Immobilization of polymeric nano-assemblies for antibacterial applications

With conventional antibiotic therapies being increasingly ineffective, bacterial infections with subsequent biofilm formation represent a global threat to human health and therefore,new strategies to fight bacteria colonization need to be found. Coimmobilization of functional, nanosized assemblies broadens the possibility to engineer dually functionalized active surfaces with a nanostructured texture. Surfaces decorated with different nanoassemblies, such as micelles, polymersomes, or nanoparticles are in high demand for various applications ranging from catalysis, biosensing up to antimicrobial surfaces. In this thesis, I present a combination of bio-orthogonal and catalyst-free strain-promoted azide-alkyne click (SPAAC) and thiol-ene reactions to simultaneously coimmobilize various nanoassemblies; polymersome-polymersome and polymersome-micelle assemblies were selected. For the first time, the immobilization method using SPAAC reaction was studied in detail to attach soft, polymeric assemblies on a solid support. Together, the SPAAC and thiol-ene reactions successfully coimmobilized two unique self-assembled structures on the surfaces. Additionally, poly-(dimethylsiloxane) (PDMS)-based polymersomes were used as "ink" for direct immobilization from a PDMS-based microstamp onto a surface creating locally defined patterns. Furthermore, an active and a passive strategy based on polymeric micelles were combined to fight bacterial growth. The passive strategy involved covalent immobilization of polymeric micelles through Michael addition between maleimide exposed micelles and thiol functionalized surfaces. Compared to the bare surface, micelle-decorated surfaces showed reduced adherence and survival of bacteria. To extend this passive defense against bacteria with an active strategy, the immobilized micelles were equipped with the antimicrobial peptide KYE28 (KYEITTIHNLFRKLTHRLFRRNFGYTLR). The peptide interacted nonspecifically with the immobilized micelles where it retained its antimicrobial property. The successful surface decoration with KYE28 was demonstrated by a combination of X-ray photoelectron spectroscopy and quartz crystal microbalance with dissipation monitoring. The initial antimicrobial activity of the nanostructured surfaces against Escherichia coli (E. coli) was found to be increased by the presence of KYE28. Combining immobilization reactions has the advantage to attach any kind of nanoassembly pairs, resulting in surfaces with desired interfacial properties. Different nanoassemblies that encapsulate multiple active compounds coimmobilized on a surface will pave the way for the development of multifunctional surfaces with controlled properties and effciency. Additionally, the combination of our active and a passive strategy represents a straightforward modular approach that can easily be adapted, for example, by exchanging the antimicrobial peptide to optimize potency against challenging bacterial strains, and/or to simultaneously achieve antimicrobial and anti-infection properties

Surfaces with Dual Functionality through Specific Coimmobilization of Self-Assembled Polymeric Nanostructures

Coimmobilization of functional, nanosized assemblies broadens the possibility to engineer dually functionalized active surfaces with a nanostructured texture. Surfaces decorated with different nanoassemblies, such as micelles, polymersomes, or nanoparticles are in high demand for various applications ranging from catalysis, biosensing up to antimicrobial surfaces. Here, we present a combination of bio-orthogonal and catalyst-free strain-promoted azide–alkyne click (SPAAC) and thiol–ene reactions to simultaneously coimmobilize various nanoassemblies; we selected polymersome–polymersome and polymersome–micelle assemblies. For the first time, the immobilization method using SPAAC reaction was studied in detail to attach soft, polymeric assemblies on a solid support. Together, the SPAAC and thiol–ene reactions successfully coimmobilized two unique self-assembled structures on the surfaces. Additionally, poly(dimethylsiloxane) (PDMS)-based polymersomes were used as “ink” for direct immobilization from a PDMS-based microstamp onto a surface creating locally defined patterns. Combining immobilization reactions has the advantage to attach any kind of nanoassembly pairs, resulting in surfaces with “desired” interfacial properties. Different nanoassemblies that encapsulate multiple active compounds coimmobilized on a surface will pave the way for the development of multifunctional surfaces with controlled properties and efficiency

Decorating Nanostructured Surfaces with Antimicrobial Peptides to Efficiently Fight Bacteria

With conventional antibiotic therapies being increasingly ineffective, bacterial infections with subsequent biofilm formation represent a global threat to human health. Here, an active and a passive strategy based on polymeric micelles were combined to fight bacterial growth. The passive strategy involved covalent immobilization of polymeric micelles through Michael addition between exposed maleimide and thiol functionalized surfaces. Compared to the bare surface, micelle-decorated surfaces showed reduced adherence and survival of bacteria. To extend this passive defense against bacteria with an active strategy, the immobilized micelles were equipped with the antimicrobial peptide KYE28 (KYEITTIHNLFRKLTHRLFRRNFGYTLR). The peptide interacted nonspecifically with the immobilized micelles where it retained its antimicrobial property. The successful surface decoration with KYE28 was demonstrated by a combination of X-ray photoelectron spectroscopy and quartz crystal microbalance with dissipation monitoring. The initial antimicrobial activity of the nanostructured surfaces against Escherichia coli was found to be increased by the presence of KYE28. The combination of the active and passive strategy represents a straightforward modular approach that can easily be adapted, for example, by exchanging the antimicrobial peptide to optimize potency against challenging bacterial strains, and/or to simultaneously achieve antimicrobial and anti-infection properties

Brushing the surface: cascade reactions between immobilized nanoreactors

Functionalization of hard or soft surfaces with, for example, ligands, enzymes or proteins, is an effective and practical methodology for the development of new applications. We report the assembly of two types of nanoreactors based upon poly(dimethylsiloxane)-block-poly(2-methyl-2-oxazoline) (PDMS-b-PMOXA) diblock copolymers as scaffold, uricase and lactoperoxidase as bio-catalysts located within the nanoreactors, and melittin as the biopores inserted into the hydrophobic shell. The nanoreactors were immobilized on poly(2-hydroxyethyl methacrylate)-co-poly(2-aminoethyl methacrylate hydrochloride) (PHEMA-co-P(2-AEMA·HCl) brushes-grafted wafer surfaces by utilizing the strong supramolecular interactions between biotin and streptavidin. The (PHEMA-co-P(2-AEMA·HCl) brushes on silicon surfaces were prepared by a surface initiating atom transfer radical polymerization (ATRP) "graft-from" technique. Cascade reactions between different surface-anchored nanoreactors were demonstrated by converting Amplex Red to the fluorescent probe resorufin by using the H2O2 produced from uric acid and H2O. The detailed properties of the nanoreactors on the functionalized surface including the binding behaviours and cascade reactions were investigated using emission spectroscopy, transmission electron microscopy (TEM), light scattering (LS), atomic force microscopy (AFM) and a quartz crystal microbalance (QCM-D). The results are proof-of-principle for the preparation of catalytically functional engineered surface materials and lay the foundation for applying this advanced functional surface material in biosensing, implanting and antimicrobial materials preparation

Enabling planetary science across light-years. Ariel Definition Study Report

Ariel, the Atmospheric Remote-sensing Infrared Exoplanet Large-survey, was adopted as the fourth medium-class mission in ESA's Cosmic Vision programme to be launched in 2029. During its 4-year mission, Ariel will study what exoplanets are made of, how they formed and how they evolve, by surveying a diverse sample of about 1000 extrasolar planets, simultaneously in visible and infrared wavelengths. It is the first mission dedicated to measuring the chemical composition and thermal structures of hundreds of transiting exoplanets, enabling planetary science far beyond the boundaries of the Solar System. The payload consists of an off-axis Cassegrain telescope (primary mirror 1100 mm x 730 mm ellipse) and two separate instruments (FGS and AIRS) covering simultaneously 0.5-7.8 micron spectral range. The satellite is best placed into an L2 orbit to maximise the thermal stability and the field of regard. The payload module is passively cooled via a series of V-Groove radiators; the detectors for the AIRS are the only items that require active cooling via an active Ne JT cooler. The Ariel payload is developed by a consortium of more than 50 institutes from 16 ESA countries, which include the UK, France, Italy, Belgium, Poland, Spain, Austria, Denmark, Ireland, Portugal, Czech Republic, Hungary, the Netherlands, Sweden, Norway, Estonia, and a NASA contribution

Probing membrane asymmetry of ABC polymersomes

We report the sensitivity of the membrane asymmetry of ABC (PEO-b-PCL-b-PMOXA) polymersomes towards the end-group modification of a shorter C block. While a non-modified ABC polymer formed polymersomes with the A block outside and the C block inside

Enzymatic Reactions in Polymeric Nanocontainers: Nanotechnology meets Nature

One of the main features of living matter is compartmentalization, that is the temporal and spatial division of biological reactions and containment of the cellular components. Nanotechnology aims to replicate this, separating tiny environments from the exterior into nano-sized and micro-sized self-assembled compartments. Those synthetic compartments can perform reactions, be tracked and act in vivo. Here, an overview of the techniques to fabricate vesicular, polymer-based catalytic compartments and the parameters affecting their architecture is presented. How communication can be ensured across their membranes, recent developments in the enzymes that have been loaded into them and the latest advances in biological applications are discussed. This review highlights the characteristics that make polymers an enticing choice, the protection they offer, and their applications in compartmentalizing biologically relevant reactions

Exploiting exciton coupling of ligand radical intervalence charge transfer transitions to tune NIR absorption

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