Planar Polymer Membranes Accommodate Functional Self-Assembly of Inserted Resorcinarene Nanocapsules.

Solid-supported polymer membranes (SSPMs) offer great potential in material and life sciences due to their increased mechanical stability and robustness compared to solid-supported lipid membranes. However, there is still a need for expanding the functionality of SSPMs by combining them with synthetic molecular assemblies. In this study, SSPMs served as a flexible matrix for the insertion of resorcinarene monomers and their self-assembly into functional hexameric resorcinarene capsules. Resorcinarene capsules provide a large cavity with affinity specifically for cationic and polyhydroxylated molecules. While the capsules are stable in apolar organic solvents, they disassemble when placed in polar solvents, which limits their application. Here, a solvent-assisted approach was used for copolymer membrane deposition on solid support and simultaneous insertion of the resorcinarene monomers. By investigation of the molecular factors and conditions supporting the codeposition of the copolymer and resorcinarene monomers, a stable hybrid membrane was formed. The hydrophobic domain of the membrane played a crucial role by providing a sufficiently thick and apolar layer, allowing for the self-assembly of the capsules. The capsules were functional inside the membranes by encapsulating cationic guests from the aqueous environment. The amount of resorcinarene capsules in the hybrid membranes was quantified by a combination of quartz-crystal microbalance with dissipation and liquid chromatography-mass spectrometry, while the membrane topography and layer composition were analyzed by atomic force microscopy and neutron reflectometry. Functional resorcinarene capsules inside SSPMs can serve as dynamic sensors and potentially as cross-membrane transporters, thus holding great promise for the development of smart surfaces.

Tailoring Polymer-Based Nanoassemblies for Stimuli-Responsive Theranostic Applications.

Polymer assemblies on the nanoscale represent a powerful toolbox for the design of theranostic systems when combined with both therapeutic compounds and diagnostic reporting ones. Here, recent advances in the design of theranostic systems for various diseases, containing-in their architecture-either polymers or polymer assemblies as one of the building blocks are presented. This review encompasses the general principles of polymer self-assembly, from the production of adequate copolymers up to supramolecular assemblies with theranostic functionality. Such polymer nanoassemblies can be further tailored through the incorporation of inorganic nanoparticles to endow them with multifunctional therapeutic and/or diagnostic features. Systems that change their architecture or properties in the presence of stimuli are selected, as responsivity to changes in the environment is a key factor for enhancing efficiency. Such theranostic systems are based on the intrinsic properties of copolymers or one of the other components. In addition, systems with a more complex architecture, such as multicompartments, are presented. Selected systems indicate the advantages of such theranostic approaches and provide a basis for further developments in the field.

Fully amorphous atactic and isotactic block copolymers and their self-assembly into nano- and microscopic vesicles.

The introduction of chirality into aqueous self-assemblies by employing isotactic block copolymers (BCPs) is an emerging field of interest as it promises special membrane properties of polymersomes not accessible by atactic BCPs. However, isotactic BCPs typically exhibit crystalline behaviour, inducing high membrane stiffness and limiting their applicability in systems involving membrane proteins or sensitive cargo. In this study, an isotactic yet fully amorphous BCP is introduced which overcomes these limitations. Three BCPs composed of poly(butylene oxide)-block-poly(glycidol) (PBO-b-PG), differing solely in their tacticities (R/S, R and S), were synthesised and characterised regarding their structural, optical and thermal properties. Their self-assembly into homogenous phases of nanoscopic polymersomes (referred to as small unilamellar vesicles, SUVs) was analysed, revealing stability differences between SUVs composed of the different BCPs. Additionally, microscopic giant unilamellar vesicles (GUVs) were prepared by double emulsion microfluidics. Only the atactic BCP formed GUVs which were stable over several hours, whereas GUVs composed of isotactic BCPs ruptured within several minutes after formation. The ability of atactic PBO-b-PG to form microreactors was elucidated by reconstituting the membrane protein OmpF in the GUV membrane by microfluidics and performing an enzyme reaction inside its lumen. The system presented here serves as platform to design versatile vesicles with flexible membranes composed of atactic or isotactic BCPs. Hence, they allow for the introduction of chirality into nano- or microreactors which is a yet unstudied field and could enable special biotechonological applications.

The rise of bio-inspired polymer compartments responding to pathology-related signals.

Self-organized nano- and microscale polymer compartments such as polymersomes, giant unilamellar vesicles (GUVs), polyion complex vesicles (PICsomes) and layer-by-layer (LbL) capsules have increasing potential in many sensing applications. Besides modifying the physicochemical properties of the corresponding polymer building blocks, the versatility of these compartments can be markedly expanded by biomolecules that endow the nanomaterials with specific molecular and cellular functions. In this review, we focus on polymer-based compartments that preserve their structure, and highlight the key role they play in the field of medical diagnostics: first, the self-assembling abilities that result in preferred architectures are presented for a broad range of polymers. In the following, we describe different strategies for sensing disease-related signals (pH-change, reductive conditions, and presence of ions or biomolecules) by polymer compartments that exhibit stimuli-responsiveness. In particular, we distinguish between the stimulus-sensitivity contributed by the polymer itself or by additional compounds embedded in the compartments in different sensing systems. We then address necessary properties of sensing polymeric compartments, such as the enhancement of their stability and biocompatibility, or the targeting ability, that open up new perspectives for diagnostic applications.