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The field of supramolecular chemistry has witnessed tremendous progress in bringing the system away from equilibrium for traditionally inaccessible structures and functions. Vesicular assemblies with complex energy landscapes and pathways, which are reminiscent of diverse cellular vesicles like exosomes, remain exceedingly rare. Here, relying on the activation of oligo(ethylene glycol) (OEG) interdigitation and the encoded conformational freedom in monodisperse Janus dendrimers, we reveal a rich landscape and a pathway selection of distinct vesicles. The interdigitation can be selectively switched on and off using temperature ramps, and the critical temperatures can be further determined by molecular design. Our findings suggest that synthetic vesicles, with different energy states and unexpected transition pathways, emulate dynamic cellular vesicles in nature. We anticipate that vesicles with an activated OEG corona conformation will open new routes for nanomedicine and advanced materials.

The enhanced membrane stability and chemical versatility of polymeric vesicles have made them promising tools in micro/nanoreactors, drug delivery, cell mimicking, etc. However, shape control over polymersomes remains a challenge and has restricted their full potential. Here we show that local curvature formation on the polymeric membrane can be controlled by applying poly(N-isopropylacrylamide) as a responsive hydrophobic unit, while adding salt ions to modulate the properties of poly(N-isopropylacrylamide) and its interaction with the polymeric membrane. Polymersomes with multiple arms are fabricated, and the number of arms could be tuned by salt concentration. Furthermore, the salt ions are shown to have a thermodynamic effect on the insertion of poly(N-isopropylacrylamide) into the polymeric membrane. This controlled shape transformation can provide evidence for studying the role of salt ions in curvature formation on polymeric membranes and biomembranes. Moreover, potential stimuli-responsive non-spherical polymersomes can be good candidates for various applications, especially in nanomedicine., (© 2023. The Author(s).)

An adaptive surface that can sense and respond to environmental stimuli is integral to smart functional materials. Here, we report pH-responsive anchoring systems onto the poly(ethylene glycol) (PEG) corona of polymer vesicles. The hydrophobic anchor, pyrene, is reversibly inserted into the PEG corona through the reversible protonation of its covalently linked pH-sensing group. Depending on the p K of the sensor, the pH-responsive region is engineered from acidic to neutral and basic conditions. The switchable electrostatic repulsion between the sensors contributes to the responsive anchoring behavior. Our findings provide a new responsive binding chemistry for the creation of smart nanomedicine and a nanoreactor.a of the sensor, the pH-responsive region is engineered from acidic to neutral and basic conditions. The switchable electrostatic repulsion between the sensors contributes to the responsive anchoring behavior. Our findings provide a new responsive binding chemistry for the creation of smart nanomedicine and a nanoreactor.

For the maintenance of a biological system, spatial organization of material condensates within the cell through the dissipation of energy is crucial. Besides directed transport via microtubules, material arrangement can be achieved via motor protein facilitated adaptive active diffusiophoresis. For example, the distribution of membrane proteins during the cell division of Escherichia coli is affected by the MinD system. Synthetic active motors exhibit the ability to simulate natural motors. Here we propose an active Au-Zn nanomotor driven by water and discovered an interesting adaptive interaction mode of the diffusiophoretic Au-Zn nanomotors with passive condensate particles in different environments. It is found that the attraction/repulsion between the nanomotor and passive particles is adaptive, while an interesting hollow pattern is formed with a negatively charged substrate and a cluster pattern is favored with a positively charged substrate.

Motion is influenced by many different aspects of a micromotor's design, such as shape, roughness and the type of materials used. When designing a motor, asymmetry is the main requirement to take into account, either in shape or in catalyst distribution. It influences both speed and directionality since it dictates the location of propulsion force. Here, we combine asymmetry in shape and asymmetry in catalyst distribution to study the motion of soft micromotors. A microfluidic method is utilized to generate aqueous double emulsions, which upon UV-exposure form asymmetric microgels. Taking advantage of the flexibility of this method, we fabricated micromotors with homogeneous catalyst distribution throughout the microbead and micromotors with different degrees of catalyst localization within the active site. Spatial control over catalyst positioning is advantageous since less enzyme is needed for the same propulsion speed as the homogeneous system and it provides further confinement and compartmentalization of the catalyst. This proof-of-concept of our new design will make the use of enzymes as driving forces for motors more accessible, as well as providing a new route for compartmentalizing enzymes at interfaces without the need for catalyst-specific functionalization.

Attributed to the miniaturized body size and active mobility, micro- and nanomotors (MNMs) have demonstrated tremendous potential for medical applications. However, from bench to bedside, massive efforts are needed to address critical issues, such as cost-effective fabrication, on-demand integration of multiple functions, biocompatibility, biodegradability, controlled propulsion and in vivo navigation. Herein, we summarize the advances of biomedical MNMs reported in the past two decades, with particular emphasis on the design, fabrication, propulsion, navigation, and the abilities of biological barriers penetration, biosensing, diagnosis, minimally invasive surgery and targeted cargo delivery. Future perspectives and challenges are discussed as well. This review can lay the foundation for the future direction of medical MNMs, pushing one step forward on the road to achieving practical theranostics using MNMs., Competing Interests: The authors declare no conflicts of interest., (© 2022 Chinese Pharmaceutical Association and Institute of Materia Medica, Chinese Academy of Medical Sciences. Production and hosting by Elsevier B.V.)

Covalent and non-covalent molecular binding are two strategies to tailor surface properties and functions. However, the lack of responsiveness and requirement for specific binding groups makes spatiotemporal control challenging. Here, we report the adaptive insertion of a hydrophobic anchor into a poly(ethylene glycol) (PEG) host as a non-covalent binding strategy for surface functionalization. By using polycyclic aromatic hydrocarbons as the hydrophobic anchor, hydrophilic charged and non-charged functional modules were spontaneously loaded onto PEG corona in 2 min without the assistance of any catalysts and binding groups. The thermodynamically favourable insertion of the hydrophobic anchor can be reversed by pulling the functional module, enabling programmable surface functionalization. We anticipate that the adaptive molecular recognition between the hydrophobic anchor and the PEG host will challenge the hydrophilic understanding of PEG and enhance the progress in nanomedicine, advanced materials and nanotechnology., (© 2022. The Author(s).)

As a novel mobile nanodevice, micro-nano motors (MNMs) can convert the energy of the surrounding environment into mechanical motion. With this unique ability, they promise revolutionary potential in bio-applications including precise drug delivery, bio-sensing, and noninvasive surgery. Yet for practically reaching the target and fulfilling these tasks in dynamically changing bio-environment, environment adaptivity beyond propulsion is important yet challenging. MNMs with taxis behavior/autonomous target-seeking ability offer a desirable solution. These motors can adaptively move to the target location and complete the task. Thanks to the persistent efforts of researchers, tactic MNMs have shown automatic navigation to target under various energy fields, not only in static environments, but also in shear rheological conditions that simulate blood flow. Therefore, tactic motors with self-targeting capability lay a concrete foundation for targeted drug delivery, cell transplantation, and thrombus ablation. This review systematically presents the moving principle, design, and biological applications of tactic MNMs under different energy fields. Through in-depth analysis of state-of-art progress, the obstacles of the field and possible solutions are discussed. With the continuous innovation and breakthroughs of multi-disciplinary researchers, MNMs with taxis behavior are expected to provide a revolutionary solution for cancer and other major diseases in the biomedical field., (© 2022 Wiley-VCH GmbH.)

Inspired by the tactic organisms in Nature that can self-direct their movement following environmental stimulus gradient, we proposed a DNase functionalized Janus nanoparticle (JNP) nanomotor system for the first time, which can be powered by ultralow nM to μM levels of DNA. The system exhibited interesting chemotactic behavior toward a DNA richer area, which is physiologically related with many diseases including tumors. In the presence of the subtle DNA gradient generated by apoptotic tumor cells, the cargo loaded nanomotors were able to sense the DNA signal released by the cells and demonstrate directional motion toward tumor cells. For our system, the subtle DNA gradient by a small amount (10 μL) of tumor cells is sufficient to induce the chemotaxis behavior of self-navigating and self-targeting ability of our nanomotor system, which promises to shed new light for tumor diagnosis and therapy.

Biomembrane curvature formation has long been observed to be essential in the change of membrane morphology and intracellular processes. The significant importance of curvature formation has attracted scientists from different backgrounds to study it. Although magnificent progress has been achieved using liposome models, the instability of these models restrict further exploration. Here, we report a new approach to mimic biomembrane curvature formation using polymersomes as a model, and poly(N-isopropylacrylamide) to induce the local curvature based on its co-nonsolvency phenomenon. Curvatures form when poly(N-isopropylacrylamide) becomes hydrophobic and inserts into the membrane through solvent addition. The insertion area can be fine-tuned by adjusting the poly(N-isopropylacrylamide) concentration, accompanied by the formation of new polymersome-based non-axisymmetric shapes. Moreover, a systematic view of curvature formation is provided through investigation of the segregation, local distribution and dissociation of inserted poly(N-isopropylacrylamide). This strategy successfully mimicks biomembrane curvature formation in polymersomes and a detailed observation of the insertion can be beneficial for a further understanding of the curvature formation process. Furthermore, polymer insertion induced shape changing could open up new routes for the design of non-axisymmetric nanocarriers and nanomachines to enrich the boundless possibilities of nanotechnology.

Polymeric self-assembled structures have been a topic of interest in the last few decades, specifically for the use of biomedical applications, such as drug delivery. It is exciting to investigate the formation of various shapes and sizes of such structures, as the morphology is crucial for their function. In this manuscript the important factors to control the morphology during self-assembly and subsequent shape transformation processes are discussed. We describe the main parameters to control and show the practical application of these parameters on biodegradable amphiphilic PEG-PDLLA block-copolymers. Thereby a variety of different morphologies, including micelles, worms, LCVs, discs, rods, stomatocytes, nested vesicles, and spherical vesicles of various sizes are created using only four diblock-copolymers and with careful tuning of two organic solvents. Further advances will lead to formation of more complex structures.