La dichotomie environnementale qui caractérise la Terre, à savoir la présence de milieux aquatiques et de terres émergées, a joué un rôle important au cours de l’évolution de la vie. L’histoire évolutive des vertébrés, par exemple, a continuellement été ponctuée d’épisodes de sorties des eaux et de retours aux milieux aquatiques, souvent soulignés dans le registre fossile par des radiations biologiques majeures. L’exemple le plus célèbre concerne probablement les épisodes de sorties des eaux des premiers tétrapodes qui bouleversent les écosystèmes terrestres il y a environ 360 millions d’années, au moment de la transition Dévonien-Carbonifère. A l’échelle des temps géologiques, ces transitions écologiques ont pu revêtir un caractère soudain ; une instantanéité apparente résultant cependant, bien souvent, de l’incomplétude du registre fossile. Au fur et à mesure que les données paléontologiques s’étoffent ces transitions écologiques nous content des histoires d’une grande complexité, s’inscrivant dans des durées de l’ordre du million, voire de la dizaine de millions d’années ! La compréhension de toutes ces histoires nécessite de connaître avec précision les milieux de vie de leurs principaux acteurs, les espèces éteintes de vertébrés. Traditionnellement, l’étude des environnements de vie des espèces fossiles s’appuie sur les analyses morpho-fonctionnelles et sédimentaires. Cependant, ces deux méthodes permettent seulement de reconstruire un environnement fonctionnel et un environnement de dépôt, qui peuvent être différents de l’environnement de vie. L’objectif principal de cette thèse est de démontrer l’intérêt de l’analyse de la composition isotopique du soufre dans les apatites de vertébrés afin de reconstituer leurs milieux de vie. Nous avons tout d’abord démontré la capacité du système VarioPyrocube©, couplé en flux continu à un spectromètre de masse à ratio isotopique, à analyser avec précision la composition isotopique du soufre dans les apatites biogènes. Nous avons ensuite démontré que l’analyse conjointe des isotopes de l’oxygène et du soufre de l’apatite de nombreuses espèces de vertébrés actuels permettait de tracer leur environnement de vie. Nous avons ensuite appliqué ce nouvel outil isotopique aux assemblages de vertébrés du Dévonien supérieur et mis en évidence l’enregistrement d’une influence marine dans les apatites de ces espèces généralement considérées comme dulçaquicoles. En guise de perspectives, nous avons souligné une première piste diagénétique susceptible de perturber la composition isotopique originelle. Face à ce problème, nous suggérons finalement d’adopter une démarche empirique, consistant à analyser la composition isotopique du soufre de nombreuses apatites fossiles afin d’obtenir une vision exhaustive de son potentiel en tant que marqueur environnemental / -

Temnospondyls are large extinct fossil tetrapods; superficially resembling crocodiles in their general size, appearance and lifestyle. Temnospondyls are a group of early tetrapods, the oldest fossils are more than 340 million years old, and they existed for more than 200 million years. This doctoral thesis examined the postcranial skeleton of temnospondyls and its evolutionary history and diversification. Standard taxonomic techniques were used to distinguish between the types of variation observed in the postcranial skeleton and for phylogenetic analysis. The thesis consists of a series of published articles, three describing the postcranial skeletons of various temnospondyls, and three summary articles, all with extensive illustrations. To provide data, the postcranial skeletons of three temnospondyl taxa were described. The articulated postcranial skeleton of a basal stereospondyl (rhinesuchid) is immature, and paedomorphism of the postcranial skeleton in stereospondyls is discussed. The robust appendicular skeleton of Eryops megacephalus is plesiomorphic, well-ossified, and terrestrially adapted. The paedomorphic postcranial skeleton of Trimerorhachis insignis is plesiomorphic, and secondarily aquatic, the description includes growth stages. This study found that extensive morphogenetic variation is present in the postcranial skeleton of temnospondyls. Many phylogenetically significant characteristics develop with morphogenesis, they may be absent in early growth stages, and may never develop even in the largest growth stages of taxa with paedomorphic postcranial skeletons. Consequently, assessment of the presence or absence of a phylogenetically significant characteristic in any taxon may be dependant on the morphogenetic stage of the specimen examined. This finding has major implications for the phylogenetic analysis of temnospondyls and other early tetrapods. An overview of phylogenetic variation in the postcranial skeleton is presented, including a large phylogenetic analysis of the Temnospondyli. The most primitive temnospondyls possess fully ossified postcranial skeletons, well adapted for terrestrial locomotion, but some of the derived clades of temnospondyls have paedomorphic postcranial skeletons and are exclusively aquatic. For the first time, the postcranial skeleton of temnospondyls is comprehensively compared with that of other early tetrapods in the largest phylogenetic analysis to date, resulting in the unexpected discovery that temnospondyls are most closely related to the ancestors of amniotes. The Temnospondyli plus Neospondyli (Seymouriamorpha plus Cotylosauria plus Lepospondyli) forms a large new clade, the Terrapoda, defined by the presence of many derived synapomorphies. Some of the cranial synapomorphies of the Terrapoda are most likely related to improvements in hearing. The postcranial synapomorphies indicate that the Terrapoda are the first vertebrates to have evolved limbs that are well adapted for terrestrial locomotion. The Terrapoda are the first truly terrestrial vertebrates, their postcranial adaptations facilitated their colonisation of the land and consequent phylogenetic radiation during the early Carboniferous. Both analyses incorporate characters from previous analyses and many new postcranial characters. The results of the phylogenetic analyses are statistically more parsimonious than previous analyses and have much lower levels of homoplasy. Comparative analyses indicate that the distinctive results are most likely due to the increased use of characters pertaining to temnospondyls, increased use of postcranial characters, and differentiation between sources of morphological variation to minimise morphogenetic and phenotypic variation and elucidate true phylogenetic signal.

Magister Scientiae (Biodiversity and Conservation Biology) - MSc (Biodiv & Cons Biol) / Gaps in our knowledge of the functional roles of snakes within ecosystems limit our ability to predict the potentially cascading effects their removal from an ecosystem might create. Extirpation of snake species could potentially result in losses of ecosystem functionality if those taxa are ecologically unique. I used pitfall and funnel trap arrays, artificial cover object surveys, active searching, and passive camera trapping, as well as pre-existing faunal diversity data to identify terrestrial tetrapod species within the Koeberg Private Nature Reserve. This resulted in a list of 265 species, of which 13 were snakes. I then gathered data on dietary and four additional functional traits for each species from the literature. Next, using hierarchical and partitioning around medoids clustering, I identified ten broad dietary guilds and 54 functional guilds within the terrestrial tetrapod community. Of the dietary guilds Dasypeltis scabra was the only snake species that formed a unique single species guild and was one of four snake species (Pseudaspis cana, Homoroselaps lacteus and Lamprophis guttatus) to form four unique single species functional guilds. The remaining snakes clustered together within groups of other vertebrate predators. Functional diversity analysis was then used to simulate losing eight major taxonomic groups (birds, passerines, non-passerines, mammals, reptiles, snakes, non-snake reptiles and amphibians) and gauge the effects of those losses on overall community dietary and functional diversity. Functional diversity analysis revealed that the loss of certain snake species resulted in disproportionate losses of overall community dietary and functional diversity while losing others had negligible effects. These findings provide ambivalent support for the dietary and functional uniqueness of snakes suggesting that certain snake species are fulfilling unique functional roles within the ecosystem. Additionally, it is likely that losing those non-redundant species would result in significant losses of ecosystem functionality.

This dissertation contains six chapters detailing recent advances that have been made in the synthesis and characterization of metal-semiconductor hybrid nanocrystals (HNCs), and the applications of these materials. Primarily focused on the synthesis of well-defined II-VI semiconductor nanorod (NR) and tetrapod (TP) based constructs of interest for photocatalytic and solar energy applications, the research described herein discusses progress towards the realization of key design rules for the synthesis of functional semiconductor nanocrystals (NCs). As such, a blend of novel synthesis, advanced characterization, and direct application of heterostructured nanoparticles are presented. Additionally, for chapters two through six, a corresponding appendix is included containing supporting data pertinent to the experiments described in the chapter. The first chapter is a review summarizing the design, synthesis, properties, and applications of multicomponent nanomaterials composed of disparate semiconductor and metal domains. By coupling two compositionally distinct materials onto a single nanocrystal, synergistic properties can arise that are not present in the isolated components, ranging from self-assembly to photocatalysis. While much progress was made in the late 1990s and early 2000s on the preparation of a variety of semiconductor/metal hybrids towards goals of photocatalysis, comprehensive understanding of nanoscale reactivity and energetics required the development of synthetic methods to prepare well-defined multidimensional constructs. For semiconductor nanomaterials, this was first realized in the ability to tune nanomaterial dimensions from 0-D quantum dot (QD) structures to cylindrical (NR) and branched (TP) structures by exploitation of advanced colloidal synthesis techniques and understandings of NC facet reactivities. Another key advance in this field was the preparation of "seeded" NR and TP constructs, for which an initial semiconductor QD (often CdSe) is used to "seed" the growth of a second semiconductor material (for example, CdS). These advances led to exquisite levels of control of semiconductor nanomaterial composition, shape, and size. Concurrently, many developments were made in the functionalization of these NCs with metallic nanoparticles, allowing for precise tuning of metal nanoparticle deposition position on the surface of preformed semiconductor NCs. To date, photoinduced and thermally induced methods are most widely used for this, providing access to metal-semiconductor hybrid structures functionalized with Au, Pt, Ag2S, Pd, Au/Pt, Ni, and Co nanoparticles (to name a few). With colloidal nanomaterial preparation becoming analogous to traditional molecular systems in terms of selectivity, property modulation, and compositional control, the field of nanomaterial total synthesis has thus emerged in the past decade. With a large toolbox of reactions which afford selectivity at the nanoscale developed, to date it is possible to design a wider array of materials than ever before. Only recently (the past ~ 5 years), however, has the transition from design of model systems for fundamental characterization to realization of functional materials with optimized properties begun to be demonstrated. The emphasis of chapter 1 is thus on the key advances in the preparation of metal-semiconductor hybrid nanoparticles made to date, with seminal synthetic, characterization, and application milestones being highlighted. The second chapter is focused on the synthesis and characterization of well-defined CdSe-seeded-CdS (CdSe@CdS) NR systems synthesized by overcoating of wurtzite (W) CdSe quantum dots with W-CdS shells. 1-dimensional NRs have been interesting constructs for applications such as solar concentrators, optical gains, and photocatalysis. In each of these cases, a critical step is the localization of photoexcited excitons from the light-harvesting CdS NR "antenna" into the CdSe QD seed, from which emission is primarily observed. However, effects of seed size and NR length on this process remained unexplored prior to this work. Previous work had demonstrated that, for core@shell CdSe@CdS systems, small CdSe seed sizes (< 2.8 nm in diameter) resulted in quasi-type II alignment between semiconductor components (with photoexcited electrons delocalized across the structure and holes localized in the CdSe seed), and large seed sizes (> 2.8 nm) resulted in type I alignment (with photoexcited electrons and holes localized in the CdSe seed). Through synthetic control over CdSe@CdS NR systems, materials with small and large CdSe seeds were prepared, and for each seed size, multiple NR lengths were prepared. Through transient absorption studies, it was found that band alignment did not affect the efficiency of charge localization in the CdSe core, whereas NR length had a profound effect. This work indicated that longer NRs resulted in poor exciton localization efficiencies owing to ultrafast trapping of photoexcited excitons generated in the CdS NR. Thus, with increasing rod length, poorer efficiencies were observed. This work served to highlight the ideal size range for CdSe@CdS NR constructs targeted towards photocatalysis, with ~ 40 nm NRs exhibiting the best rod-to-seed localization efficiencies. Additionally, it served to expand the understanding of exciton trapping in colloidal NC systems, allowing development of a predictive model to help guide the preparation of other nanorod based photocatalytic systems. The third chapter describes the synthesis of Au-tipped CdSe NRs and studies of the effects of selective metal nanoparticle deposition on the band edge energetics of these model photocatalytic systems. Previous studies had demonstrated ultrafast localization of photoexcited electrons in Au nanoparticles (AuNP) (and PtNP) deposited at the termini of CdSe and CdSe@CdS NR constructs. Also, for similar systems, the hydrogen evolution reaction (HER) had been studied, for which it was found that noble metal nanoparticle tips were necessary to extract photoexcited electrons from the NR constructs and drive catalytic reactions. However, in these studies, energetic trap states, generally ascribed to surface defects on the NC surface, are often cited as contributing to loss of catalytic efficiency. In this study, we found that the literature trend of assuming the band-edge energetics of the parent semiconductor NC applies to the final metal-functionalized catalyst did not present a complete picture of these systems. Through a combination of ultraviolet photoelectron spectroscopy and waveguide based spectroelectrochemistry on films of 40 nm long CdSe NRs before and after AuNP functionalization, we found that metal deposition resulted in the formation of mid-gap energy states, which were assigned as metal-semiconductor interface states. Previously these states had only been seen in single particle STS studies, and their identification in this study from complementary characterization techniques highlighted a need to further understand the nature of the interface between metal/semiconductor components for the design of photoelectrochemical systems with appropriate band alignments for efficient photocatalysis. The fourth chapter transitions from NR constructs to highly absorbing CdSe@CdS TP materials, for which a single zincblende (ZB) CdSe NC is used to seed the growth of four identical CdS arms. These arms act as highly efficient light absorbers, resulting in absorption cross sections an order of magnitude greater than for comparable NR systems. In the past, many studies have been published on the striking properties of TP nanocrystals, such as dual wavelength fluorescence, multiple exciton generation, and inherent self-assembly owing to their unique geometry. Nonetheless, these materials have not been exploited for photocatalysis, primarily owing to challenges in preparing TP from ultrasmall ZB-CdSe seed size (owing to phase instability of the zincblende crystal structure), thus preventing access to quasi-type II structures necessary for efficient photocatalysis. In this study, we successfully break through the type I/quasi-type II barrier for TP NCs, reclaiming lost ground in this field and demonstrating for the first time quasi-type II behavior in CdSe@CdS TPs through transient absorption measurements. This was enabled by new synthetic protocols for the synthesis and stabilization of ultrasmall (1.8 – 2.8 nm) ZB-CdSe seeds, as well as for the synthesis of CdSe@CdS TPs with arm lengths of 40 nm. Easily scalable, TPs were prepared on gram scales, and the quasi-type II systems showed dramatically enhanced rates of selective photodeposition of AuNP tips under ultraviolet and solar irradiation. These are promising materials for photocatalytic and solar energy applications. The fifth chapter continues with the study of CdSe@CdS TPs, and elaborates on a new method for the selective functionalization of the highly symmetrical TP construct. Previous studies had demonstrated that access to single noble metal NP tips was vital for efficient photocatalytic HER from NR constructs. However, TP materials have been notoriously difficult to selectively functionalize, owing to their symmetric nature. Using a novel photoinduced electrochemical Ostwald ripening process, we found that initially randomly deposited AuNPs could be ripened to a single, large (~ 7 nm) AuNP tip at the end of one arm of a type I CdSe@CdS TP with 40 nm arms. To demonstrate the selectivity of this tipping process, dipolar cobalt was selectively overcoated onto the AuNP tips of these TPs, resulting in dipolar Au@Co-CdSe@CdS TP nanocrystals. These particles were observed to spontaneous self-assemble into 1-D mesoscopic chains, owing to pairing of N-S dipoles of the ferromagnetic CoNPs, resulting in the first example of “colloidal polymers” (CPs) bearing bulky, tetrapod ("giant t-butyl") pendant groups. The sixth chapter elaborates further on the preparation of colloidal polymers, further extending the analogy between molecular and colloidal levels of synthetic control. One challenge in the field of colloidal science is the realization of new modes of self-assemble for compositionally distinct nanoparticles. In this work, it was found that Au@Co nanoparticle dipole strength could be systematically varied by tuning of AuNP size on CdSe@CdS nanorods/tetrapods. In the first example of a colloidal analogue to reactivity ratios observed for traditional chain growth polymerization systems, highly disparate AuNP tip sizes (and thus final Au@Co NP dipole strength) were found to result in segmented colloidal copolymers upon dipolar self-assembly, whereas similar AuNP tip sizes ultimately led to random dipolar assemblies. Clearly visualized through incorporation of NR and TP sidechains into these colloidal polymers, this study presented a compelling case for continued exploration of colloidal analogues to traditional molecular levels of synthetic control.

The impact of the end-Devonian mass extinction (the Hangenberg extinction) on tetrapods is not well understood. One issue is that we have very little knowledge of the Devonian tetrapod fauna that immediately preceded, and experienced, the mass extinction. New specimens from an early tetrapod bone bed of the latest Famennian, Stensiö Bjerg Formation of Celsius Bjerg, East Greenland have the potential to shed light on this problem. In this study, five new well-preserved specimens are presented: a partial skull, two humeri, a left pelvis, and a strange vertebral element. The specimens were imaged using propagation phase-contrast synchrotron microtomography (PPC-SRμCT), and then virtually segmented and rendered.  The partial skull and left pelvis share many similarities with Ichthyostega and Acanthostega, but also have some distinctive features. Notably, the epipterygoid does not articulate with the skull roof, the fenestra vestibuli appears to have an anterior lobe, the postorbital has a posteroventral process, and there is a sharp contrast between the rugose dermal ornament of the skull roof and the unornamented cheek. In addition, the partial skull is box-like in shape and has a laterally facing orbit, which are features seen in some Carboniferous tetrapods. Among other characters, the left pelvis has a differently curving posterior iliac process, and differently shaped ischium and anterior pubic margin compared to Ichthyostega and Acanthostega. The acetabulum of the left pelvis is also lacking a posterior notch, a feature seen in many other early tetrapods. The humeri presented in this thesis are curiously similar to the isolated tetrapod humerus from the Catskill Formation, Pennsylvania, USA known as ANSP 21350. In fact, they are more similar to each other and to ANSP 21350 than to any other early tetrapod humeri. This is in large part due to a distinctly distal supinator ridge which was previously only known from ANSP 21350. The mysterious vertebral element does not resemble any known early tetrapod bone due to its large, ventral, concave saddle-shaped projections. It consists of five fused vertebrae and is interpreted here to be a unique sacrum of an early tetrapod. The specimens described and interpreted in this study represent at least two new species, none of which can be assigned to known Devonian early tetrapods from Greenland. It is clear that a new and important faunal assemblage is emerging.

Diese Habilitationsschrift konzentriert sich auf die Evolution osteologischer Korrelate, anhand derer Rückschlüsse auf die Struktur der Haut sowie die Art der Atmung und der Nahrungsaufnahme früher Tetrapoden gezogen werden können. Die äußere Skulptur der Hautknochen früher Tetrapoden trug zur Konsolidierung der darüber liegenden Dermis bei; dies und die zahlreichen Hautverknöcherungen deuten darauf hin, dass Hautatmung im Gegensatz zu heutigen Lissamphibien keinen wesentlichen Teil des Gasaustausches ausmachen konnte. Es wird die Hypothese aufgestellt, dass eine weitere Funktion der Knochenskulptur in der Pufferung von CO2-induzierter Azidose bestand, wenn sich die Tiere an Land aufhielten. Mehrere Gruppen früher Tetrapoden entwickelten unabhängig voneinander Osteoderme im Rumpf, die unter anderem die Wirbelsäule bei der Fortbewegung an Land unterstützen konnten oder als Kalzium-Reservoir dienten. Die Veränderungen in der Morphologie, Histologie und Anordnung der Dermalschuppen während des Fisch-Tetrapoden-Überganges erfolgte etwa simultan zur Entwicklung der Tetrapodenextremität und ermöglichte eine größere Flexibilität des Körpers und der Beine. Der Bau des Kiemenskeletts ihrer Fischvorfahren wurde bei einer unerwartet großen Anzahl früher Tetrapoden beibehalten. Dies zeigt, dass viele frühe Tetrapoden sowohl der Stamm- als auch der Kronengruppe als Adulte über innere Kiemen atmeten, während ihre Larven äußere Kiemen besaßen. Das Kiemenskelett und die Rekonstruktion assoziierter Muskeln zeigen, dass viele aquatische frühe Tetrapoden ihre Nahrung durch akinetisches Saugschnappen erbeuteten. Trotz spärlicher Fossilüberlieferung gibt es Hinweise darauf, dass die ersten an Land fressenden Tetrapoden noch keine bewegliche Zunge besaßen. Ein ontogenetischer Umbau des larvalen, kiementragenden Kiemenskelets in einen zungenstützenden Apparat kann bei frühen Tetrapoden nur in Ausnahmefällen belegt werden. / This habilitation thesis focuses on the evolution of skeletal correlates from which the integumentary structure and the mode of breathing and feeding in early tetrapods can be inferred. Sculpture on the external surface of dermal bones contributed to the consolidation of a dense integument; this and numerous dermal ossifications render substantial cutaneous respiration as in extant lissamphibians unlikely. It is hypothesised that a further function of dermal bone sculpture was to buffer CO2-induced acidosis while the animals were on land. Numerous early tetrapods independently developed osteoderms in the trunk that may have served among other things for support of the vertebral column in terrestrial locomotion or as a physiological calcium reservoir. The alterations in morphology, histology and arrangement of dermal scales during the fish-to-tetrapod transition occurred at roughly the same time when digits appeared and enabled greater flexibility of body and limbs. The structure of the hyobranchium of their fish-like ancestors was retained in an unexpected large number of early tetrapods, showing that many early tetrapods of both the stem- and crown-group breathed via the associated internal gills as adults, and via external gills as larvae. The hyobranchial apparatus and reconstruction of the associated musculature indicate that many aquatic early tetrapods fed by akinetic suction feeding. There is evidence that the earliest terrestrial tetrapods captured prey on land by jaw prehension rather than by tongue based feeding. Ontogenetic remodelling into a tongue supporting adult hyobranchium in early tetrapods can only be demonstrated in exceptional cases.