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Core-crosslinked polymeric micelles (CCPMs) are an attractive class of nanocarriers for drug delivery. Two crosslinking approaches to form CCPMs exist: either via a low-molecular-weight crosslinking agent to connect homogeneous polymer chains with reactive handles or via cross-reactive handles on polymers to link them to each other (complementary polymers). Previously, CCPMs based on methoxy poly(ethylene glycol)-b-poly[N-(2-hydroxypropyl) methacrylamide-lactate] (mPEG-b-PHPMAmLacn) modified with thioesters were crosslinked via native chemical ligation (NCL, a reaction between a cysteine residue and thioester resulting in an amide bond) using a bifunctional cysteine containing crosslinker. These CCPMs are degradable under physiological conditions due to hydrolysis of the ester groups present in the crosslinks. The rapid onset of degradation observed previously, as measured by the light scattering intensity, questions the effectiveness of crosslinking via a bifunctional agent. Particularly due to the possibility of intrachain crosslinks that can occur using such a small crosslinker, we investigated the degradation mechanism of CCPMs generated via both approaches using various analytical techniques. CCPMs based on complementary polymers degraded slower at pH 7.4 and 37 °C than CCPMs with a crosslinker (the half-life of the light scattering intensity was approximately 170 h versus 80 h, respectively). Through comparative analysis of the degradation profiles of the two different CCPMs, we conclude that partially ineffective intrachain crosslinks are likely formed using the small crosslinker, which contributed to more rapid CCPM degradation. Overall, this study shows that the type of crosslinking approach can significantly affect degradation kinetics, and this should be taken into consideration when developing new degradable CCPM platforms.

Oil-soluble poly(meth)acrylate-based polymers play a vital role in the thermorheological modification of a wide variety of lubricants and formulated consumer products, where increased viscosity at elevated temperatures ensures sufficient viscosity over a broad temperature range. The assumed mechanism of viscosity modification for many such polymers is based on temperature-induced swelling due to marginal solvent quality. Although this mechanism is widely accepted, direct and consistent experimental proof is limited due to a lack of structural characterization over a wide temperature range. Additionally, the effect of polymer architecture on the temperature-dependent solution behavior is not fully understood, despite the trend toward branched polymers in recent years. Here, we provide a comprehensive set of data relying on detailed temperature-dependent viscosity measurements, dynamic light scattering (DLS), and small-angle neutron scattering (SANS) experiments to confirm the existence of temperature-induced coil expansion for industrially relevant poly(stearyl methacrylate-co-methyl methacrylate) (p(SMA-co-MMA)) polymers with various architectures including linear, randomly branched, and star-shaped topologies. Compared to the linear and randomly branched polymers, the degree of coil expansion for the star-shaped additives is significantly lower. Regardless of the polymer architecture, the propensity to undergo temperature-induced chain swelling proved to be highly specific toward the type of base oil, underlining the sensitive interplay between polymer and oil chemistry required for designing successful thermorheological modifiers.

Transient assembled structures play an indispensable role in a wide variety of processes fundamental to living organisms including cellular transport, cell motility, and proliferation. Typically, the formation of these transient structures is driven by the consumption of molecular fuels via dissipative reaction networks. In these networks, building blocks are converted from inactive precursor states to active (assembling) states by (a set of) irreversible chemical reactions. Since the activated state is intrinsically unstable and can be maintained only in the presence of sufficient fuel, fuel depletion results in the spontaneous disintegration of the formed superstructures. Consequently, the properties and behavior of these assembled structures are governed by the kinetics of fuel consumption rather than by their thermodynamic stability. This fuel dependency endows biological systems with unprecedented spatiotemporal adaptability and inherent self-healing capabilities. Fascinated by these unique material characteristics, coupling the assembly behavior to molecular fuel or light-driven reaction networks was recently implemented in synthetic (supra)molecular systems. In this invited feature article, we discuss recent studies demonstrating that dissipative assembly is not limited to the molecular world but can also be translated to building blocks of colloidal dimensions. We highlight crucial guiding principles for the successful design of dissipative colloidal systems and illustrate these with the current state of the art. Finally, we present our vision on the future of the field and how marrying nonequilibrium self-assembly with the functional properties associated with colloidal building blocks presents a promising route for the development of next-generation materials.

Dimple colloids with well-defined cavities were synthesized by a modified dispersion polymerization. The key step in the procedure is the delayed addition of cross-linkers into the reaction mixture. By systematically studying the effect of the delayed addition time and the concentration of the cross-linker on the resulting particle morphology, we identified the dominating driving force that underlies dimple formation. The delayed addition of cross-linkers results in colloids with a core–shell morphology consisting of a core rich in linear polymers and a cross-linked shell. This morphology was confirmed by selectively etching non-cross-linked material using dimethylformamide. With polymerization proceeding, consumption of monomers present in the swollen particles leads to contraction of the particles, which is larger for the core composed of linear polymers compared to the stiffer cross-linked shell. To accommodate this decrease in volume, the outer cross-linked shell has to buckle, resulting in a well-defined dimple. Furthermore, we extended the procedure to incorporate functional monomers, yielding chemically modifiable dimple particles. Subsequently, we showed that by leveraging the core–shell structure, these dimple particles can be used to prepare dumbbell-shaped colloids with one hollow and one solid lobe. These partially hollow anisotropic particles assemble into strings with well-defined orientations in an alternating current electric field.

Colloidal structures and lattices made of patchy particles with chemically distinct lobes are formed by exploring site-specific depletion forces. This approach introduces a simple route to assemble colloidal superlattices.

Inspired by nanotechnologies based on DNA strand displacement, herein we demonstrate that synthetic helical strand exchange can be achieved through tuning of poly(methyl methacrylate) (PMMA) triple-helix stereocomplexes. To evaluate the utility and robustness of helical strand exchange, stereoregular PMMA/polyethylene glycol (PEG) block copolymers capable of undergoing crystallization driven self-assembly via stereocomplex formation were prepared. Micelles with spherical or wormlike morphologies were formed by varying the molecular weight composition of the assembling components. Significantly, PMMA strand exchange was demonstrated and utilized to reversibly switch the micelles between different morphologies. This concept of strand exchange with PMMA-based triple-helix stereocomplexes offers new opportunities to program dynamic behaviors of polymeric materials, leading to scalable synthesis of “smart” nanosystems.

Polymer-based lubricant additives for friction reduction, wear protection, or viscosity improvement have been widely studied. However, single additives achieving all three functions are rare. To address this need, we have explored the combination of polymer topology with organic–inorganic hybrid chemistry to simultaneously vary the temperature- and shear-dependent properties of polymer additives in solution and at solid surfaces. A topological library of lubricant additives, based on statistical copolymers of stearyl methacrylate and methyl methacrylate, ranging from linear to branched star architectures, was prepared using ruthenium-catalyzed controlled radical polymerization. Control over the polymerization yielded additives with low dispersity and comparable molecular weights, allowing evaluation of the influence of polymer architecture on friction reduction, wear protection, and bulk viscosity improvement in a commercial base oil (Yubase 4). Structure–performance relationships for these functions were assessed by a combination of a high-speed surface force apparatus (HS-SFA) experiments, wear track profilometry, quartz crystal microbalance analysis, and solution viscometry. The custom-built HS-SFA provides a unique experimental environment to measure the boundary lubrication performance under extreme shear rates (≈107s–1) for prolonged times (24 h), mimicking the extreme conditions of automotive applications. These experiments revealed that the performance of the additives as boundary lubricants and wear protectants scales with the degree of branching. The branched architectures prohibit ordering of the additives in thin films under high-load conditions, leading to a thicker absorbed polymer brush boundary layer and therefore enhanced film fluidity and lubricity. Additionally, star polymers with increasing arm number lead to bulk viscosity modification, reflected by a significant increase in the viscosity index compared to the commercial base oil. Although outperformed by linear polymers for bulk viscosity improvement, the (hybrid) star polymers successfully combine the three distinct lubricant additive functions: friction reduction, wear protection, and bulk viscosity improvement—in a single polymeric structure. It should also be noted that, judging from HS-SFA experiments, hybrid stars carrying a silicate-based core outperform their fully organic analogues as boundary lubricants. The enhanced performance is most likely driven by attractive forces between the silicate cores and the employed metallic surfaces. Combining three function in one minimizes formulation complexity and thus opens a route to fundamentally understand and formulate key design parameters for the development of novel multifunction lubricant additives.

Conditions for the synthesis of star-shaped polymers via controlled radical polymerization (CRP) with minimized star–star coupling are presented. By systematically grafting a variety of polyacrylates (methyl acrylate, tert-butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate) from cores carrying 4–8 initiating sites, it was found that traditional factors increasing star–star coupling, (i) the number of arms, (ii) the length of the arms, and (iii) the steric bulk of the monomer side-chain, could be controlled. This allows high monomer conversion (>95%) and low-dispersity polymers (Đ< 1.08) to be obtained for molecular weights up to ∼300 000 g mol–1. In addition to the suppression of coupling events, these improved reaction conditions maximize chain-end fidelity and permit the synthesis of well-defined (multi)block copolymer stars through in situchain extension reactions. These advantages significantly broaden the synthetic scope and structural integrity for CRP-derived star polymers.

We disclose a method for the synthesis of chiral colloids from spontaneously formed hollow sugar-surfactant microtubes with internally confined mobile colloidal spheres. Key feature of our approach is the grafting of colloid surfaces with photoresponsive coumarin moieties, which allow for UV-induced, covalent clicking of colloids into permanent chains, with morphologies set by the colloid-to-tube diameter ratio. Subsequent dissolution of tube confinement yields aqueous suspensions that comprise bulk quantities of a variety of linear chains, including single helical chains of polystyrene colloids. These colloidal equivalents of chiral (DNA) molecules are intended for microscopic study of chiral dynamics on a single-particle level.

In the past decade, stimuli-responsive hydrogels are increasingly studied as biomaterials for tissue engineering and regenerative medicine purposes. Smart hydrogels can not only replicate the physicochemical properties of the extracellular matrix but also mimic dynamic processes that are crucial for the regulation of cell behavior. Dynamic changes can be influenced by the hydrogel itself (isotropic vs anisotropic) or guided by applying localized triggers. The resulting swelling–shrinking, shape-morphing, as well as patterns have been shown to influence cell function in a spatiotemporally controlled manner. Furthermore, the use of stimuli-responsive hydrogels as bioinks in 4D bioprinting is very promising as they allow the biofabrication of complex microstructures. This perspective discusses recent cutting-edge advances as well as current challenges in the field of smart biomaterials for tissue engineering. Additionally, emerging trends and potential future directions are addressed.