Adhesives are widespread. They hold together the furniture, cars and electronics that we use on a daily basis. The majority of commercially available glues are sourced from petroleum-based monomers and are not degradable in any practical way. The permanent nature of these adhesive materials makes disassembly for recycling difficult. Current bio-based glues such as hide and starch glue are not strong enough to compete with commercial glues. Inspiration from nature is helping us to tackle this problem. Marine mussels achieve strong bonding to underwater surfaces through the use of adhesive plaques containing the uncommon amino acid 3,4-dihydroxyphenylalanine. Incorporating this chemistry into a degradable polylactic acid backbone allows for the development of strong bonding biodegradable glue. Throughout this work, the synthesis of these materials is discussed as well as methods to improve the bonding of these materials to compete with commercial glues. The degradation of these materials as well as their cytocompatibility is discussed.

Dans ce travail de thèse, nous présentons une méthode originale s’inspirant des comportements des fourmis réelles pour la résolution de problème de classification non supervisée non hiérarchique. Cette approche créée dynamiquement des groupes de données. Elle est basée sur le concept des fourmis artificielles qui se déplacent en même temps de manière complexe avec les règles de localisation simples. Chaque fourmi représente une donnée dans l’algorithme. Les mouvements des fourmis visent à créer des groupes homogènes de données qui évoluent ensemble dans une structure de graphe. Nous proposons également une méthode de construction incrémentale de graphes de voisinage par des fourmis artificielles. Nous proposons deux méthodes qui se dérivent parmi les algorithmes biomimétiques. Ces méthodes sont hybrides dans le sens où la recherche du nombre de classes, de départ, est effectuée par l’algorithme de classification K-Means, qui est utilisé pour initialiser la première partition et la structure de graphe. / In this work, we present a novel method based on behavior of real ants for solving unsupervised non-hierarchical classification problem. This approach dynamically creates data groups. It is based on the concept of artificial ants moving complexly at the same time with simple location rules. Each ant represents a data in the algorithm. The movements of ants aim to create homogenous data groups that evolve together in a graph structure. We also propose a method of incremental building neighborhood graphs by artificial ants. We propose two approaches that are derived among biomimetic algorithms, they are hybrid in the sense that the search for the number of classes starting, which are performed by the classical algorithm K-Means classification, it is used to initialize the first partition and the graph structure.

Au cours de ce travail, nous avons abordé la synthèse biomimétique sous des angles variés. Une déclinaison des approches bio-inspirées a en effet permis de réaliser plusieurs synthèses totales d'alcaloïdes polycycliques complexes. La biogenèse des substances naturelles considérées est placée au centre de la démarche. Au départ, pour définir la stratégie de synthèse puis, en conclusion, lorsque les synthèses réalisées mènent a des hypothèses biosynthétiques plus abouties.Le squelette des drimentines, alcaloïdes hybrides possédant une partie sesquiterpénique, a été obtenu grâce à une séquence de désaromatisation-cyclisation qui mime l'étape-clé de la biogenèse de ces métabolites spécialisés.Une stratégie d'auto-assemblage par dimérisation a été adoptée afin d'étudier les liens synthétiques et biosynthétiques qui unissent les alcaloïdes marins de la famille des aplysinopsines. Au cours de cette étude, les premières synthèses totales du dictazole B et du tubastrindole B ont été réalisées. De plus, l'obtention d'analogues proches des substances décrites et d'un intermédiaire biogénétique supposé a permis de développer une hypothèse de biogenèse se fondant sur la spontanéité et les réactivités chimiques observés au cours de l'étude. L'application de la catalyse à l'ADN à ces travaux a également conduit à des résultats prometteurs.Enfin, une méthode bio-informatique récente appelée "molecular networking" peut être mise à profit afin d'exploiter la diversité de mélanges synthétiques complexes générés par la mise en présence de quelques précurseurs simples. La démarche s'applique à des mélanges connus dans lesquels la nitraramine ou la nitrarine se forment ainsi qu'à des mélanges inédits pouvant conduire, par exemple, au myrifabral A.Ces études montrent encore une fois que la synthèse biomimétique est un outil puissant pour la synthèse totale de substances naturelles polycycliques complexes et ce de bien des manières. On peut retenir que ces stratégies permettent d'accéder à des cibles extrêmement complexes avec simplicité, sobriété et élégance. / This work features various approaches of biomimetic organic syntheses. Biosynthetic considerations have been placed at the center of our analysis in order to define the synthetic plans and later to propose biosynthetic hypotheses.First, the skeleton of drimentines, hybrid alkaloids containing a sesquiterpenic unit, has been obtained by mimicking the main event of their postulated biosynthesis.In a wider study, the marine alkaloid family of the aplysinopsins has been treated with two total syntheses, of dictazole B and tubastrindole B, as well as a full bio-relevant aplysinopsins’ cascade and the application of DNA catalysis principles to the series.Finally, novel dereplication techniques relying on "molecular networking are currently tested on complex synthetic mixtures to merge one step total syntheses and diversity oriented synthesis.

Le but de ce travail de doctorat est l’étude chimique et biosynthétique de familles d’alcaloïdes guanidiniques d’origine marine provenant d’éponges de Méditerranée.Le travail est divisé en trois parties successives : 1) l’isolement d’alcaloïdes produits par des éponges marines de l’ordre des Poeciloscerida; 2) l’élucidation de la biosynthèse de la crambescine C1 par des études in vivo d’incorporation de précurseurs marqués au 14C; 3) la synthèse biomimétique de la crambescine A2 448 et de dérivés proches.La famille des alcaloïdes guanidiniques cycliques des crambescines est au coeur de la thèse, ces substances naturelles sont produites par l’éponge incrustante Crambe crambe. Ces alcaloïdes ont été découverts dans les années 1990 et ont suscité beaucoup d’intérêt pour leurs propriétés biologiques et écologiques et leurs synthèses totales. Par contre, leur biosynthèse était encore inconnue à ce jour. La seule synthèse biomimétique disponible était basée sur une hypothèse d’origine polyacétique. Les hypothèses récentes de nos groupes ont permis de mettre en avant une origine mixte: la partie cyclique guanidinique proviendrait d’un pyrrolidinium issu de l’arginine et d’un précurseur “céto-acide” proche des acides gras. Sur la base de cette hypothèse, nous avons mis au point une expérience d’incorporation qui a ensuite inspirée une voie de synthèse biomimétique pour l’accès aux crambescines et dérivés. Les premières conclusions quant à l’origine biosynthétique de ces molécules sont les faits les plus marquants de ce travail. Nous apportons une meilleure compréhension de la biochimie des alcaloïdes guanidiniques marins de structures complexes. / This thesis aims at the study of the chemical and biogenetic origin of specialized guanidine-alkaloid metabolites produced by sponges from the Mediterranean Sea.The work is divided into three main parts: 1) isolation of alkaloids produced by sponges of the Poeciloscerida order; 2) biosynthesis of crambescin C1 by in-vivo 14C-feeding experiments with Crambe crambe sponge; 3) biomimetic synthesis of crambescin A2 448 and derivatives. The main focus of the thesis will be the family of cyclic-guanidine alkaloids "crambescins", produced by the red incrusting sponge Crambe crambe.These alkaloids were discovered in the early 90s and despite the large interest on their biological activities, ecological roles, and synthesis, their biosynthesis is still unknown.The only available biomimetic synthesis of crambescins was based on a fully polyketide origin hypothesis. Recently our groups suggested an alternative biosynthetic hypothesis in which the guanidine-core would be originated from a condensation between a guanidinated pyrrolidinium derived from arginine and a beta-keto fatty acid. Based on this hypothesis, we designed a biosynthesis experiment that inspired a biomimetic synthesis route to access the crambescins and derivatives. The insights from these studies are the first experimental conclusions about the biosynthesis of crambescins. Finally, this work leads to a better comprehension of the biochemistry involved in guanidine marine alkaloids of complex structures.

<p>With a stable center of mass, pneumatic-aided movement, and the ability to scale multiple terrain types, the uniquely efficient and lightweight form of spiders has changed the way we think about robotic design. While the number of papers on arachnid biomechanics and spider-based biomimetic robots has been increasing in recent years, the style of analysis and the motion-types analyzed have barely changed since the 1980s. Current analyses are based on a force plate and treadmill design, in which the spider is induced into an escape run. This environmental change can affect the movements of the spider. Here I propose a novel method of testing the biomechanical and kinematic properties of spiders using a tank with a built-in sensor matrix which allows for a more natural environment for the specimens and provides force data from individual legs. The system detects a minimum force of .0196 N and has a sampling rate of 1,000 samples /second, which allows for the analysis of forces during the step. <i>Aphonopelma seemanni</i>, a tarantula commonly used in such research, but whose forces during movement have to date not been analyzed, was recorded walking across the matrix, and the forces, step patterns, joint angles, and center of mass deviations were recorded. Walking indicated significantly different step pattern traits than current literature, and forces per leg (.07281 N±.0235) recorded were much smaller than expected in comparison to other spiders. Statistical analysis also indicated no changes in walking movement over a range of temperatures, which also varies from literature. These findings indicate that further research on spiders should be done with respect to walking gaits in order to improve upon current biomimetic models. </p> <br>

The study explores the possibility that a transition zone can become a ‘filter’ that surrounds an urban core. As a filter, the transition zone can regulate and rehabilitate ecosystem services to support human well-being. The main research question focusses on how eco-systemic development can act as a filter while supporting human well-being. The two sub-questions concern (a) how architecture can become a buffer between urban and suburban areas in Pretoria, and (b) how architecture can aid in ecosystem rehabilitation to regenerate urban and human well-being. Through the research done in this study, it is evident that transitional zones around city centres are commonly derelict and unsafe. Human well-being is under pressure as a result of the increasing degradation of ecosystem services, which is brought about by human misuse and urban densification. As cities and human populations grow, urban cores expand. This expansion results in constant re-zoning as well as the demolition and degradation of existing spaces (Preston, 1966:240). Basic human well-being is dependent on successful ecosystem services and the biodiversity of urban environments (Bolund & Hunhammar, 1999:299). This study aims to identify, reintroduce and rehabilitate ecosystem services on an urban edge to facilitate the health and well-being of the community living there. The study addresses three main themes, namely: (1) urban zoning and development, (2) human well-being, and (3) ecosystem-service rehabilitation and reintroduction. By analysing the themes of urban development, well-being as well as social sustainability and ecosystem services, different theories and principles are identified to provide lenses through which the dissertation will be approached. The main lens is that of Vitruvius and the principles he sets out in Ten books on architecture, which relates all design decisions back to nature. Other theories, such as Ernest Burgess’ concentric circle model and the circular economy theory, and the guidelines of the Living Building Institute led to the selection of the site, the development of the urban framework and the design of the intervention. By combining these theories with a programmatic intervention, which was derived from the site and themes, the end result aims to revive the community, the well-being of its members and to reinforce the existing development while ensuring ongoing rehabilitation of the ecosystem services. This intervention aspires to become a catalyst according to which all transition zones in urban environments can be transformed from eye sores and barriers to filters and activators. / Mini Dissertation (MArch (Prof))--University of Pretoria, 2020. / Architecture / MArch (Prof) / Unrestricted

The synthesis and evaluation of a molecularly imprinted polymer has been undertaken using an oxazine-based tryptophanamide transition state analogue (TSA) as template. An efficient route to the synthesis of oxazine-based TSAs for the reaction of pyridoxamine and indole-3-pyruvic acid has been established, with yields of up to 80%. NMR titration studies were performed to examine the interactions between the functional monomer, methacrylic acid and the template. Complexation of the template by functional monomer in the presence of crosslinker showed an apparent KD of 0.63-0.79 ± 0.04 M (293 K, acetonitrile-d3) based upon the chemical shift of the template amide protons. TSA-imprinted and non-imprinted reference polymers were synthesized by free radical polymerization in acetonitrile. Polymer monoliths were ground and fractionated into a 25-63 μm size range. Polymer-ligand recognition studies were conducted using the polymers as HPLC stationary phases. An imprinting factor (IF) of 2.93 was observed for the TSA, indicating the selectivity of the imprinted sites for the template. Studies using the D- and L-enantiomers of the phenylalaninamide analogue of the template showed enantioselectivity in the case of the imprinted polymer, α = 1.10, though not in the case of the non-imprinted reference polymer (1.00). Using UV-spectroscopy based polymer-ligand binding studies, a maximum theoretical capacity (Bmax) of 0.059 ± 0.004 mmol·g-1 was observed for the imprinted polymer. Conclusively, an imprinted polymer with binding sites selective for the TSA was successfully prepared and shall subsequently be studied with respect to its capacity to catalyse the transamination reaction between pyridoxamine and indole-3-pyruvic acid to yield pyridoxal and tryptophan.

This study developed and characterized phospholipid vesicles, or liposomes, that mimic cell surfaces. Microemulsified liposomes contained biotinylated phosphatidylethanolamine, allowing them to be immobilized to avidin-coated glass. Laminin (LN), glycosphingolipids (GMl and GM3), and Escherichia coli's mechanosensitive channel of large conductance (EcoMscL) were embedded into liposome membranes. It was determined whether these embedded molecules exhibited their physiological roles of adhesion, cell recognition, and mechanosensation, respectively. Confocal laser scanning microscopy (CLSM) was employed to examine the interaction of fluorescently probed proteins, toxins, and bacteria with the immobilized microemulsified liposomes. Capture of individual and simultaneous multiple species of bacteria by GMl, GM3, or LN liposomes was quantified using ELISA and PCR. Surface-bound liposomes were unilamellar and immovable, allowing removal of unincorporated probes and biomolecules. Liposomes remained intact and stable against leakage of encapsulated sulforhodamine B for several months after immobilization. Functional reconstitution of EcoMscL was examined using CLSM during modulations in the immursing solution. Cholera toxin(Β subunit) (CTB), bovine lactoferrin (BLF), and E. coli O157:H7 were co-localized proximate to the surface of GMl liposomes. ELISAs determined E. coli O157:H7 and Salmonella enteritidis were captured on GMl liposomes containing GMI at 8.9 molar percent of total lipid. Listeria monocytogenes and Listeria innocua were not captured on the same liposomes. PCR identified the capture of specific bacterial species from individual species and mixtures of several species on liposomes. Simultaneous assays with mixtures of multiple species showed that the receptor-associated binding of bacteria, described with PCR assays of an individual species, were independent of competitive microorganisms. L. monocytogenes and L. innocua were more frequently bound to LN liposomes than other liposomes, indicating LN promotes adhesion of both the pathogenic and a nonpathogenic strain of Listeria. E. coli O157:H7 was more frequently captured on GMI liposomes than other liposomes, indicating a specificity for this bacteria. S. enteritidis bound to all liposomes, indicating a non-specific interaction. Known eukaryotic biomolecules implicated in cell recognition, adhesion, and mechanosensation were embedded in a system of artificial bilayers immobilized on a solid support. Liposomes constitute a biomimetic capable of specifically interacting and capturing proteins, toxins, and bacteria in solution.

No description available.

Today, the majority of materials used for single-use packaging are petroleum-based synthetic polymers. With increased concern about the environmental protection, efforts have been made to develop alternative biodegradable materials from renewable resources. Starch offers an attractive alternative since it is of low cost and abundant. However, the starch material is brittle without plasticizer and the mechanical properties of starch materials are highly sensitive to moisture. In nature, the plant cell walls combine mechanical stiffness, strength and toughness despite a highly hydrated state. This interesting combination of properties is attributed to a network based on cellulose microfibrils. Inspired by this, microfibrillated cellulose (MFC) reinforced starch-based nanocomposites films and foams were prepared. Films with a viscous matrix and MFC contents from 10 to 70wt% were successfully obtained by solvent casting. The films were characterized by DSC, DMA, FE-SEM, XRD, mercury density measurements, and dynamic water vapor sorption (DVS). At 70wt% MFC content a high tensile strength together with high modulus and high work of fracture was observed. This was due to the nanofiber and matrix properties, favourable nanofiber-matrix interaction, a good dispersion of nanofibers and the MFC network. Novel nanocomposite foams were obtained by freeze-drying aquagels prepared from 8wt% solutions of amylopectin starch and MFC. The MFC content was varied from 10 to 70wt%. For composite foam with MFC contents up to 40wt%, improved mechanical properties were observed in compression. The mechanical properties depended both on the cell wall properties and the cell-structure of the foam. The effect of moisture (20-80% RH) on the dynamical properties of composite foam with 40wt% MFC was also investigated and compared to those of neat starch foam. Improved storage modulus was noted with MFC content, which was a result of the nanofiber network in the cell-wall. In addition, the moisture content decreased with MFC content, due to the less hydrophilic nature of MFC. / QC 20101118