of the release liner can be assessed by diverse methods usually performed when the coating process has been finished. Rarely an online control of the reaction is possible. Fluorescence spectroscopy was found to be a non-invasive useful method to control the reaction during the whole process by introducing very small concentration of fluorescent molecules in the polymer formulations; those fluorophores are sensitive to environmental changes as the silicone polymer molecules crosslink. In response to that stimulus, the fluorescence intensity varies along the time upon reaction allowing the identification of the gel point and further modifications or molecules rearrangements in a post-curing stage within weeks that are non-observable with conventional quality control methods. It was found that the fluorescent molecules do not require to be attached covalently to the polysiloxanes, thus fluorescence spectroscopy is a simple method to implement for controlling the production of silicone coatings. Moreover, the characterization of several silicone formulations was performed to find the optimal conditions for the production of release liners and to understand the effect of every component in the formulation on the performance of the silicones. The kinetics of the reaction was also studied and even a mechanism for the hydrosilylation reaction was proposed.

Submitted by Maicon Juliano Schmidt (maicons) on 2015-06-11T18:29:09Z No. of bitstreams: 1 Maria Cristina Furtado da Silva.pdf: 764706 bytes, checksum: 895ab39648c68f2f22cf494c989f77e0 (MD5) / Made available in DSpace on 2015-06-11T18:29:09Z (GMT). No. of bitstreams: 1 Maria Cristina Furtado da Silva.pdf: 764706 bytes, checksum: 895ab39648c68f2f22cf494c989f77e0 (MD5) Previous issue date: 2015-03-06 / Nenhuma / Este trabalho tem como objetivo avaliar a compreensão da representação gráfica das informações nutricionais presentes nos rótulos de alimentos por adolescentes escolares. Foi realizado um estudo transversal com 56 adolescentes escolares (n=56), com idades compreendidas entre 15 e 17 anos, matriculados em uma escola particular de Porto Alegre/RS. Para a realização da pesquisa foi utilizado um questionário específico estruturado com nove perguntas fechadas dicotômicas e de múltipla escolha. Os resultados mostram que 41% dos adolescentes escolares costumam ler os rótulos antes da compra, 71% afirmam conhecer o significado de valor energético dos alimentos, 63% declaram compreender as informações escritas nos rótulos e 61% confiam nas informações escritas nas embalagens de alimentos. A maioria dos adolescentes compreende os componentes nutricionais presentes nos rótulos de alimentos brasileiros, e apenas 45% entendeu as informações nutricionais presentes no modelo de rótulo Traffic Light Labelling ou “Semáforo Nutricional”, evidenciando que a rotulagem utilizada no Brasil apresentou resultados mais positivos de compreensão. Os resultados do estudo indicam que um número relevante de adolescentes (63%) compreende os componentes nutricionais presentes nos rótulos de alimentos brasileiros e um número significativo de indivíduos compreendeu e identificou a informação nutricional mais saudável descritas nos rótulos; no entanto, sugere-se o desenvolvimento de programas de educação nutricional para potencializar a compreensão das informações nutricionais contidas nos rótulos para este perfil de consumidor. / This paper aims at evaluating the understanding of graphical representation of nutritional information on food labels by young adolescent students. Therefore, it was carried out a cross-sectional study with 56 young adolescent students (n = 56), aged between 15 and 17 years, enrolled in a private school in Porto Alegre / RS. A specific questionnaire containing nine dichotomous and multiple choice closed questions was used for data gathering. The results showed that 41% of young adolescent students usually read the labels before purchasing, 71% of them claim to know the meaning of the energetic value of food, 63% say they understand the information written on the labels, and 61 % trust the information written on food packages. Most adolescents understand the nutritional components present on the labels of Brazilian foods, and only 45% understood the nutrition information on the Traffic Light labelling system, showing that the labels used in Brazil are better understood. The results indicate that a meaningful number of adolescents (63%) understands the nutritional components on the labels of Brazilian food, and a meaningful number of individuals understood and identified the healthiest nutritional information given on labels; however, it is suggested the development of nutrition education programs to enhance the understanding of the nutritional information on the labels for this consumer profile.

Dans ce mémoire de thèse, je rapporte les résultats des études réalisées durant ces trois dernières années à l'Institut Non Linéaire de Nice. D'une part, je présente nos expériences de miroir de rétro-action conduisant à la formation spontanée de patterns dans la section transversale d'un faisceau laser (pompe) traversant le centre d'un nuage d'atomes froids de 87Rb et rétro-réfléchi par un miroir placé à une distance du nuage. Dans ces expériences nous discernons trois types de mécanismes de nonlinéarités : la nonlinéarité de spin qui est liée au pompage Zeeman, la nonlinéarité électronique existant pour un atome à deux niveaux et la nonlinéarité opto-mécanique qui est liée à la force dipolaire. Ces mécanismes dépendant des paramètres du MOT et de la pompe (intensité, désaccord, durée) sont étudiés séparément en jouant sur ces paramètres. Ces études expérimentales sont comparées avec des résultats obtenus avec des modèles théoriques. D'autre part, je présente nos observation concernant la densité d'état intégrée et les la densité d'états locale des bandes d'un quasi-cristal bidimensionnel. Dans cette expérience réalisée au Laboratoire de Physique de la Matière Condensée, nous avons réalisé des quasi-cristaux en disposant des résonateurs diélectriques agissant dans le domaine micro-onde sur des pavages de Penrose 2D. Un modèle numérique prenant en compte les paramètres expérimentaux est utilisé pour comparer les résultats obtenus. / First, I present our feedback experiment leading to the spontaneous formation of patterns in the cross section of a laser beam passing through a cloud of cold 87Rb atoms and retroreflected by a mirror. In these experiments we were able to identify three mechanisms of nonlinearity: the spin nonlinearity associated with the Zeeman degrees of freedom, the electronic nonlinearity due to the saturation of a two-level atom and the optomechanical nonlinearity due to the spatial bunching of atoms by the dipole force. The instabilities corresponding to each nonlinear mechanism occurs in different range of the experimental parameters and can be selected and studied independently. The experimental observations are compared with various theoretical models. In the second part of the thesis, I present our study of the integrated density of states (IDOS) and the local density of states (LDOS) of the bands of a two-dimensional quasicrystal. In an experiment conducted at Laboratoire de Physique de la Matière Condensée (LPMC), we realized quasicrystals by disposing dielectric resonators operating in the microwave regime on 2D Penrose tiling. A numerical model including experimental parameters is used to compare to the experimental findings.