Ces travaux de thèse ont permis, au cours de deux projets, de s’attacher à la synthèse de structures complexes au moyen de réaction en cascade et de catalyse au rhodium.Dans une première partie, une méthodologie robuste pour la synthèse de 2,4,6-cycloheptatriénones entièrement substituées et non-symétriques par réaction de cycloaddition carbonylative [2+2+2+1] catalysée par des complexes de rhodium a été développée. Des mécanismes expliquant la formation des différents composés ont été proposés. Dans une seconde partie, l’application de l’hydroformylation désymétrisante catalysée au rhodium à la synthèse totale d’alcaloïdes indoliques de la famille Aspidosperma a été étudiée. Un intermédiaire clé de la synthèse de composés de type eburnane a ainsi été obtenu et sa transformation par différente stratégies été explorée. La synthèse totale de composés de type aspidosperma a été étudié, et les voies de synthèse explorées pourront être appliquées à des aldéhydes issus d’hydroformylation désymétrisante. / Through the course of two projects, this thesis work was concerned with the synthesis of complex scaffolds by means of cascade reactions and rhodium catalysis.In a first part, a new methodology was developed for the synthesis of non-symmetrical and fully substituted 2,4,6-cycloheptatrienones by rhodium-catalysed [2+2+2+1] carbonylative cycloaddition. Mechanisms for the formations of the observed compounds were proposed.In a second part, the application of rhodium-catalysed desymmetrising hydroformylation to the total synthesis of Aspidosperma indole alkaloids was studied. A key intermediate in the synthesis of eburnan-type alkaloids was thus obtained, and its transformation into th desired compounds using various strategies was explored. The total synthesis of aspidosperma-type alkaloids was studied, and the explored syntheses will be applied to aldehydes obtained by desymmetrising hydroformylation.

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Quantifying and modeling processes involved in the global carbon cycle is important to evaluate the temporal and spatial variability of these processes and understand the effect of this variability on future response to changing climate and land use patterns. Biomass accumulation and Net Primary Productivity (NPP) are large components of ecosystem carbon exchange with the atmosphere and thus are the focus of many modeling efforts. When scaling estimates of NPP temporally from days to years and spatially from square meters to landscapes and regions the spatial coherence of these processes through time must be taken into account. Spatial coherence is the degree to which pairs of sites across space are synchronous (i.e., correlated) through time with respect to a given process or variable. In this thesis I determined the spatial coherence of a major component of NPP, tree bole productivity (NPP[subscript B]), and examine how it influences scaling and our ability to predict NPP and forecast change of this flux. In Chapter 2 I developed and tested a method modeling radial tree increment growth from sub-sampled trees and estimating annual site-level biomass accumulation that allows quantification of the uncertainty in these estimates. Results demonstrated that a simple model using the mean and standard deviation of growth increments underestimated bole biomass increment in all three age classes examined by 1% at the largest sample sizes and up to 15% at the smallest sample sizes. The long term average NPP[subscript B] and inter-annual variability were also underestimated by as much as 10% and 22%, respectively. Stratification of trees by size in sampling and modeling methods increased accuracy and precision of estimates markedly. The precision of both models was sufficient to detect patterns of inter-annual variability. To estimate bole biomass accumulation with acceptable levels of accuracy and precision our results suggest sampling at least 64 trees per site, although one site required a sample size of more than 100 trees. In Chapter 3 I compared year to year variability of NPP for tree boles (NPP[subscript B]) for two adjacent small watersheds (second-growth and old-growth) in the western Cascades of Oregon using the methods developed in Chapter 2. Spatial coherence of NPP[subscript B] within and between watersheds was assessed using multivariate analysis techniques. NPP[subscript B] was found to be less coherent between watersheds than within watersheds, indicating decreased spatial coherence with differences in age class and increased spatial scale. However, a larger degree of spatial coherence existed within the old-growth watershed compared to the second-growth watershed, which may be a result of the smaller degree of variation in environmental characteristics in the former watershed. Within a watershed, potential annual direct incident radiation and heat load were more strongly associated with the variation of NPP[subscript B] than climate. Climatic factors correlated with the temporal variation of annual NPP[subscript B] varied between the two watersheds. Results suggest that inter-annual variability and spatial coherence of forest productivity is a result of both internal (e.g., environment and stand dynamics) and external (climate) factors. An unexpected conclusion was that spatial coherence was not consistent and changed through time. Therefore, the coherence of sites over time is not a simple relationship. Instead the patterns of spatial coherence exhibit complex behaviors that have implications for scaling estimates of productivity. This result also indicates that a correlation coefficient alone may not capture the complexity of change through time across space. In Chapter 4 I estimated year to year variation of NPP[subscript B] for eleven sites of varying age, elevation, moisture, and species composition in the Western Cascades of Oregon. Spatial coherence of tree growth within sites and NPP[subscript B] between sites was assessed using Pearson's product-moment correlation coefficient (r). Results suggest that spatial coherence is highly variable between sites (r=-O.18 to 0.92). The second-growth sites exhibited the greatest temporal variability of annual NPP[subscript B] due to the large accumulation of biomass during stand initiation, but old-growth sites exhibited the greatest variation of coherence of NPP[subscript B] between sites. In some years all sites behaved similarly, but for other years some sites were synchronous while others were not. As growth of individual trees and NPP[subscript B] at the site scale increased, inter-annual variability of those variables increased. Climate in part affected annual NPP[subscript B], but intrinsic factors and spatial proximity also affected the coherence between sites in this landscape. / Graduation date: 2006

Forest stands were studied to determine if old-growth forest structure could be mimicked in younger stands via overstory manipulation. Cover and species composition of understory plants were systematically sampled in sixteen thinned second-growth stands and sixteen adjacent unthinned second-growth Douglas fir (Pseudotsuga menziesii (Mirabel) Franco.) stands. The stands were thinned twenty-four to thirteen years ago. These were compared to seven nearby old-growth stands. Thinned and unthinned stands had matching elevations, aspect, and soils, yet differed primarily in management treatment. Leaf area indices were determined for these stands. Thinned stands differed from the old-growth and unthinned stands in having significantly higher cover values and species numbers, apparently resulting from increased light to the forest floor and a greater variety of microhabitats created by thinning. Young unthinned and old-growth stands were comparable in terms of cover and richness, but differed in species composition. Diversity indices showed no difference in species diversity between the three types of stands. Ordination of the species/sample data using Detrended Correspondence Analysis showed that understory species composition of the young unthinned and thinned stands was nearly identical. Species composition of old-growth stands differed from thinned and unthinned stands. The ordination indicated that age of the stands, structure of the canopy layers and climate were major determining factors in the species composition of the understory plant communities. Management manipulation of the second growth stands did not yield stands with understory vegetation communities that mimicked those of old-growth stands. The conclusions of this study were: 1) Shrub cover increased with thinning as compared to unthinned and old-growth stands. 2) Thinning increased the species richness of the stands, without increasing the number of exotics. 3) Diversity was not altered by thinning. Old-growth, thinned and unthinned stands did not differ in diversity values. 4) Patterns of community composition in thinned stands were more similar to unthinned equivalent stands than to nearby old-growth. / Graduation date: 1996

Graduation date: 1993

This desertation shows that a unique class of network disruption exists that can be regarded in isolation of other classes of network disturbances, namely cascade disruption of generation (COG). This class of disturbance is being defined in terms of the cascading effect that it exhibits in terms of the disruption of power generating units in an interconnected power system. Through a literature survey it is shown that a lack of formal acknowledgement exists in the recognition of this class of disturbance both locally and abroad, and that therefore there is a general absence of a policy framework to manage the threat that is associated with the cascade disruption of generation. The analysis of the records of such events in the Southern African power pool are analised, and the properties and characteristics of COG events are explored. The extent of the threat to the interconnected power system that is posed by COG, as a phenomenon, is quantified in the conte·xt of industry practice and weaknesses are identified. It is shown that the occurrence of this class of event is not entirely random, and that statistical methods can be used in the development of mitigation strategies. A management framework is developed with metrics for the monitoring, evaluation and trending of the phenomenon, and to evaluate the ongoing risk. Roles and responsibilities are sugested and a outline for the systematic investigation of such events is developed. In the conclusion, the possible benefits of the an COG managenent framework are discussed and scope for future work in this regard is suggested. / Thesis (MIng (Electrical and Electronic Engineering))--North-West University, Potchefstroom Campus, 2013

This desertation shows that a unique class of network disruption exists that can be regarded in isolation of other classes of network disturbances, namely cascade disruption of generation (COG). This class of disturbance is being defined in terms of the cascading effect that it exhibits in terms of the disruption of power generating units in an interconnected power system. Through a literature survey it is shown that a lack of formal acknowledgement exists in the recognition of this class of disturbance both locally and abroad, and that therefore there is a general absence of a policy framework to manage the threat that is associated with the cascade disruption of generation. The analysis of the records of such events in the Southern African power pool are analised, and the properties and characteristics of COG events are explored. The extent of the threat to the interconnected power system that is posed by COG, as a phenomenon, is quantified in the conte·xt of industry practice and weaknesses are identified. It is shown that the occurrence of this class of event is not entirely random, and that statistical methods can be used in the development of mitigation strategies. A management framework is developed with metrics for the monitoring, evaluation and trending of the phenomenon, and to evaluate the ongoing risk. Roles and responsibilities are sugested and a outline for the systematic investigation of such events is developed. In the conclusion, the possible benefits of the an COG managenent framework are discussed and scope for future work in this regard is suggested. / Thesis (MIng (Electrical and Electronic Engineering))--North-West University, Potchefstroom Campus, 2013

The thesis entitled “Organocatalytic Cascade Cyclizations for the Enantioselective Synthesis of Spirooxindoles” is divided into three chapters. Chapter 1: Catalytic Enantioselective Michael Addition/Cyclization Cascade of 3-Isothiocyanato Oxindoles with Nitroolefins A myriad of spirocyclic frameworks present in natural product, and pharmaceutically important compounds, has attracted the synthetic organic chemists to explore their preparation in enantioselective manner. Consequently various strategies have been devised for efficiently accessing highly functionalized spirooxindoles. Among these strategies, the use of 3-isothiocyanato oxindoles as the building block appeared as the most popular one. The combination of 3-isothiocyanato oxindoles and a variety of electrophiles have already been reported. However one of the most popular electrophiles, nitroolefins, has never been used in the reaction with 3-isothiocyanato oxindoles. In this chapter, a highly efficient catalytic asymmetric Michael addition/cyclization cascade reaction between 3-isothiocyanato oxindoles and β-substituted nitroolefins with the help of a cinchonidine-derived bifunctional thiourea catalyst has been discussed. Highly functionalized spirooxindoles containing three successive stereocenters were obtained in high yield with moderate to good diastereo- and enantioselectivity. Reference: Kayal, S.; Mukherjee, S. Eur. J. Org. Chem. 2014, 6696-6700. Chapter 2: Catalytic Aldol-Cyclization Cascade of 3-Isothiocyanato Oxindoles with α-Ketophosphonates for the Enantioselective Synthesis of β-Amino-α-Hydroxyphosphonates The oxindole scaffold containing a quaternary stereocenter at the C3 position is a privileged structural motif present in many biologically active molecules and natural products. In this respect, spirooxindoles have received special attention during the past few years. Similarly, β-Amino and/or hydroxy functionalized phosphonic acids and their derivatives are found to display inhibitory activities towards a range of enzymes such as renin, HIV protease, thrombin, and various classes of protein tyrosine kinases and phosphatases. Considering the importance of both oxindole and β-amino-α-hydroxyphosphonic acid, we reasoned that highly functionalized phosphonic acid derivatives based on a spirooxindole framework could be of potential biological significance, if synthesized in enantiopure form This chapter deals with a cascade aldol-cyclization reaction between 3-isothiocyanato oxindoles and α-ketophosphonates for the enantioselective synthesis of spirooxindole-based β-amino-α-hydroxyphosphonate derivatives. Catalyzed by cinchona alkaloid-based bifunctional thiourea derivatives, this protocol delivers 2-thioxooxazolidinyl phosphonates bearing two adjacent quaternary stereogenic centers, generally in high yields with excellent diastereo- and enantioselectivities. Both the product enantiomers are accessible with nearly equally high level of enantioselectivity. Reference: Kayal, S.; Mukherjee, S. Org. Lett. 2015, 17, 5508-5511. Chapter 3: Catalytic Michael Addition/Cyclization Cascade of 3-Isothiocyanato Oxindoles with Cyclic α,β-Unsaturated Ketones: A Concise Enantioselective Synthesis of Bispiro[indoline-3,2'-pyrrolidine] Among different spirocyclic cores, the spirooxindole framework containing pyrrolidinyl ring represents a very important class owing to their biological activities such as antimicrobial, anticancer, antihypertensive, antidiabetic, antimycobacterial and antitubercular properties. Similarly, the bispirooxindole scaffold recently has drawn considerable interests because of its exclusive structural and stereochemical diversity. Only a few examples have been reported till date for enantioselective construction of the pharmaceutically important bispirooxindole architectures. Considering the importance of bispirooxindoles and pyrrolidinyl spirooxindole scaffolds, we were interested in merging them in a single molecular framework. In this chapter, a Michael addition/cyclization cascade reaction between 3-isothiocyanato oxindoles and exocyclic enones for the enantioselective synthesis of 3,2′-pyrrolidinyl bispirooxindole derivatives has been illustrated. With the help of a quinine-derived bifunctional squaramide as the catalyst, this protocol delivers bispirooxindoles bearing three contiguous stereogenic centers, in high yields and generally with outstanding diastereo- and enantioselectivity. Reference: Kayal, S.; Mukherjee, S. manuscript under preparation.

Les Lasers à Cascade Quantique (QCL) sont de "nouvelles" sources THz dont les progrès en termes de puissance, température de fonctionnement et qualité de faisceau sont remarquables. Les QCL sont utilisés dans des dispositifs d'imagerie THz continue pour le Contrôle Non Destructif de matériaux. Une première application de CND sur des matériaux composites permet de mettre en évidence de manière qualitative les défauts d'imprégnation des fibres par la résine ou les dommages causés par un impact. Des images à 3,8 THz, en transmission et ré flexion, ont pu être comparées avec une technique de CND par ultrasons. Une seconde application quantitative porte sur la concentration d'eau dans deux matériaux polymères à tendance hydrophobe : le polystyrène et le polypropylène. L'établissement d'une relation entre la transmittance de l'échantillon et sa prise de masse d'eau permet d'établir une cartographie quantifiée de la concentration d'eau. Ces cartographies sont nécessaires à la connaissance du processus de diffusion de l'eau dans les matériaux polymères. / Quantum Cascade Lasers (QCL) are "new" THz sources that have enjoyed remarkable progress in terms of power, operating temperature and beam quality. QCLs are used in continuous wave THz imaging setups applied to Non Destructive Testing of materials. A first qualitative application of NDT allows us to highlight defects in the fibers impregnation by resin or damages caused by an impact on composite materials. Transmission and reflection images at 3.8 THz are compared with a NDT ultrasonic technique. A second quantitative application relates to the water concentration in two hydrophobic polymeric materials: polystyrene and polypropylene. Establishing a relationship between the transmittance of the sample and mass water content enables us to draw up a quantified mapping of the latter. These maps are necessary for the understanding of the water diffusion process in polymeric materials.

Les plasmas d’air à pression atmosphérique ont de nombreuses applications. Nous pouvons par exemple citer les applications biomédicales, le traitement des matériaux, la bio-décontamination environnementale et la combustion assistée par plasma. La polyvalence des décharges plasma résulte de leur capacité à produire des densités élevées d’espèces actives, sans toutefois chauffer substantiellement le gaz. Les décharges nanosecondes répétitivement pulsées (NRP) ont particulièrement reçu une grande attention en raison de leur capacité à produire des densités électroniques élevées, qui conduisent à la création de fortes densités d’espèces actives telles que l’oxygène atomique (O). Par ailleurs, des mesures de spectroscopie d’émission ont montré que des états excités du monoxyde d’azote (NO) sont produits par les décharges NRP opérant dans l’air ou dans des mélanges combustibles. Bien que les décharges NRP aient déjà fait l’objet de plusieurs investigations, les mécanismes cinétiques conduisant à la production de NO sont toujours incertains. C’est la motivation première des travaux menés dans le cadre de cette thèse. En outre, les décharges NRP se sont avérées produire une grande quantité d’oxygène d’atomique, espèce de grande importance pour la combustion assistée par plasma. Il a été en particulier démontré que grâce à la production élevée d’espèces actives, les décharges NRP peuvent stabiliser efficacement des flammes pauvres, à pression atmosphérique. Cependant la production de NO par les décharges NRP et les flammes stabilisées à l’aide des décharges NRP reste à étudier. Cela constitue le second objectif de cette thèse. Les mesures in-situ de densités absolues de NO dans les décharges plasmas et/ou en combustion sont très difficiles. Les techniques de fluorescence telle que la fluorescence induite par laser (LIF) nécessitent de complexes méthodes de calibration. Ces techniques requièrent également la connaissance des taux de quenching des états excités (en particulier à pression atmosphérique). Or ces taux de quenching sont très fortement dépendants de la température, de la nature des espèces en présence et de leur densité, et peuvent donc énormément différer entre un plasma opérant dans l’air et en combustion. D’autres techniques telles que l’utilisation des sondes à chimiluminescence sont tout aussi sujettes aux problèmes de calibration et de quenching des états excités tandis que les mesures ex-situ à l’aide d’analyseurs à gaz réalisant de l’absorption dans l’UV et l’IR peuvent conduire à des erreurs, surtout lorsqu’il s’agit de mesurer des radicaux. Dans cette étude, nous avons développé la spectroscopie d’absorption par laser à cascade quantique (QCLAS), pour des mesures in-situ de densités de NO dans l’air et en combustion. Cette technique permet de surmonter les difficultés des autres méthodes par utilisation d’une spectroscopie rotationnelle-vibrationnelle de haute résolution spectrale (10-3 cm-1). La QCLAS a les avantages d’être spectralement sélective, d’avoir une grande sensibilité et de ne pas nécessiter de calibration. Deux dispositifs expérimentaux ont été développés pour mesurer des densités de NO et des températures (1) dans une décharge NRP dans l’air, avec une résolution spatiale de 300-µm, et (2) en aval de la décharge NRP opérant dans l’air et dans des flammes méthane/air assistée par plasma, par utilisation d’une cellule multi-passages. [...] / Atmospheric pressure plasmas have numerous potential applications. These applications include for instance biomedicine, material processing, environmental biodecontamination and plasma-assisted combustion. The versatility of plasma discharges results from their ability to produce high quantities of active species without increasing the temperature of the gas appreciably. Nanosecond Repetitively Pulsed discharges (NRP) have received great attention owing to their capacity to generate high electron densities, which lead to the creation of a high density of active species such as atomic oxygen. Optical Emission Spectroscopy (OES) showed that excited nitric oxide (NO) was released by NRP discharges in air or in air/fuel mixtures.Although NRP discharges have already been the object of several investigations, the kinetic mechanisms of NO production by NRP discharges at atmospheric pressure remain somewhat unclear. This is one of the motivations for the investigations conducted in this thesis. In addition, NRP discharges were found to produce large amounts of atomic oxygen, which is of great interest for applications such as plasma-assisted combustion. It was shown in particular that thanks to this high production of active species, NRP discharges can effectively stabilize lean flames at atmospheric pressure. However, the production of NO in NRP discharges and in plasma-stabilized flames remains to be investigated. This is the second purpose of this thesis.Absolute and in-situ NO density measurements in atmospheric pressure plasma or/and flame environments are very challenging. Fluorescence-based techniques such as Laser Induced Fluorescence (LIF) require complex calibration methods. These techniques also require the knowledge of the quenching rates of the excited states (particularly at atmospheric pressure), which strongly depend on the temperature, density and nature of the species and can be very different for plasma or/and flame environments. Other techniques, such as chemiluminescence probe sampling also have quenching and calibration issues, and ex-situ UV and IR absorption-based gas analyzers can lead to errors, in particular for radicals.In this study, we developed Quantum Cascade Laser Absorption Spectroscopy (QCLAS) for in-situ nitric oxide absolute density measurements in open-air and in combustion environments. This technique overcomes the difficulties of the previous ones by using high-resolution (10-3 cm-1) rotational-vibrational absorption spectroscopy. This technique presents the advantages of high spectral selectivity, no calibration requirement, and high sensitivity. Two experimental setups were developed to measure NO densities and temperature, (1) within a NRP discharge in air, with 300-µm spatial resolution, and (2) downstream of NRP discharges in air and in plasma-assisted methane/air flames, using multi pass cell. [...]