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      Self-Assembly of Octapod-Shaped Colloidal Nanocrystals into a Hexagonal Ballerina Network Embedded in a Thin Polymer Film

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          Nanoparticles with unconventional shapes may exhibit different types of assembly architectures that depend critically on the environmental conditions under which they are formed. Here, we demonstrate how the presence of polymer (polymethyl methacrylate, PMMA) molecules in a solution, in which CdSe(core)/CdS(pods) octapods are initially dispersed, affects the octapod-polymer organization upon solvent evaporation. We show that a fast drop-drying process can induce a remarkable two-dimensional (2D) self-assembly of octapods at the polymer/air interface. In the resulting structure, each octapod is oriented like a “ballerina”, that is, only one pod sticks out of the polymer film and is perpendicular to the polymer–air interface, while the opposite pod (with respect to the octapod’s center) is fully immersed in the film and points toward the substrate, like a ballerina performing a grand battement. In some areas, a hexagonal-like pattern is formed by the ballerinas in which the six nonvertical pods, which are all embedded in the film, maintain a pod–pod parallel configuration with respect to neighboring particles. We hypothesize that the mechanism responsible for such a self-assembly is based on a fast adsorption of the octapods from bulk solution to the droplet/air interface during the early stages of solvent evaporation. At this interface, the octapods maintain enough rotational freedom to organize mutually in a pod–pod parallel configuration between neighboring octapods. As the solvent evaporates, the octapods form a ballerina-rich octapod-polymer composite in which the octapods are in close contact with the substrate. Finally, we found that the resulting octapod-polymer composite is less hydrophilic than the polymer-only film.

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          Properties and emerging applications of self-assembled structures made from inorganic nanoparticles.

          Just as nanoparticles display properties that differ from those of bulk samples of the same material, ensembles of nanoparticles can have collective properties that are different to those displayed by individual nanoparticles and bulk samples. Self-assembly has emerged as a powerful technique for controlling the structure and properties of ensembles of inorganic nanoparticles. Here we review different strategies for nanoparticle self-assembly, the properties of self-assembled structures of nanoparticles, and potential applications of such structures. Many of these properties and possible applications rely on our ability to control the interactions between the electronic, magnetic and optical properties of the individual nanoparticles.
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            Nanoscale forces and their uses in self-assembly.

             S Soh,  T Wilmer,  Kyle Bishop (2009)
            The ability to assemble nanoscopic components into larger structures and materials depends crucially on the ability to understand in quantitative detail and subsequently "engineer" the interparticle interactions. This Review provides a critical examination of the various interparticle forces (van der Waals, electrostatic, magnetic, molecular, and entropic) that can be used in nanoscale self-assembly. For each type of interaction, the magnitude and the length scale are discussed, as well as the scaling with particle size and interparticle distance. In all cases, the discussion emphasizes characteristics unique to the nanoscale. These theoretical considerations are accompanied by examples of recent experimental systems, in which specific interaction types were used to drive nanoscopic self-assembly. Overall, this Review aims to provide a comprehensive yet easily accessible resource of nanoscale-specific interparticle forces that can be implemented in models or simulations of self-assembly processes at this scale.
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              Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions.

               Stephen Mann (2009)
              Understanding how chemically derived processes control the construction and organization of matter across extended and multiple length scales is of growing interest in many areas of materials research. Here we review present equilibrium and non-equilibrium self-assembly approaches to the synthetic construction of discrete hybrid (inorganic-organic) nano-objects and higher-level nanostructured networks. We examine a range of synthetic modalities under equilibrium conditions that give rise to integrative self-assembly (supramolecular wrapping, nanoscale incarceration and nanostructure templating) or higher-order self-assembly (programmed/directed aggregation). We contrast these strategies with processes of transformative self-assembly that use self-organizing media, reaction-diffusion systems and coupled mesophases to produce higher-level hybrid structures under non-equilibrium conditions. Key elements of the constructional codes associated with these processes are identified with regard to existing theoretical knowledge, and presented as a heuristic guideline for the rational design of hybrid nano-objects and nanomaterials.

                Author and article information

                Nano Lett
                Nano Lett
                Nano Letters
                American Chemical Society
                21 January 2014
                12 February 2014
                : 14
                : 2
                : 1056-1063
                []Istituto Italiano di Tecnologia (IIT) , via Morego 30, IT-16163 Genova, Italy
                []Institute for Computational Physics (ICP), University of Stuttgart , Allmandring 3, 70569 Stuttgart, Germany
                [§ ]Soft Condensed Matter, Debye Institute for Nanomaterials Science, Utrecht University , Princetonplein 5, 3584 CC Utrecht, The Netherlands
                []Institute for Theoretical Physics, Utrecht University , Princetonplein 5, 3584 CE Utrecht, The Netherlands
                Author notes
                Copyright © 2014 American Chemical Society
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                interface adsorption, self-assembly, octapods, nanocomposite, polymer


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