Yes / For the development of applications and novel uses for peptide nanostructures, robust routes for their surface functionalization, that ideally do not interfere with their self‐assembly properties, are required. Many existing methods rely on covalent functionalization, where building blocks are appended with functional groups, either pre‐ or post‐assembly. A facile supramolecular approach is demonstrated for the formation of functionalized nanofibers by combining the advantages of biocatalytic self‐assembly and surfactant/gelator co‐assembly. This is achieved by enzymatically triggered reconfiguration of free flowing micellar aggregates of pre‐gelators and functional surfactants to form nanofibers that incorporate and display the surfactants’ functionality at the surface. Furthermore, by varying enzyme concentration, the gel stiffness and supramolecular organization of building blocks can be varied. / FP7 Marie Curie Actions of the European Commission. Grant Number: 289723; EPSRC; HFSP; ERC; Leverhulme Trust

In the summer of 2022, a co-assembly of metagenome was created using the microbes found at Barres Woods in Harvard Forest. 14 samples were taken, and sample was split into the organic and mineral layer, which totals 28 Bulk MAGs. Within this Co-assembly, 4 different genomes were found which were designated with the phylum of FCPU426. Three of which were considered medium quality and one being assigned high quality. The novel phyla first appeared in NCBI and GTDB databases in June 2018. The name FCPU426 dates to 2010 and was named based on the 16s amplicon sequencing. The novel phylum is shown to have common ancestors with the phyla of Goldbacteria and Firestonebacteria. Goldbacteria was determined to have the ability to break down cellulose to further enhance carbon cycling. In this analysis of FCPU426, the taxonomy of the phyla will be further investigated. FCPU426 was then annotated to determine if any of the cellulase genes are shared between itself and Goldbacteria. Further annotations were done to spot any genes of interest that create any distinctions between any of its counterparts.

Cette thèse se focalise sur le design, la synthèse et la caractérisation photophysiques de complexes de platine(II) neutres contenant un ligand chromophore tridenté et un ligand auxiliaire monodenté avec des groupes fonctionnels différents. De tels complexes montrent des changements drastiques de leurs propriétés de photoluminescence à cause de leur auto-assemblage, déclenché par l’établissement de faibles liaisons non covalents tels que l’empilement p-p et des interactions métallophiliques. Il a été démontré que ces complexes de platine(II) peuvent être attaché de manière covalente à des surfaces de silice et d’or mais aussi encapsulé dans des particules de polymère. Les propriétés d’autoassemblage de complexes de platine(II) amphiphiles ont également été étudiées en détails. Comprendre le comportement d’un complexe de platine dans un mélange de solvant nous a permis d’en apprendre plus sur le co-assemblage supramoléculaire de deux complexes de platine(II) différents. Cette approche conduit à la formation de fibres solvatochromiques avec des propriétés photophysiques spécifiques et réversibles. Les composés étudiés et leur auto-assemblage sonti ntéressant pour le développement de nouveaux matériaux fonctionnels aux applications sensoriels et réactives à certains stimuli. / This thesis focuses on the design, synthesis and the photophysical characterisation of luminescent neutral platinum(II) compounds containing a tridentate chromophoric ligand and a monodentate ancillary moiety with different functionalities. Such complexes exhibited drastic changes to their photoluminescence properties upon self-assembly, triggered by the establishment of weak noncovalent p-p stacking and metallophilic interactions. It was demonstrated that these platinum(II) complexes can be covalently attached to silicon and gold substrates but also encapsulated into polymer particles. The self-assembly properties of amphiphilic platinum(II) complexes have also been intensively studied. Understanding the behaviour of one complex in a solvent mixture allowed further investigation into the supramolecular co-assembly of two different platinum(II) complexes. This approach leads to the formation of solvatochromic fibers with specific and reversible phototophysical properties. The investigated compounds and their assemblies were useful for the development of novel functional materials for sensing or stimuli-responsiveness applications.

Les complexes de polyélectrolytes (PECs) sont typiquement formés par interaction électrostatique entre deux polyélectrolytes de charge opposée. Alors que de nombreuses études ont été consacrées aux propriétés de ces complexes, l'objectif de la thèse est de mieux comprendre le rôle de l’intensité de l’interaction entre deux polyélectrolytes sur la morphologie des complexes ainsi que la cinétique et la thermodynamique de la complexation. Différents systèmes complexants, faibles et forts, donnant lieu à la formation de coacervats ou de précipités ont été choisis et étudiés sur une large gamme de rapport de charges (Z[+]/[-]) afin d'obtenir différents états physiques (soluble, colloïdal, phase dense). La morphologie des complexes a été déterminée par microscopie (optique, fluorescence, force atomique) et diffusion de rayonnement (lumière, neutrons). La cinétique et la thermodynamique de complexation ont été étudiées par utilisation respective d'un mélangeur à flux stoppé et de la calorimétrie de titration isotherme. Les résultats obtenus permettent de mettre en évidence un certain nombre de caractéristiques permettant de distinguer les systèmes complexants forts et faibles. En particulier, les complexes forts sont hors équilibre d'un point de vue thermodynamique et en conséquence ils présentent une forte dépendance aux conditions initiales de complexation. Un autre aspect important et qui pourrait être à l'origine de la distinction entre les complexes forts et faibles est l'énergie d'hydratation des polyélectrolytes qui a été déterminée pour de nombreux polyélectrolytes et corrélée aux propriétés des complexes. / Complexes of polyelectrolytes (PECs) are oppositely charged polymers assemblies held together by electrostatic interaction. As the non-covalent assembly of macromolecules/colloids in solution has been thoroughly investigated over the last decade with a particular emphasis put on the morphology of the final aggregates as a function of the building blocks-chemistry, the objective of this thesis is to come to a better understanding of the influence of interaction strength between polyelectrolytes on complexes morphologies, as well as kinetics and thermodynamics of the complexation. For this study, weakly and strongly interacting systems given rise to coacervate and precipitate phases has been elected. Those systems have been studied on a wide charge ratio scale (Z[+]/[-]) to span several physical states of the PECs (soluble and colloidal PECs, dense phases). Morphologies of assemblies are assessed by microscopy (optical, fluorescence, atomic force) and scattering techniques (neutron, light). Kinetics and thermodynamics of the complexation process are studied by use of a stopped-flow mixing device and an isothermal titration calorimeter. Results gave us keys to discriminate strongly interacting systems from weakly interacting ones. In particular, the ‘strong systems’ are showed to be non-equilibrium assemblies, ie. the formulation pathway or the way these different macromolecules are coming into contact is then a key step. Another important aspect that could explain the complexation process behavior is the hydration energy of the polyelectrolytes. Calorimetry measurements have been performed for numerous polyelectrolytes and then correlated to complexes properties.

Title: Self-assembly of polymers with amphiphilic compounds (surfactants) in aqueous solutions Abstract: This PhD Thesis is devoted to the co-assembly in systems containing electrically charged polymers (polyelectrolytes and block copolymers containing polyelectrolyte sequences). I studied the interactions between block copolymers and oppositely charged surfactants in aqueous solutions, and the structure and properties of co-assembled nanoparticles by a combination of several experimental methods. I found that the spontaneous formation, solubility and stability of complex nanoparticles depend not only on the electrostatic attractive forces but also on the hydrophobic effects. In a major part of my Thesis, I studied the interaction of polyelectrolytes with oppositely charged gemini surfactants (containing two charged head-groups interconnected by a short linker and two hydrophobic tails) which is a relatively new topic - much less studied than the co-assembly with conventional single tail surfactants. Better understanding of the formation and properties of complexes containing gemini surfactants and polymers provides knowledge that should lead to novel tailor-made nanoparticles with desired properties for applications in medicine and new technologies (including nano-technologies). We have shown that the...

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Cellulose is the most abundant biopolymer on Earth as it is found in every plant cell wall; therefore, it represents one of the most promising natural resources for the fabrication of sustainable materials. In plants, cellulose is mainly used for structural integrity, however, some species organise cellulose in helicoidal nano-architectures generating strong iridescent colours. Recent research has shown that cellulose nanocrystals, CNCs, isolated from natural fibres, can spontaneously self-assemble into architectures that resemble the one producing colouration in plants. Therefore, CNCs are an ideal candidate for the development of new photonic materials that can find use to substitute conventional pigments, which are often harmful to humans and to the environment. However, various obstacles still prevent a widespread use of cellulose-based photonic structures. For instance, while the CNC films can display a wide range of colours, a precise control of the optical appearance is still difficult to achieve. The intrinsic low thermal stability and brittleness of cellulose-based films strongly limit their use as photonic pigments at the industrial scale. Moreover, it is challenging to integrate them into composites to obtain further functionality while preserving their optical response. In this thesis, I present a series of research contributions that make progress towards addressing these challenges. First, I use an external magnetic field to tune the CNC films scattering response. Then, I demonstrate how it is possible to tailor the optical appearance and the mechanical properties of the films as well as to enhance their functionality, by combining CNCs with other polymers. Finally, I study the thermal properties of CNC films to improve the retention of the helicoidal arrangement at high temperatures and to explore the potential use of this material in industrial fabrication processes, such as hot-melt extrusion.