Surface grafting and modification of poly(acrylic acid) (PAA) were performed on nylon 6,6 carpet fibers to achieve permanent stain and soil resistance. PAA was grafted to nylon and modified with 1H, 1H-pentadecafluorooctyl amine (PDFOA) using an amidation agent, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)-4-methylmorpholinium chloride (DMTMM). The first goal was to optimize acrylamide modification of PAA in solution. Aqueous reactions with taurine, hydroxyethyl amine, and butyl amine progressed ~100%, while PDFOA reactions in MeOH progressed ~80%. Reaction products precipitated at 77% butyl or 52% PDFOA acrylamide contents. The second goal was to optimize the PAA grafting process. First, PAA was adsorbed onto nylon 6,6 films. Next, DMTMM initiated grafting of adsorbed PAA. PAA surface coverage was ~78%, determined by contact angle analysis of the top 0.1-1 nm and x-ray photoelectron spectroscopy (XPS) analysis of the top 3-10 nm. The third goal was to modify PAA grafted nylon films with butyl amine and PDFOA. Randomly methylated beta-cyclodextrin (RAMEB) solubilized PDFOA in water. Contact angle detected ~ 100% surface reaction for each amine, while XPS detected ~77% butyl amine (H2O) and ~50% for PDFOA (MeOH or H2O pH=7) reactions. In H2O pH=12, the PDFOA reaction progressed ~89%, perhaps due to greater efficiency, access and solubility. The fourth goal was to perform surface depth profiling via angle-resolved XPS analysis (ARXPS). The PAA surface coverage from contact angle and XPS was confirmed. Further, adsorbed PAA was thicker than grafted PAA, supporting the theory that PAA adsorption occurs in thick layers onto nylon followed by DMTMM-activated spreading and grafting of thinner PAA layers across the surface. The PDFOA reaction in MeOH produced a highly fluorinated but thin exterior and an unreacted PAA interior. The PDFOA reaction in H2O pH=12 produced a completely fluorinated exterior and highly fluorinated interior. Thus surface modification levels from contact angle and XPS were confirmed. The final goal was to PAA-graft and PDFOA-modify nylon 6,6 fabrics and carpets. PDFOA modification achieved significant water and oil repellency. Stainblocking was slightly improved for ionized PAA-g-nylon and greatly improved for PDFOA-modified PAA-g-nylon. However, traditional stainblockers may be necessary to completely prevent dye penetration into carpet tufts.

3,5-Dimethylorsellinic acid (DMOA)-derived meroterpenoids are an extensive natural product family with significant structural complexity and diverse biological activity. Their structures feature various fused, bridged, spirocyclic skeletons and unconventional stereochemistries with significant strain, especially the trans-syn-trans fused drimane system, and extensive oxidative, skeletal rearrangements. Despite a long isolation history and extensive biosynthesis studies and encouraging biological activities, chemical synthesis of those natural products appeared only recently compared with other well-studied diterpene families such as the ent-kauranes, daphanes, and tiglianes. Thus, this thesis will present our work as an incremental advancement on the total syntheses of DMOA-derived meroterpenoids. In Chapter 1, a thorough biosynthetic relationship of DMOA-derived meroterpenoid subfamilies is reviewed and the most updated isolation and syntheses are covered with the purpose to provide the reader an understanding and appreciation of the origin of the exceptional diversity of DMOA-derived meroterpenoids. In Chapter 2, three generations of routes towards DMOA-derived spiromeroterpenoid are discussed in detail. The oxidative [3+2] cyclization approach was found to generate several complex dimers and the simplicission core. Lessons learned therein pointed to a successful strategy. In Chapter 3, a successful fragment coupling strategy culminated in a concise, modular, and collective synthesis of five spiromeroterpenoid natural products. The synthesis features a sterically hindered bis-neopentyl 1,2-addition coupling/oxidative Michael addition/MHAT reduction sequence to rapidly construct the conserved spirocycle with full stereo-control. The gateway natural product asnovolin A was secured in deca-milligram amounts which laid the foundation for chemoenzymatic synthesis of the highly oxidized spiromeroterpenoid novofumigatonin. In Chapter 4, significant progress was made towards the synthesis of the complex meroterpenoid andiconin. We developed a late stage de novo construction of the dearomatized biosynthetic precursor. A biomimetic radical fragmentation [4+2] cascade was designed to establish the highly congested [2.2.2] octane core of the natural product. / 2026-03-15T00:00:00Z

L'estimation de crues de projet est requise pour le dimensionnement de barrages et de bassins de rétention, de même que pour la gestion des inondations lors de l’élaboration de cartes d’aléas ou lors de la modélisation et délimitation de plaines d’inondation. Généralement, les crues de projet sont définies par leur débit de pointe à partir d’une analyse fréquentielle univariée. Cependant, lorsque le dimensionnement d’ouvrages hydrauliques ou la gestion de crues nécessitent un stockage du volume ruisselé, il est également nécessaire de connaître les caractéristiques volume, durée et forme de l’hydrogramme de crue en plus de son débit maximum. Une analyse fréquentielle bivariée permet une estimation conjointe du débit de pointe et du volume de l’hydrogramme en tenant compte de leur corrélation. Bien qu’une telle approche permette la détermination du couple débit/volume de crue, il manque l’information relative à la forme de l’hydrogramme de crue. Une approche attrayante pour caractériser la forme de la crue de projet est de définir un hydrogramme représentatif normalisé par une densité de probabilité. La combinaison d’une densité de probabilité et des quantiles bivariés débit/volume permet la construction d’un hydrogramme synthétique de crue pour une période de retour donnée, qui modélise le pic d’une crue ainsi que sa forme. De tels hydrogrammes synthétiques sont potentiellement utiles et simples d’utilisation pour la détermination de crues de projet. Cependant, ils possèdent actuellement plusieurs limitations. Premièrement, ils reposent sur la définition d’une période de retour bivariée qui n’est pas univoque. Deuxièmement, ils décrivent en général le comportement spécifique d’un bassin versant en ne tenant pas compte de la variabilité des processus représentée par différents types de crues. Troisièmement, les hydrogrammes synthétiques ne sont pas disponibles pour les bassins versant non jaugés et une estimation de leurs incertitudes n’est pas calculée.Pour remédier à ces manquements, cette thèse propose des avenues pour la construction d’hydrogrammes synthétiques de projet pour les bassins versants jaugés et non jaugés, de même que pour la prise en compte de la diversité des types de crue. Des méthodes sont également développées pour la construction d’hydrogrammes synthétiques de crue spécifiques au bassin et aux événements ainsi que pour la régionalisation des hydrogrammes. Une estimation des diverses sources d’incertitude est également proposée. Ces travaux de recherche montrent que les hydrogrammes synthétiques de projet constituent une approche qui s’adapte bien à la représentation de différents types de crue ou d’événements dans un contexte de détermination de crues de projet. Une comparaison de différentes méthodes de régionalisation montre que les hydrogrammes synthétiques de projet spécifiques au bassin peuvent être régionalisés à des bassins non jaugés à l’aide de méthodes de régression linéaires et non linéaires. Il est également montré que les hydrogrammes de projet spécifiques aux événements peuvent être régionalisés à l’aide d’une approche d’indice de crue bivariée. Dans ce contexte, une représentation fonctionnelle de la forme des hydrogrammes constitue un moyen judicieux pour la délimitation de régions ayant un comportement hydrologique de crue similaire en terme de réactivité. Une analyse de l’incertitude a montré que la longueur de la série de mesures et le choix de la stratégie d’échantillonnage constituent les principales sources d’incertitude dans la construction d’hydrogrammes synthétiques de projet. Cette thèse démontre qu’une approche de crues de projet basée sur un ensemble de crues permet la prise en compte des différents types de crue et de divers processus. Ces travaux permettent de passer de l’analyse fréquentielle statistique de crues vers l’analyse fréquentielle hydrologique de crues permettant de prendre en compte les processus et conduisant à une prise de décision plus éclairée. / Design flood estimates are needed in hydraulic design for the construction of dams and retention basins and in flood management for drawing hazard maps or modeling inundation areas. Traditionally, such design floods have been expressed in terms of peak discharge estimated in a univariate flood frequency analysis. However, design or flood management tasks involving storage, in addition to peak discharge, also require information on hydrograph volume, duration, and shape . A bivariate flood frequency analysis allows the joint estimation of peak discharge and hydrograph volume and the consideration of their dependence. While such bivariate design quantiles describe the magnitude of a design flood, they lack information on its shape. An attractive way of modeling the whole shape of a design flood is to express a representative normalized hydrograph shape as a probability density function. The combination of such a probability density function with bivariate design quantiles allows the construction of a synthetic design hydrograph for a certain return period which describes the magnitude of a flood along with its shape. Such synthetic design hydrographs have the potential to be a useful and simple tool in design flood estimation. However, they currently have some limitations. First, they rely on the definition of a bivariate return period which is not uniquely defined. Second, they usually describe the specific behavior of a catchment and do not express process variability represented by different flood types. Third, they are neither available for ungauged catchments nor are they usually provided together with an uncertainty estimate.This thesis therefore explores possibilities for the construction of synthetic design hydrographs in gauged and ungauged catchments and ways of representing process variability in design flood construction. It proposes tools for both catchment- and flood-type specific design hydrograph construction and regionalization and for the assessment of their uncertainty.The thesis shows that synthetic design hydrographs are a flexible tool allowing for the consideration of different flood or event types in design flood estimation. A comparison of different regionalization methods, including spatial, similarity, and proximity based approaches, showed that catchment-specific design hydrographs can be best regionalized to ungauged catchments using linear and nonlinear regression methods. It was further shown that event-type specific design hydrograph sets can be regionalized using a bivariate index flood approach. In such a setting, a functional representation of hydrograph shapes was found to be a useful tool for the delineation of regions with similar flood reactivities.An uncertainty assessment showed that the record length and the choice of the sampling strategy are major uncertainty sources in the construction of synthetic design hydrographs and that this uncertainty propagates through the regionalization process.This thesis highlights that an ensemble-based design flood approach allows for the consideration of different flood types and runoff processes. This is a step from flood frequency statistics to flood frequency hydrology which allows better-informed decision making.