Nanoparticles are known to self-assemble into larger structures through growth processes that typically occur continuously and depend on the uniformity of the individual nanoparticles. Here, we show that inorganic nanoparticles with non-uniform size distributions can spontaneously assemble into uniformly sized supraparticles with core-shell morphologies. This self-limiting growth process is governed by a balance between electrostatic repulsion and van der Waals attraction, which is aided by the broad polydispersity of the nanoparticles. The generic nature of the interactions creates flexibility in the composition, size and shape of the constituent nanoparticles, and leads to a large family of self-assembled structures, including hierarchically organized colloidal crystals.
The collective properties of nanoparticles manifest in their ability to self-organize into complex microscale structures. Slow oxidation of tellurium ions in cadmium telluride (CdTe) nanoparticles results in the assembly of 1- to 4-micrometer-long flat ribbons made of several layers of individual cadmium sulfide (CdS)/CdTe nanocrystals. Twisting of the ribbons with an equal distribution of left and right helices was induced by illumination with visible light. The pitch lengths (250 to 1500 nanometers) varied with illumination dose, and the twisting was associated with the relief of mechanical shear stress in assembled ribbons caused by photooxidation of CdS. Unusual shapes of multiparticle assemblies, such as ellipsoidal clouds, dog-bone agglomerates, and ribbon bunches, were observed as intermediate stages. Computer simulations revealed that the balance between attraction and electrostatic repulsion determines the resulting geometry and dimensionality of the nanoparticle assemblies.
Increasingly detailed structural and dynamic studies are highlighting the precision with which biomolecules execute often complex tasks at the molecular scale. The efficiency and versatility of these processes have inspired many attempts to mimic or harness them. To date, biomolecules have been used to perform computational operations and actuation, to construct artificial transcriptional loops that behave like simple circuit elements and to direct the assembly of nanocrystals. Further development of these approaches requires new tools for the physical and chemical manipulation of biological systems. Biomolecular activity has been triggered optically through the use of chromophores, but direct electronic control over biomolecular 'machinery' in a specific and fully reversible manner has not yet been achieved. Here we demonstrate remote electronic control over the hybridization behaviour of DNA molecules, by inductive coupling of a radio-frequency magnetic field to a metal nanocrystal covalently linked to DNA. Inductive coupling to the nanocrystal increases the local temperature of the bound DNA, thereby inducing denaturation while leaving surrounding molecules relatively unaffected. Moreover, because dissolved biomolecules dissipate heat in less than 50 picoseconds (ref. 16), the switching is fully reversible. Inductive heating of macroscopic samples is widely used, but the present approach should allow extension of this concept to the control of hybridization and thus of a broad range of biological functions on the molecular scale.
We present a microscopic theory that describes the ordering of two distinct ligands on the surface of a faceted nanoparticle. The theory predicts that when one type of ligand is significantly bulkier than all others, the larger ligands preferentially align themselves along the edges and vertices of the nanoparticle. Monte Carlo simulations confirm these predictions. We show that the intrinsic conformational entropy of the ligands stabilizes this novel edge-aligned phase.
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