Self-assembly of diblock molecular polymer brushes in the spherical confinement of nanoemulsion droplets

Understanding the self-assembly behavior of polymers of various topologies is key to a reliable design of functional polymer materials. Self-assembly under confinement conditions emerges as a versatile avenue to design polymer particles with complex internal morphologies while simultaneously facilitating scale-up. However, only linear block copolymers have been studied to date, despite the increasing control over macromolecule composition and architecture available. This study extends the investigation of polymer self-assembly in confinement from regular diblock copolymers to diblock molecular polymer brushes (MPBs). Block-type MPBs with polystyrene (PS) and polylactide (PLA) compartments of different sizes are incorporated into surfactant-stabilised oil-in-water (chloroform/water) emulsions. The increasing confinement in the nanoemulsion droplets during solvent evaporation directs the MPBs to form solid nano/microparticles. Microscopy studies reveal an intricate internal particle structure, including interpenetrating networks and axially-stacked lamellae of PS and PLA, depending on the PS/PLA ratio of the brushes.Australian Research Council. Grant Number: DE180100007 endowed professorship. Grant Number: 2016‐2022 German Research Foundation (DFG). Grant Numbers: 2017‐2022, 37692067

Synthese und Anwendung von kompartibilisierten molekularen Polymerbürsten

Polymerwissenschaften haben in kürzester Zeit die Entwicklung von hochpräzisen Architekturen synthetischer Makromoleküle mit hoher Komplexität ermöglicht. Neben den Vorzügen von Polymeren bezüglich der Kontrolle über deren Zusammensetzung und Einheitlichkeit, erhöht der Einbau von Kompartibilisierungen in polymere Strukturen deren Funktionalität über die der einzelnen Bausteine hinaus. Hierdurch ergibt sich ein immenses Potential für die Herstellung von maßgeschneiderten Nanomaterialien. In diesem Review diskutieren wir Syntheserouten zur Herstellung von komplexen Molekularbürsten mit wohldefinierten chemischen Kompartimenten. Hierbei wollen wir außerdem deren Potential für die Entwicklung von hochentwickelten Materialien und Anwendung im Bereich der Nanofabrikationen von optischen und anderen Funktionsmaterialien hervorheben

Stiffness-Dependent Intracellular Location of Cylindrical Polymer Brushes

Cylindrical polymer brushes (CPBs) are macromolecules with nanoparticle proportions. Their modular synthesis enables tailoring of their chemical composition as well as the dialing-up of overall dimensions and physicochemical properties. In this study, two rod-like poly[(ethylene glycol) methyl ether methacrylate] (PEGMA)-based CPBs with varying stiffness but otherwise comparable features and functionality, are synthesized. Differences in particle stiffness are assessed using small angle neutron scattering (SANS). It is observed that the fate of the two CPBs within cells is distinctly different. Stiffer CPBs seem to gravitate toward the mitochondria, whereas CPBs with reduced stiffness are present in different intracellular vesicles

Nanostructured Soft Matter from Compartmentalised Molecular Polymer Brushes

Polymer science is rapidly advancing towards the precise construction of synthetic macromolecules of formidable complexity. The impressive advances in control over polymer composition, topology and uniformity, enabled by the living polymerisation revolution, now permit the introduction of compartmentalisation within macromolecules. Despite the straightforward and versatile synthetic approaches to produce block copolymer, nanostructures built-up from these linear building-blocks rarely reaches dimensions beyond the 5–50 nm range and can be sensitive to their environment. The development of robust controlled polymerisation techniques has enabled the synthesis of covalently-bond polymer architectures that can be used as nano-scale building-blocks. One of these architectures are molecular polymer brushes (also known as bottlebrush polymers or cylindrical polymer brushes). Molecular polymer brushes (MPBs) are unique materials that possess astonishing properties arising from their densely grafted and extended chain structure. The field of MPBs, especially as compartmentalised entities, is rapidly growing. Recent efforts have focussed on achieving MPBs with programmed complexity and the introduction of orthogonal chemical functionality. Compartmentalised brushes can elevate their functionality beyond that of their linear constituent parts, thus offering immense potential in self-assembly and template chemistry. The aim of this thesis is to demonstrate how the compartmentalisation in MPBs can be used for the construction of complex, yet precise, polymer nano- and microstructures with the scope to develop advanced functional materials