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A similarity between chemical reactions and self-assembly of nanoparticles offers a strategy that can enrich both the synthetic chemistry and the nanoscience fields. Synthetic methods should enable quantitative control of the structural characteristics of nanoparticle ensembles such as their aggregation number or directionality, whereas the capability to visualize and analyze emerging nanostructures using characterization tools can provide insight into intelligent molecular design and mechanisms of chemical reactions. We explored this twofold concept for an exemplary system including the polymerization of bifunctional nanoparticles in the presence of monofunctional colloidal chain stoppers. Using reaction-specific design rules, we synthesized chain stoppers with controlled reactivity and achieved quantitative fine-tuning of the self-assembled structures. Analysis of the nanostructures provided information about polymerization kinetics, side reactions, and the distribution of all of the species in the reaction system. A quantitative model was developed to account for the reactivity, kinetics, and side reactions of nanoparticles, all governed by the design of colloidal chain stoppers. This work provided the ability to test theoretical models developed for molecular polymerization.

Chiral packing of ligands on the surface of nanoparticles (NPs) is of fundamental and practical importance, as it determines how NPs interact with each other and with the molecular world. Herein, for gold nanorods (NRs) capped with end‐grafted nonchiral polymer ligands, we show a new mechanism of chiral surface patterning. Under poor solvency conditions, a smooth polymer layer segregates into helicoidally organized surface‐pinned micelles (patches). The helicoidal morphology is dictated by the polymer grafting density and the ratio of the polymer ligand length to nanorod radius. Outside this specific parameter space, a range of polymer surface structures was observed, including random, shish‐kebab, and hybrid patches, as well as a smooth polymer layer. We characterize polymer surface morphology by theoretical and experimental state diagrams. The helicoidally organized polymer patches on the NR surface can be used as a template for the helicoidal organization of other NPs, masked synthesis on the NR surface, as well as the exploration of new NP self‐assembly modes. Gold nanorods, end‐grafted with achiral polymer ligands, show a new mechanism of chiral surface patterning giving a helicoidal morphology. This morphology is dictated by the relationship between the polymer grafting density and the ratio of the polymer length to the nanorod radius. [ABSTRACT FROM AUTHOR]

The fabrication of multifunctional materials with tunable structure and properties requires programmed binding of their building blocks. For example, particles organized in long-ranged structures by external fields can be bound permanently into stiff chains through electrostatic or van der Waals attraction, or into flexible chains through soft molecular linkers such as surface-grafted DNA or polymers. Here, we show that capillarity-mediated binding between magnetic nanoparticles coated with a liquid lipid shell can be used for the assembly of ultraflexible microfilaments and network structures. These filaments can be magnetically regenerated on mechanical damage, owing to the fluidity of the capillary bridges between nanoparticles and their reversible binding on contact. Nanocapillary forces offer opportunities for assembling dynamically reconfigurable multifunctional materials that could find applications as micromanipulators, microbots with ultrasoft joints, or magnetically self-repairing gels. [ABSTRACT FROM AUTHOR]

The resemblance between colloidal and molecular polymerization reactions is very useful in fundamental studies of polymerization reactions, as well as in the development of new nanoscale systems with desired properties. Future applications of colloidal polymers will require nanoparticle ensembles with a high degree of complexity that can be realized by hetero-assembly of NPs with different dimensions, shapes, and compositions. A method has been developed to apply strategies from molecular copolymerization to the co-assembly of gold nanorods with different dimensions into random and block copolymer structures (plasmonic copolymers). The approach was extended to the co-assembly of random copolymers of gold and palladium nanorods. A kinetic model validated and further expanded the kinetic theories developed for molecular copolymerization reactions. [ABSTRACT FROM AUTHOR]

Organized arrays of anisotropic nanoparticles show electronic and optical properties that originate from the coupling of shape-dependent properties of the individual nanorods. The organization of nanorods in a controllable and predictable way provides a route to the fabrication of new materials and functional devices. So far, significant progress has been achieved in the self-assembly of nanorod arrays, yet the realization of a range of different structures requires changing the surface chemistry of the nanoparticles. We organized metal nanorods in structures with varying geometries by using a striking analogy between amphiphilic ABA triblock copolymers and the hydrophilic nanorods tethered with hydrophobic polymer chains at both ends. The self-assembly was tuneable and reversible and it was achieved solely by changing the solvent quality for the constituent blocks. This approach provides a new route to the organization of anisotropic nanoparticles by using the strategies that are established for the self-assembly of block copolymers. [ABSTRACT FROM AUTHOR]

Die Selbstorganisation kolloidaler Analoga von molekularen Copolymeren kann grundlegende Erkenntnisse für die Gebiete der molekularen Copolymerisation und der Nanotechnologie liefern. In ihrer Zuschrift auf S. 2686 ff. präsentieren K. Liu, E. Kumacheva et al. eine mikroskopische und spektroskopische Analyse, mit deren Hilfe sie Design ‐ Regeln und ein kinetisches Modell für das Wachstum kolloidaler Zufalls ‐ und Blockcopolymere aus plasmonischen Nanostäben unterschiedlicher Länge und Zusammensetzung formulieren. [ABSTRACT FROM AUTHOR]

The motion of nanoparticles (NPs) in entangled melts of linear polymers and nonconcatenated ring polymers are compared by large-scale molecular dynamics simulations. The comparison provides a paradigm for the effects of polymer architecture on the dynamical coupling between NPs and polymers in nanocomposites. Strongly suppressed motion of NPs with diameter d larger than the entanglement spacing a is observed in a melt of linear polymers before the onset of Fickian NP diffusion. This strong suppression of NP motion occurs progressively as d exceeds a and is related to the hopping diffusion of NPs in the entanglement network. In contrast to the NP motion in linear polymers, the motion of NPs with d > a in ring polymers is not as strongly suppressed prior to Fickian diffusion. The diffusion coefficient D decreases with increasing d much slower in entangled rings than in entangled linear chains. NP motion in entangled nonconcatenated ring polymers is understood through a scaling analysis of the coupling between NP motion and the self-similar entangled dynamics of ring polymers. [ABSTRACT FROM AUTHOR]

Self-organization of nanoparticles is an efficient strategy for producing nanostructures with complex, hierarchical architectures. The past decade has witnessed great progress in nanoparticle self-assembly, yet the quantitative prediction of the architecture of nanoparticle ensembles and of the kinetics of their formation remains a challenge. We report on the marked similarity between the self-assembly of metal nanoparticles and reaction-controlled step-growth polymerization. The nanoparticles act as multifunctional monomer units, which form reversible, noncovalent bonds at specific bond angles and organize themselves into a colloidal polymer. We show that the kinetics and statistics of step-growth polymerization enable a quantitative prediction of the architecture of linear, branched, and cyclic self-assembled nanostructures; their aggregation numbers and size distribution; and the formation of structural isomers. [ABSTRACT FROM AUTHOR]