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Patchy nanoparticles (NPs) show many important applications, especially for constructing structurally complex colloidal materials, but existing synthetic strategies generate patchy NPs with limited types of symmetry. This article describes a versatile copolymer ligand‐based strategy for the scalable synthesis of uniform Au‐(SiO2)x patchy NPs (x is the patch number and 1 ≤ x ≤ 5) with unusual symmetry at high yield. The hydrolysis and condensation of tetraethyl orthosilicate on block‐random copolymer ligands induces the segregation of copolymers on gold NPs (AuNPs) and hence governs the structure and distribution of silica patches formed on the AuNPs. The resulting patchy NPs possess unique configurations where the silica patches are symmetrically arranged at one side of the core NP, resembling the geometry of polar small molecules. The number, size, and morphology of silica patches, as well as the spacing between the patches and the AuNP can be precisely tuned by tailoring copolymer architectures, grafting density of copolymers, and the size of AuNPs. Furthermore, it is demonstrated that the Au‐(SiO2)x patchy NPs can assemble into more complex superstructures through directional interaction between the exposed Au surfaces. This work offers new opportunities of designing next‐generation complex patchy NPs for applications in such as biomedicines, self‐assembly, and catalysis. [ABSTRACT FROM AUTHOR]

Ultrasmall silica‐based nanoparticles (SNPs) are attractive for application in many fields, but existing synthetic approaches show limited control over the size and morphology of these SNPs. This study describes a general single copolymer chain‐mediated strategy for the scalable synthesis of highly monodispersed symmetric and asymmetric SNPs with sub‐50 nm diameter. Random copolymers of poly(acrylic acid‐r‐styrene) intramolecularly collapse into ultrasmall single‐chain nanoparticles and serve as seeds to template the hydrolysis of silica precursors to produce uniform SNPs. It is shown in experiments and simulations that the composition and random architecture of the copolymers are crucial to the formation of ultrasmall seeds and the uniform deposition of silica. Furthermore, tailoring the architecture of copolymers can be used to produce ultrasmall asymmetric Janus‐like and dumbbell‐like SNPs with well‐defined polymer and silica domains. This study paves a new route to the scalable production of ultrasmall SNPs with tailored morphologies. [ABSTRACT FROM AUTHOR]

The stepwise self-assembly of hollow plasmonic vesicles with vesicular membranes containing strings of gold nanoparticles (NPs) is reported. The formation of chain vesicles can be controlled by tuning the density of the polymer ligands on the surface of the gold NPs. The strong absorption of the chain vesicles in the near-infrared (NIR) region leads to a much higher efficiency in photoacoustic (PA) imaging than for non-chain vesicles. The chain vesicles were further employed for the encapsulation of drugs and the NIR light triggered release of pay loads. This work not only offers a new platform for controlling the hierarchical self-assembly of NPs, but also demonstrates that the physical properties of the materials can be tailored by controlling the spatial arrangement of NPs within assemblies to achieve a better performance in biomedical applications. [ABSTRACT FROM AUTHOR]

The hierarchical assembly of multifunctional materials is challenging. In their Communication on page 15809 ff., Z. H. Nie, X. Y. Chen, and co‐workers report the stepwise assembly of block‐copolymer‐tethered gold nanoparticles into strings that subsequently fold into vesicles with chain‐like ordering of the nanoparticles in the membrane. The resulting vesicular assemblies can be used for photoacoustic imaging and drug delivery owing to their strong absorption in the near‐infrared region. [ABSTRACT FROM AUTHOR]