Thesis (Ph.D.)--University of Adelaide, Dept. of Genetics, 1983. / Typescript (photocopy).

Ces dernières années, l’intérêt porté à l'obtention de nouveaux systèmes catalytiques a connu un essor fulgurant. Ceci est lié, en particulier, aux applications industrielles variées qui s'étendent de la chimie fine à la chimie pharmaceutique. De nombreux catalyseurs ont ainsi été développés pour un nombre toujours croissant de réactions organiques. Néanmoins, la plupart des catalyseurs homogènes sont difficiles à adapter aux procédés industriels du fait de problèmes de séparation et de régénération. De plus, même efficaces, la plupart des catalyseurs contiennent des métaux nobles, coûteux et difficiles à recycler. C’est pourquoi, de nouveaux protocoles plus économiques et plus respectueux de l’environnement ont besoin d’être recherchés. L’utilisation de nanoparticules magnétiques comme support catalytique en synthèse organique représente une solution innovante pour répondre aux problèmes catalytiques rencontrés. Le but de ce travail consiste à concevoir des nano-catalyseurs magnétiques et à évaluer leur activité catalytique ainsi que leur recyclage pour des réactions de couplage carbone-carbone très utilisées en synthèse organique. Des nanoparticules de Maghémite synthétisées dans en milieux aqueux sont ensuite stabilisées en surface par des agents complexants possédant une fonction terminale qui permettra de les fonctionnaliser avec le catalyseur désiré (L- Proline, peptides, alcaloïde, Palladium). Ces nanomatériaux hybrides, constitués d'un cœur inorganique et d'une couche organique, ont été caractérisés par diverses techniques afin de déterminer leurs propriétés. Leurs activités ont été évaluées sur des réactions de couplage carbone-carbone modèles d'aldolisation, d'addition 1,4 de Michael et la réaction de Suzuki-Miyaura. / In the last decades, the interest for new catalysts and new catalytic reactions dramatically increased due to their miscellaneous industrial applications in fine or pharmaceutical chemistry for example. Lots of catalysts have been developed for an increasing number of organic reactions. Nevertheless, most of homogeneous catalysts are difficult to adapt to industrial process due to separation and regeneration problems. Furthermore, even if they are highly efficient, most of the catalysts contain noble metals often expensive and difficult to recycle. That’s why greener and much more economic protocols need to be developed. The use of nanoparticles as solid support for catalysts in organic chemistry appears as an innovative solution for solving these problems. Among the different inorganic nanomaterials, iron oxide nanoparticles represent an attractive tool due to their magnetic properties and easiness of obtaining. The aim of these work consist in designing magnetic nanocatalysts and evaluating their catalytically activity and recycling in C-C bond formation reactions which are commonly used in organic chemistry. Iron oxide nanoparticles (γ-Fe₂O₃) have been synthesized by soft chemistry in aqueous media. Particles have then been stabilized on surface by bidendate coating agents bearing a terminal function which enables post functionnalization with the desired catalyst (L-Proline, peptides, alkaloid, Palladium). These hybrids nanomaterials, with an inorganic core and an organic shell, have been characterized with various techniques in order to determine their properties. Catalysts activities have been evaluated on model C-C bond formation reactions such as aldolisation, 1, 4-Michael addition and cross coupling Suzuki-Miyaura cross coupling.

Hybridization is thought to have played an important role in human evolution, with hybridizing groups having significant differences in soft tissue trait variation. Ectodermal trait variation is of interest because primate hybrids show increased atypical non-metric dental and cranial trait variation thought to be the result of interactions between parental genomes which have diverged for ectodermal trait development (including hair and tooth development). There were also differences between hybridizing hominin groups for limb measurements which have changed significantly throughout human evolution. Here a mouse model is used to look at the effect of hybridization on coat morphology and long bone length. Using standardized photographs, the differences in mean RGB values for the dorsal and ventral coat were used to determine whether the hybrids were different from their parents for pelage colour of different regions of the body, dorsal ventral colour contrast, and levels of variation in coat colour. The sample is composed of parents from one specific and three sub-specific crosses, as well as F1, F2 and first generation backcrossed (B1) hybrids. Long bone measurements of the forelimbs and hind-limbs were collected from micro-CT scans of the sub-specific F1 hybrids and their parents. Previous data have shown that hybridization can have variable morphological outcomes: hybrids can look like one of the parents, they can be intermediate, or they can have extreme traits outside of the range of variation of the parents. Our results indicate that morphological outcomes for coat colour in F1 hybrids depends on factors such as genetic distance. However, the genetic background of one of the strains used for this experiment might contribute the transgressive phenotype of some of the F1 hybrids. Hybrid morphology also changes in subsequent generations (F2 and B1) as new recombinants formed, with transgressive coat colour phenotypes sometimes appearing even if they are not present in the F1 hybrid groups. Phenotypes produced in F1 hybrids are also seen in subsequent generations of hybrids. All sub-specific F1 hybrids were transgressive for long bone length. Compared to parental groups hybrids have a different relationship between the long bones of the forelimb (ratio of humerus to ulna). This is in line with previous data from primate hybrids, that shows that changes in the relationships between different regions of the body occurs in hybrids producing novel phenotypes. The inter-membral indexes are not significantly different from one of the parents for two of the crosses. This data shows that hybridization can produce novel pelage phenotypes over multiple generations. There were many transitions in hair/skin morphology during human evolution and these tissue groups were and are under a great deal of selective pressure due to their direct interaction with the environment. Thus, understanding how these traits are impacted by hybridization will be important for disentangling how hybridization affected our evolutionary trajectory and ability to occupy new regions of the world. Post cranial data, indicates that F1 hominin hybrids might have longer limbs in relation to parental populations, more work needs to be done on the post cranial remains of posited hominin hybrids as well as pedigreed mammalian hybrids to determine if this is a pattern which can be used to identify hybrids in the fossil record.

No description available.

A novel approach for the design and synthesis of membrane separation systems has been developed. The theory is shown to be applicable to both batch and continuous membrane operations, and has been formulated in such a way that it is valid for any type of membrane. In this thesis, however, only vapour permeation and pervaporation membranes are incorporated for illustration purposes. The method, which employs a graphical technique, allows one to calculate and visualise the change in composition of the retentate. An integral part of the approach was the derivation of the Membrane Residue Curve Map (M-RCM), and the related differential material balance which describes it. By definition, this plot shows the change, in time, of the retentate composition in a batch still. However, it has been shown that the M-RCM is applicable to conventional continuously-operated membrane units, as well as infinite reflux membrane columns. Finite reflux columns and cascades have been examined by using column sections (CS): any column, or arrangement, no matter how complex, can be broken down into smaller units, namely CS. The development of the Difference Point Equation (DPE) for non-constant flow allowed one to generate, and interpret, profiles for individual CS’s, which can ultimately be connected to form a membrane column arrangement. The profiles, which are more complex than those obtained in the M-RCM, exhibit a unique behavior. Since there is varying flow, the reflux is continually changing, orientating the profile so as to seek a stable node that is “mobile”. Thus, the movement of CS profile is dictated by the location and direction of the pinch point locus. Finally, having membrane permeators examined in an analogous manner to other separation methods, allows for easy synthesis and design of combinations of different processes. Hybrid distillation-membrane systems are analyzed by incorporating CS’s and the appropriate DPE’s which describe each. Investigating the arrangement as a thermally-coupled column introduces a novel way of synthesizing hybrids. Regions of feasibility, which are dictated by the relevant pinch point loci of each separation method, are ultimately sought.

The presence of organic micropollutants (OMPs) in water is of great environmental concern. OMPs such as endocrine disruptors and certain pharmaceuticals have shown alarming effects on aquatic life. OMPs are included in the priority list of contaminants in several government directorate frameworks. The low levels of OMPs concentration (ng/L to μg/L) force the use of sophisticated analytical instruments. Although, the techniques to detect OMPs are progressing, the focus of current research is only on limited, important OMPs due to the high amount of time, cost and effort involved in analyzing them. Alternatively, quantitative structure activity relationship (QSAR) models help to screen processes and propose appropriate options without considerable experimental effort. QSAR models are well-established in regulatory bodies as a method to screen toxic chemicals. The goal of the present thesis was to develop QSAR models for OMPs removal by oxidation. Apart from the QSAR models, a decision support system (DSS) based on multi-criteria analysis (MCA) involving socio-economic-technical and sustainability aspects was developed. Also, hybrids of different water treatment processes were studied to propose a sustainable water treatment train for OMPs removal. In order to build the QSAR models, the ozone/hydroxyl radical rate constants or percent removals of the OMPs were compiled. Several software packages were used to 5 compute the chemical properties of OMPs and perform statistical analyses. For DSS, MCA was used since it allows the comparison of qualitative (non-monetary, non-metric) and quantitative criteria (e.g., costs). Quadrant plots were developed to study the hybrid of natural and advanced water treatment processes. The QSAR models satisfied both chemical and statistical criteria. The DSS resulted in natural treatment and ozonation as the preferred processes for OMPs removal. The QSAR models can be used as a screening tool for OMPs removal by oxidation. Moreover, the QSAR - defining molecular descriptors help in detailed understanding of oxidation. The DSS can be considered as an aid in assessing a multi-barrier approach to remove OMPs. Hybrids of natural and advanced treatment processes help to develop a more sustainable multi-barrier approach for OMPs removal.

Paleontological documentation of hybridization events has the potential to address a multitude of evolutionary and paleobiological issues unanswerable by purely biological means. However, previous studies of modern hybrids suggest that their morphology is often insufficient for their reliable discrimination. This study analyzes the morphology of an extant, genetically-identified <i>Mercenaria</i> spp. (Bivalvia: Veneridae) hybrid zone using Bookstein coordinates and multivariate methods to answer two questions: (1) can hybrid <i>Mercenaria</i> spp. individuals be identified based on morphology alone, and (2) would a <i>Mercenaria</i> spp. hybrid zone be recognizable in the fossil record? Multivariate statistical procedures (principal components analysis, canonical variate analysis, etc.) using Bookstein coordinates demonstrate that, within the hybrid zone, hybrid individuals cannot be identified due to extreme overlap with the parental taxa. The hybrid zone as a whole, however, can be identified by comparison with pure-species populations sampled from outside the hybrid zone. Hybrid zones occupy parental species morphospace plus intermediate morphospace. The technique of using multiple pure-species populations to establish species morphospace is introduced to control for processes that may also result in morphological intermediates at ecological time scales (dimorphism, ecophenotypy, and geographic variation). Four alternative causal explanations of morphological intermediates through geological time (primary intergradation, uncoupled genetic and morphological divergence, time-averaged evolving populations, and developmentally instable populations) are evaluated. A literature survey strongly suggests that neither time-averaging nor developmental instability is occurring at the beginning of a lineage's evolutionary history, and that hybridization may be much more extensive than paleontological data suggest. / Master of Science

Doctor of Philosophy / Department of Chemistry / Eric A. Maatta / The thesis focuses on the design and synthesis of novel organoimido delivery reagents capable of forming bimetallic polyoxometalate (POM) hybrids, and their use in the assembly of bimetallic hexamolybdate derivatives. These delivery reagents have been designed thoughtfully and separate organic moieties have been selected for coordinating to both the POM cluster and the second metal atom. A series of three ligands [4-aminopiperidine, 4-(4-aminophenyl) piperazine, and 4-(4-aminophenyl) piperidine] were selected and used to synthesize the dithiocarbamate metal-coordinating ligands, which in turn were used for preparing the corresponding metal (M = Cr, Mn, Fe, Co, Ni, Cu, Zn, Ag) complexes. All the complexes were characterized by infrared spectroscopy (IR). Reported routes were followed for the covalent grafting of these metal complexes onto hexamolybdate. But, the poor solubility of these metal complexes was found to be a major stumbling block in our endeavors to synthesize the dithiocarbamate based polyoxometalate hybrids. The observed poor solubility of metal dithiocarbamate complexes was overcome by synthesizing [potassium(I) tris(3,5-diphenylpyrazole)borate] and [potassium(I) tris(3,5-dimethylpyrazole)borate] via thermal dehydrogenative condensation between tetrahydroborate and the respective pyrazole molecule. A series of corresponding transition metal (M = Co, Ni, Cu, Mn) complexes of tris(3,5-diphenylpyrazole)borate and tris(3,5-dimethylpyrazole)borate were synthesized, and characterized by IR and UV-visible spectroscopy, and single crystal X-ray diffraction. The single crystal structure of [manganese(II) (tris(3,5-dimethylpyrazole)borate)2] turned out to an outlier as it displayed the formation of a bis-complex, thus having no substitutable anion for further reaction with dithiocarbamates. Thereafter, a series of metal dithiocarbamate complexes of these [hydrotris(pyrazolyl)borates] (M = Co, Ni, Cu ) were prepared using [sodium 4-aminopiperidyldithiocarbamate] and were characterized by IR and UV-visible spectroscopy. A remarkable improvement in the solubility of these metal dithiocarbamates in organic solvents was observed. Furthermore, attempts to covalently graft these complexes onto hexamolybdate cluster were undertaken, and found to be unsuccessful possibly due to the strong oxidizing nature of PPh[subscript]3Br[subscript]2 and hexamolybdate. Although, we were able to successfully tailor the solubility of the dithiocarbamate complexes to suit our needs, our efforts to achieve the primary goal of synthesizing dithiocarbamate based polyoxometalate hybrids have so far been unsuccessful. A series of three pyridyl based ligands i.e., 3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-amine, 4-(pyridin-4-ylethynyl)aniline and 4-(pyridin-3-ylethynyl)aniline were synthesized and characterized. Covalent attachment of these ligands to hexamolybdate were attempted following various well-known routes. Although, no evidence of covalent attachment of 3,5-di(pyridin-2-yl)-4H-1,2,4-triazol-4-amine to hexamolybdate was observed, the covalent grafting of 4-(pyridin-4-ylethynyl)aniline and 4-(pyridin-3-ylethynyl)aniline to hexamolybdate cluster was successfully achieved. Characterization of these novel organic-inorganic hybrids was done using IR and NMR spectroscopy as analytical tools. Attempts have been undertaken to obtain single crystals of these hybrids. Also, a novel route involving halogen bonding as a purification and separation technique for pyridyl functionalized hexamolybdate hybrids is also being explored. The novel acetylacetonate moiety has been explored as an imidodelivery reagent for synthesizing hexamolybdate covalent hybrids, wherein [3-(4-((4-aminophenyl)ethynyl)phenyl)-4-hydroxypent-3-en-2-one] ligand has been successfully synthesized and characterized. Traditional methods along with unconventional methods such as heating at elevated temperatures and microwave reaction conditions, have so far proved to be unsuccessful in the synthesis of the hybrids. A series of the corresponding metal complexes have been synthesized and characterized, where the ligand and its corresponding copper(II) complex have been characterized by single crystal XRD. In the crystal structure of the copper complex, the metal ion sits in a slightly distorted square-planar pocket, where no coordination to the -NH[subscript]2 group is observed, which highlights the potential of using it as an imidodelivery reagent.

The vibration damping property of plant fibres composites is of practical interest for commercial applications of biobased and eco-composites. Damping behaviour has been observed by experimentation and exploited in the marketing of sporting equipment but the origins of this behaviour have so far been only based on conjectures. In this thesis, the damping capacity of plant fibre composites was attributed to their chemical composition and the reversible interactions enabled by the breaking and reforming of hydrogen bonds under stress. The approach to explaining the mechanisms started with the characterisation of different plant fibre types to search for correlations between their physical and chemical structure. The investigation continued with quantifying the effect of hydrogen bonding compounds such as water, glycerol and polyglycerol on the damping coefficient of fibres and reinforced composites. The results of the polyol impregnation indicated that applying a pretreatment enhanced the vibration damping performance of flax reinforced composites, validating the hypothesis of the essential role played by hydrogen bonds in the fibres. The improvement in the damping coefficient of the composites was shown to be to the detriment of their stiffness. The compromised between the two properties was investigated in the final part of this thesis by using hybrid flax-carbon fibre reinforced composites.

No description available.