Linear Assembly of Two-Patch Silica Nanoparticles and Control of Chain Length by Coassembly with Colloidal Chain Stoppers

Liu, Bin; Li, Weiya; Duguet, Étienne; Ravaine, Serge

doi:10.1021/acsmacrolett.1c00699

Cited by 10 publications

(16 citation statements)

References 30 publications

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“…The NP amphiphiles could be coassembled with polymer amphiphilic molecules. ,,− The coassembly of PS- b -PEO-tethered iron oxide NPs (SPIONs) and poly(styrene)- b -poly(acrylic acid) (PS- b -PAA) yielded magnetic vesicles, in which the membrane thickness was tunable in the range of 9.8–93.2 nm by controlling the molar ratio of copolymer to SPIONs. This effect was caused by a transition from the NP monolayer to a bilayer and eventually to a multilayer.…”

Section: Directional Assembly Of Polymer-tethered Nanoparticles Guide...mentioning

confidence: 99%

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

et al. 2022

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Conspectus Current interest in nanoparticle ensembles is motivated by their collective synergetic properties that are distinct from or better than those of individual nanoparticles and their bulk counterparts. These new advanced optical, electronic, magnetic, and catalytic properties can find applications in advanced nanomaterials and functional devices, if control is achieved over nanoparticle organization. Self-assembly offers a cost-efficient approach to produce ensembles of nanoparticles with well-defined and predictable structures. Nanoparticles functionalized with polymer molecules are promising building blocks for self-assembled nanostructures, due to the comparable dimensions of macromolecules and nanoparticles, the ability to synthesize polymers with various compositions, degrees of polymerization, and structures, and the ability of polymers to self-assemble in their own right. Moreover, polymer ligands can endow additional functionalities to nanoparticle assemblies, thus broadening the range of their applications. In this Account, we describe recent progress of our research groups in the development of new strategies for the self-assembly of nanoparticles tethered to macromolecules. At the beginning of our journey, we developed a new approach to patchy nanoparticles and their self-assembly. In a thermodynamically driven strategy, we used poor solvency conditions to induce homopolymer surface segregation in pinned micelles (patches). Patchy nanoparticles underwent self-assembly in a well-defined and controlled manner. Following this work, we overcame the limitation of low yield of the generation of patchy nanoparticles, by using block copolymer ligands. For block copolymer-capped nanoparticles, patch formation and self-assembly were “staged” by using distinct stimuli for each process. We expanded this work to the generation of patchy nanoparticles via dynamic exchange of block copolymer molecules between the nanoparticle surface and micelles in the solution. The scope of our work was further extended to a series of strategies that utilized the change in the configuration of block copolymer ligands during nanoparticle interactions. To this end, we explored the amphiphilicity of block copolymer-tethered nanoparticles and complementary interactions between reactive block copolymer ligands. Both approaches enabled exquisite control over directional and self-limiting self-assembly of complex hierarchical nanostructures. Next, we focused on the self-assembly of chiral nanostructures. To enable this goal, we attached chiral molecules to the surface of nanoparticles and organized these hybrid building blocks in ensembles with excellent chiroptical properties. In summary, our work enables surface engineering of polymer-capped nanoparticles and their controllable and predictable self-assembly. Future research in the field of nanoparticle self-assembly will include the development of effective characterization techniques, the synthesis of new functional polymers, and the development of environmentally responsive se...

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Section: Directional Assembly Of Polymer-tethered Nanoparticles Guide...mentioning

confidence: 99%

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

et al. 2022

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“…Among others, we expect that the interlocking of aggregated cubes will lead to much more rigid structures compared to the ones formed by patchy spheres, e.g., self-assembly of two-patch particles into rigid rods instead of flexible colloidal polymers. 23,24 Patchy particle models can also be regarded as heavily coarsegrained representations of proteins; 25 although this description appears rather reductionistic at first glance, previous simulations have demonstrated excellent agreement between the phase diagrams of such patchy particles and experimental results for γcrystallin and lysozyme. 26 The computational efficiency of such a modeling approach lends itself to study the mesoscopic assembly of various proteins, such as amyloid fibers and virus capsids, with impressive results despite its conceptual simplicity.…”

Section: ■ Introductionmentioning

confidence: 99%

“…In this work, we study the self-assembly behavior of amphiphilic cubescolloids that combine both shape and interaction anisotropyanticipating an interesting interplay between these properties. Among others, we expect that the interlocking of aggregated cubes will lead to much more rigid structures compared to the ones formed by patchy spheres, e.g., self-assembly of two-patch particles into rigid rods instead of flexible colloidal polymers. , …”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of Amphiphilic Cubes in Suspension

Kobayashi

Nikoubashman

2022

Langmuir

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We study the self-assembly of amphiphilic cubic colloids using molecular dynamics as well as rejection-free kinetic Monte Carlo simulations. We vary both the number and location of the solvophobic faces (patches) on the cubes at several colloid volume fractions and determine the resulting size and shape distributions of the selfassembled aggregates. When the binding energy is comparable to the thermal energy of the system, aggregates typically consist of only few spontaneously associating/dissociating colloids. Increasing the binding energy (or lowering the temperature) leads to the emergence of highly stable aggregates, e.g., small dimers in pure suspensions of one-patch cubes or large (system-spanning) aggregates in suspensions of multipatch colloids. In mixtures of one-and multipatch cubes, the average aggregation number increases with increasing number of solvophobic faces on the multipatch cubes as well with increasing fraction of multipatch cubes. The resulting aggregate shapes range from elongated rods over fractal objects to compact spheres, depending on the number and arrangement of solvophobic patches on the cubic colloids. Our findings establish the complex selfassembly pathways for a class of building blocks that combine both interaction and shape anisotropy, with the potential of forming hierarchically ordered superstructures.

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“…Patchy particles, which are particles having a zone of different chemical nature or topology, are good candidates as building units to fabricate new colloidal structures with photonic or catalytic properties by self-assembly [1,2]. In particular, two-patch particles have been assembled into colloidal clusters [3], linear chains [4][5][6] or two-dimensional lattices [7].…”

Section: Introductionmentioning

confidence: 99%

“…Patchy gold nanorods have been produced by Kumacheva et al, who took advantage of the presence of {111} facets specifically at both ends of gold nanorods to graft thiol-ended PS macromolecules only there [4]. We have reported the synthesis of silica/PS bipods by emulsion polymerisation of styrene in the presence of silica particles of a few tens of nanometres [5,6]. The exceptional morphological yield of 97% has allowed the fabrication of quasi-pure batches of 2-patch silica particles by dissolution of the nodules of so-called bipods and thus to perform self-assembly studies.…”

Section: Introductionmentioning

confidence: 99%

Silica/polystyrene bipod-like submicron colloids synthesized by seed-growth dispersion polymerisation as precursors for two-patch silica particles

Shanmugathasan

Bagur

Ducrot

et al. 2022

Colloids and Surfaces A: Physicochemical and Engineering Aspect

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Linear Assembly of Two-Patch Silica Nanoparticles and Control of Chain Length by Coassembly with Colloidal Chain Stoppers

Cited by 10 publications

References 30 publications

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

Polymer-Tethered Nanoparticles: From Surface Engineering to Directional Self-Assembly

Self-Assembly of Amphiphilic Cubes in Suspension

Silica/polystyrene bipod-like submicron colloids synthesized by seed-growth dispersion polymerisation as precursors for two-patch silica particles

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