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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]

Engineering synthetic materials that mimic the complex rhythmic oscillatory behavior of living cells is a fundamental challenge in science and technology. Up to now, the reported synthetic model system still cannot compete with nature in oscillatory modes and amplitudes. Presented here is a novel alternating copolymer vesicle that exhibits drastic and multimode shape oscillations in real time, which are controlled by polymer concentrations and driven by the Belousov—Zhabotinsky oscillatory reaction, including swelling/deswelling, twisting/detwisting, stretching/shrinking, fusion/fission, and multiple division. Some of them, especially the fission oscillation, have not been observed before. In addition, the oscillation magnitude with regard to diameter is much larger than that of previously reported self‐oscillating vesicles. Such a self‐oscillating vesicle transformer would extend the complexity and capacity of membrane deformations in synthetic systems, approaching those of natural cells. [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]

A dandelion-like supramolecular polymer (DSP) with a 'sphere-star-parachute' topological structure consisting of a spherical hyperbranched core and many parachute-like arms is constructed by the non-covalent host-guest coupling between a cyclodextrin-endcapped hyperbranched multi-arm copolymer (host) and many functionalized adamantanes with each having three alkyl chain arms (guests). The obtained DSPs can further self-assemble into nanotubes in water in a hierarchical way from vesicles to nanotubes through sequential vesicle aggregation and fusion steps. The nanotubes have a bilayer structure consisting of multiple 'hydrophobic-hyperbranched-hydrophilic' layers. Such a structure is very useful for constructing a chlorosome-like artificial aqueous light-harvesting system, as demonstrated here, via the incorporation of hydrophobic 4-(2-hydroxyethylamino)-7-nitro-2,1,3-benzoxadiazole as donors inside the hyperbranched cores of the nanotubes and the hydrophilic Rhodamine B as the acceptors immobilized on the nanotube surfaces. This as-prepared nanotube light harvesting system demonstrates unexpectedly high energy transfer efficiency (above 90%) in water. This extends supramolecular polymers with more complex topological structure, special self-assembly behavior, and new functionality. [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]

Highlights • Simple and efficient polymer based aqueous detection system for toxic Hg2+. • Turn-on response visible to naked eye. • Real-time detection of Hg2+ in raw water samples. • Excellent quantifying ability in terms of percentage recovery. Abstract In recent years, there has been an ever-increasing demand to develop highly sensitive and selective colorimetric detection systems to tackle the growing threat of potentially toxic mercuric ions (Hg2+) exposure at the global level. However, most of the reported chemosensors for Hg2+ detection worked only in organic or in mixed solutions (organic/aqueous). The properties of the reported aqueous chemosensors for Hg2+ are not satisfactory. Herein, we take the advantage and present the first vesicular chemical sensor for the aqueous detection of Hg2+ with a high efficiency and selectivity. The vesicles were obtained through the aqueous self-assembly of the newly synthesized amphiphilic alternating copolymer poly(2, 3-dihydroxybutylene-alt-2,3-dihydroxybutylenedithioether) [P(DHB-a-DHBDT)] grafted with 2-(5-bromopyridine-2-yl)-3′,6′-bis(diethylamino)spiro[isoindoline-1,9′-xanthene]-3-thione (PST) probes. After the addition of Hg2+, the colorless aqueous solution of the vesicles changed into pink color accompanied by the significant enhancement of photophysical (emission and absorption) intensities at 580 nm and 559 nm, respectively. This color transition from colorless to pink allows the "bare-eye" detection of Hg2+ ions in the aqueous medium. The vesicular sensor also shows high selectivity for Hg2+ detection among miscellaneous metal cations. The detection limit (LOD) is about 53.0 nM, which is approximately one or two order of magnitude higher than those of the reported aqueous Hg2+ chemosensors. The mechanism study indicates the significant enhancement of emission and absorption intensities in response to Hg2+ should be attributed to the spirolactam ring opening via photoinduced electron transfer (PET) of xanthene moiety in the PST probes. Most importantly, the newly developed polymeric vesicle sensors shows great potential for the detection and quantification of Hg2+ with excellent selectivity in real water samples with the percentage recovery of 102–98%. [ABSTRACT FROM AUTHOR]