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This work reports novel alternating copolymer vesicles and their facile functionalization with carboxyl and amino groups through click copolymerization.

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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 nm) after functionalization with amino groups through click copolymerization.

This study reports the first polymer vesicle sensor for the visual detection of SO and its derivatives in water. A strong binding ability between tertiary alkanolamines and SO has been used as the driving force for the detection by the graft of tertiary amine alcohol (TAA) groups onto an amphiphilic hyperbranched multiarm polymer, which can self-assemble into vesicles with enriched TAA groups on the surface. The polymer vesicles will undergo proton exchange with cresol red (CR) to produce CR-immobilized vesicles (CR@vesicles). Subsequently, through competitive binding with the TAA groups between CR and SO or HSO, the CR@vesicles (purple) can quickly change into SO@vesicles (colorless) with the release of protonated CR (yellow). Such a fast purple to yellow transition in the solution allows the visual detection of SO or its derivatives in water by the naked eye. A visual test paper for SO gas has also been demonstrated by the adsorption of CR@vesicles onto paper. Meanwhile, the detection limit of CR@vesicles for HSO is approximately 25 nM, which is improved by approximately 30 times when compared with that of small molecule-based sensors with a similar structure (0.83 μM). Such an enhanced detection sensitivity should be related to the enrichment of TAA groups as well as the CR in CR@vesicles. In addition, the CR@vesicle sensors also show selectivity and specificity for the detection of SO or HSO among anions such as F, Br, Cl, SO, NO, CO, SO, SCN, AcO, SO, S, and HCO.