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Artificial vesicles are recognized as powerful platforms for a large body of research across the disciplines of chemistry, physics and biology. Despite the great progress, control of the size distribution to make uniform vesicles remains fundamentally difficult due to the highly uncontrollable growth kinetics, especially for micron‐sized vesicles. Here we report a template‐free living self‐assembly method to prepare monodisperse vesicles around 1 μm from an alternating copolymer. The polymer forms nanodisks (ca. 9 nm) in N,N‐dimethylformamide (DMF), acting as seeds for subsequent growth. By adding water, the nanodisks gradually grow into larger circular bilayer nanosheets, which bend to crowns and continue to grow into uniform micron‐sized vesicles. The first‐order growth kinetics as well as the small size polydispersity index (<0.1) suggests the living self‐assembly characteristics. This work paves a new way in both living self‐assembly and monodisperse polymer vesicles. [ABSTRACT FROM AUTHOR]

Hierarchical self‐assembly of synthetic polymers in solution represents one of the sophisticated strategies to replicate the natural superstructures which lay the basis for their superb functions. However, it is still quite challenging to increase the degree of complexity of the as‐prepared assemblies, especially in a large scale. Liquid–liquid phase separation (LLPS) widely exists in cells and is assumed to be responsible for the formation of many cellular organelles without membranes. Herein, through integrating LLPS with the polymerization‐induced self‐assembly (PISA), a coacervate‐assisted PISA (CAPISA) methodology to realize the one‐pot and scalable preparation of hierarchical bishell capsules (BCs) from nanosheets with ultrathin lamellae phase (sub‐5 nm), microflakes, unishell capsules to final BCs in a bottom‐up sequence is presented. Both the self‐assembled structure and the dynamic formation process of BCs have been disclosed. Since CAPISA has combined the advantages of coacervates, click chemistry, interfacial reaction and PISA, it is believed that it will become a promising option to fabricate biomimetic polymer materials with higher structural complexity and more sophisticated functions. [ABSTRACT FROM AUTHOR]

The cytoskeleton is one of the most important cellular components. Up to now, most of the reported artificial cytoskeletons are based on a gel‐in‐vesicle strategy. Herein, we report a membrane‐bound inward‐growth pathway to prepare cytoskeleton‐like and radially aligned nanofibers grown from capsule membranes to get membrane‐bound artificial cytoskeletons (MACs). The mechanism therein is disclosed through the direct observation of the intermediates in both dried and liquid states. Furthermore, the as‐prepared MACs show a selective disassembly behavior in the presence of reductants: both capsule membranes and MACs can be disassembled or only MACs can be disassembled through the selective introduction of dynamic disulfide bonds (DS) into them and by the switch of ultraviolet (UV) irradiation. The present work provides a new hierarchical self‐assembly way to construct artificial cytoskeletons with controlled compositions and orientations. [ABSTRACT FROM AUTHOR]

Marine mussels have the ability to cling to various surfaces at wet or underwater conditions, which inspires the research of catechol‐functionalized polymers (CFPs) to develop high‐performance adhesive materials. However, these polymeric adhesives generally face the problems of complex synthetic route, and it is still high challenging to prepare CFPs with excellent adhesive performance both at dry and underwater conditions. Herein, a mussel‐inspired alternating copolymer, poly(dopamine‐alt‐2,2‐bis(4‐glycidyloxyphenyl)propane) (P(DA‐a‐BGOP)), is synthesized in one step by using commercially available monomers through epoxy‐amino click chemistry. The incorporation of polar groups and rigid bisphenol A structures into the polymer backbone enhances the cohesion energy of polymer matrix. The alternating polymer structure endows the polymers with high catechol content and controlled polymer sequence. As a result, P(DA‐a‐BGOP) exhibits a strong bonding strength as high as 16.39 ± 2.13 MPa on stainless steel substrates after a hot pressing procedure and displays a bonding strength of 1.05 ± 0.05 MPa on glass substrates at an under‐seawater condition, which surpasses most commercial adhesives. [ABSTRACT FROM AUTHOR]

Polymer self‐assembly has been a hot research topic for several decades. Different types of polymers with various architectures, like block copolymers, brush polymers, hyperbranched polymers and dendrimers, etc. are currently being investigated. Alternating copolymers (ACPs) are regular copolymers with an alternating monomeric unit structure in the polymer backbones. However, despite the great progress in the synthesis of ACPs, their self‐assembly is still in an infant stage. Very recently, our group reported a new type of amphiphilic ACPs through click copolymerization and obtained spheres, vesicles, nanotubes, and even hierarchical sea urchin‐like aggregates through the self‐assembly process. In addition, we have found some intriguing features in the self‐assembly of amphiphilic ACPs when compared with other copolymers, including their facile syntheses, readily functionalization, novel self‐assembly structures, new folding‐chain mechanisms, and uniform but ultrathin feature length. In this Concept article, we present the self‐assembly of amphiphilic ACPs together with their unique features by reviewing our latest results and related studies. Moreover, the future perspective on the self‐assembly of amphiphilic ACPs is also proposed. Our aim is to capture the attention and interest of chemists in this new area of polymerization. Click polymerization: Self‐assembly of amphiphilic alternating copolymers into diverse structures by solvent switching or emulsion‐assisted polymerization‐induced self‐assembly methods is summarized (see figure). The unique characteristics of these structures are determined both experimentally and theoretically. [ABSTRACT FROM AUTHOR]

Abstract: Hierarchical solution self‐assembly has become an important biomimetic method to prepare highly complex and multifunctional supramolecular structures. However, despite great progress, it is still highly challenging to prepare hierarchical self‐assemblies on a large scale because the self‐assembly processes are generally performed at high dilution. Now, an emulsion‐assisted polymerization‐induced self‐assembly (EAPISA) method with the advantages of in situ self‐assembly, scalable preparation, and facile functionalization was used to prepare hierarchical multiscale sea urchin‐like aggregates (SUAs). The obtained SUAs from amphiphilic alternating copolymers have a micrometer‐sized rattan ball‐like capsule (RBC) acting as the hollow core body and radiating nanotubes tens of micrometers in length as the hollow spines. They can capture model proteins effectively at an ultra‐low concentration (ca. 10 n m) after functionalization with amino groups through click copolymerization. [ABSTRACT FROM AUTHOR]

Well-defined ultrathin nanotubes (30 nm in diameter and of micrometer-scale length) were generated through the self-assembly of a novel alternative copolymer synthesized using an epoxy-thiol click-chemistry reaction. The self-assembly mechanism was investigated both by experiments and using dissipative particle dynamics (DPD) simulations. The obtained nanotubes can be readily functionalized with carboxy groups, amino groups, peptides, or other groups by simple modular click copolymerization. [ABSTRACT FROM AUTHOR]

Self‐assembly is a powerful bottom‐up strategy for preparing objects with specific ordered‐patterns in a biomimetic way. Subunits that are amenable to the self‐assembly include small molecules, polymers, and even metal nanoparticles, etc. In their Concept article on page 4255 ff., Y. Zhou et al. describe the self‐assembly of amphiphilic ACPs together with their unique features by reviewing their latest results and related studies. [ABSTRACT FROM AUTHOR]