The unique corona structure of patchy micelles, featuring alternating, chemically distinct patches, opens various applications owing to their outstanding interfacial activity and potential for regio-selective functionalization. Crystallization-driven self-assembly of triblock terpolymers with a crystallizable polyethylene middle block and two incompatible end blocks (polystyrene (PS) and poly(methyl methacrylate) (PMMA)) is an efficient method for the production of patchy core-crystalline micelles (CCMs).[1] Depending on the solvent quality, either worm-like (wCCMs) or spherical (sCCMs) core-crystalline micelles with a patchy PS/PMMA corona are formed. Introducing tertiary amino-groups in one of the patches facilitates regio-selective loading with different metal and metal oxide nanoparticles. Immobilizing functional wCCMs on electrospun nonwovens employing coaxial electrospinning and subsequent loading with gold nanoparticles gives access to patchy hybrid nonwovens with excellent catalytic activity and reusability in the alcoholysis of silanes. Moreover, wCCMs with functional patches can induce the molecular self-assembly of 1,3,5-benzenetricarboxamides (BTAs) to form well-defined, fir-tree-like superstructures if the tertiary amino-groups in the patches match with the peripheral substituents of the BTA.[3]
An alternative route to patchy sCCMs is stereo¬complex-driven self-assembly of diblock copolymers with enantiomeric poly(L-lactide) (PLLA) and poly(D-lactide) (PDLA) blocks, yielding sCCMs with a PLLA/PDLA stereocomplex core and a patchy PS/PtBMA corona (PtBMA = poly(tert-butyl methacrylate)).[4] These micelles are highly efficient compatibilizers for polymer blends.[5] This is attributed to their adaptive corona structure, resulting in a selective swelling/collapse of the respective miscible/immiscible corona patches at the blend interface. A superior interfacial activity was also proven for patchy wCCMs, being comparable to that of Janus cylinders.

Compartmentalization on the micro- and nanoscale represents a ubiquitous phenomenon enabling living cells to organize and regulate metabolic processes. Inspired by this concept, various strategies to create synthetic compartmentalized structures exploiting the association of oppositely charged polymer chains have been developed over the last years. These compartments are mostly assembled upon (direct) mixing of pre-made macromolecules. In natural systems, however, polymerization and assembly usually occur in concert. The spatiotemporal colocalization of these processes results in the formation of reaction-assembly networks, in which the formation of covalent and supramolecular bonds are coupled and mutually influence each other via chemical feedback. Depending on the polymerization conditions a variety of multi-responsive, polymeric nanostructures with defined size, shape and composition can be accessed. Performing the polymerization of ionic monomers under highly dilute conditions allows switching the process ON and OFF on demand via the reversible association and confinement of monomers on an oppositely charged template. Consecutive ON/OFF switching steps alter the assembly pathway by fine-tuning the structural relaxation times of the interacting chains and as well as induce preferential incorporation of charged over neutral monomers via modulation of polymerization rates. Specific block sequences and compositions of strong ionic-neutral copolymers can be precisely programmed, and even unique, alternating multiblock-like topologies become accessible in a straightforward, one-pot process.

Background: The elucidation of material nanostructure under elevated pressures is quite relevant for devices used in deep sea research, including tactile sensors and soft robotics . To accommodate resistance to harsh underwater environments, multicomponent systems need to be utilized with orthogonal properties. Technical challenges had so far hampered the investigation of thin film nanostructures of varying compositional complexity under elevated hydrostatic pressures.
Methods: By utilizing a custom-made pressure cell and performing Grazing Incidence Small Angle Neutron Scattering under pressure (HP - GISANS) at D22 and neutron reflectometry (NR) at FIGARO instruments of the ILL, we compare effects of pressure and temperature at the solid-liquid interface between two homopolymer mixed brushes in thin (< 100 nm) film using D2O solvent: A weakly incompatible (poly(methyl methacrylate) / poly(2-(dimethylamino)ethyl methacrylate)) (PMMA / PDMAEMA) and strongly incompatible ((poly((2,2,3,3,4,4,5,5-octafluoro)pentyl methacrylate))/ poly(2-(dimethylamino)ethyl methacrylate) ) (POFPMA/PDMAEMA) mixed brush.
Results: We record distinct pressure-dependent response in lateral (HP - GISANS) and transversal (specular NR) nanostructure depending on the chemical compatibility between the polymers. GISANS simulations indicate buried hydrophobic dimple-like patches within a PDMAEMA-based swollen matrix. Specular ToF-NR suggests that temperature effects are counteracted by pressure. Off-specular NR reveals large (>100 nm) lateral domains associated to the hydrophilic PDMAEMA compound, being both pressure-dependent and polymer-compatibility dependent.
Conclusion: The length scale of phase separation on the sample surface strongly depends on the compositional variation in the mixed brushes. Also, non-idealities of mixing are polymer-compatibility dependent as evidenced by enhanced D2O retention within the brush by the more strongly incompatible POFPMA/PDMAEMA.

Polymers can self-assemble into biomolecular condensates / coacervates. This is widely used in cells, is crucial in materials and food science and has great potential in nanomedicine. The structure and function of these systems are closely related to their function. Notably, in cells we observe structures that are difficult to recreate in vitro. Having access to a wider variety of structures will allow us to perform a wider variety of functions with our systems. I present on a general mechanism to create complex structures using out-of-equilibrium conditions. Recently, we've published a method so that researchers working on an arbitrary system can create different structures. Key are polymer properties and phase diagrams. Using this tool, the meso-scale structure becomes an independent variable in experiments, rather than a consequence of the materials mixed and environmental conditions.

We present an innovative µCP technique that enables precise patterning of capillary-active surfaces and hydrogels. This method combines high printing accuracy with specific chemical functionality at the printed regions. It utilizes a polymer brush-supported printing process, where polymer brushes attached to an elastomeric polydimethylsiloxane (PDMS) stamp are used to transfer ink reactively. Initially, the ink is immobilized within the brush matrix and is then transferred to the substrate only during the physical contact between the stamp and the substrate, preventing uncontrolled ink smearing (Figure 1a).
This technique is versatile and can be applied to various substrates, allowing for microscale patterning. We demonstrated the transfer of small patterns on inorganic substrates using reactive silanes as ink.[1,2] The printing procedure is also adaptable to other substrates, such as cellulose surfaces or hydrogel surfaces with glycan functionalities (Figure 1b).[3] Additionally, the protocol can be used on curved surfaces. For instance, we structured the surface of SiO2 microspheres, creating patchy particles with intricate surface patterns (Figure 1b).[4]

Hierarchical supramolecular assemblies constitute an important class of functional materials exhibiting diverse structures and applications. Polydiacetylenes (PDA) are a class of conjugated polymers formed by the 1,4-addition of diacetylene (DA) units. Herein, we discuss designing and constructing diverse hierarchically organized macrocyclic diacetylene (MCDA) based nanostructures. Self-assembled hollow nanotubes formed by the photopolymerization of MCDA amphiphilic monomers, as revealed by single-particle cryo-electron microscopy (cryo-EM) and tomographic analysis, shows tubes consisting of six pairs of covalently bonded filaments held together by hydrophobic interactions. The hollow MCDA nanotubes efficiently scavenge amphiphilic pollutants in water and subsequently photodegrade the guest species. Hierarchically coassembled nanotoroids comprising MCDA and 8-anilino-1-naphthalene sulfonate (ANS) show nanofibers formed by stacked DA monomers as the basic units, which are further bent and aligned into toroids by electrostatic and hydrophobic interactions with the ANS. The amine moieties on the nanotoroid's surface are employed for deposition of gold nanostructures – Au nanoparticles or Au nanosheets – which constitute effective platforms for photocatalysis and surface-enhanced Raman scattering (SERS)-based sensing. Modulating noncovalent interactions between the MCDA, anthraquinone DA, and carbon dots facilitates the formation of thin films exhibiting a long-range, uniform “honeycomb” porous structure. Wavelength-induced coassembly plays a key role by both initiating interactions between the carbon dots and the anthraquinone moieties and giving rise to the topotactic polymerization of the DA network. Macro-porous films were utilized as a photocatalytic platform for water pollutant degradation and as potential supercapacitor electrodes, taking advantage of the high surface area, hydrophobicity, and pore structure of the film.