Carborane-capped gold nanoparticles (Au/carborane NPs, 2–3 nm) can act as artificial ion transporters across biological membranes. The particles themselves are large hydrophobic anions that have the ability to disperse in aqueous media and to partition over both sides of a phospholipid bilayer membrane. Their presence therefore causes a membrane potential that is determined by the relative concentrations of particles on each side of the membrane according to the Nernst equation. The particles tend to adsorb to both sides of the membrane and can flip across if changes in membrane potential require their repartitioning. Such changes can be made either with a potentiostat in an electrochemical cell or by competition with another partitioning ion, for example, potassium in the presence of its specific transporter valinomycin. Carborane-capped gold nanoparticles have a ligand shell full of voids, which stem from the packing of near spherical ligands on a near spherical metal core. These voids are normally filled with sodium or potassium ions, and the charge is overcompensated by excess electrons in the metal core. The anionic particles are therefore able to take up and release a certain payload of cations and to adjust their net charge accordingly. It is demonstrated by potential-dependent fluorescence spectroscopy that polarized phospholipid membranes of vesicles can be depolarized by ion transport mediated by the particles. It is also shown that the particles act as alkali-ion-specific transporters across free-standing membranes under potentiostatic control. Magnesium ions are not transported.
29 December 2014 in ACS Applied Materials & Interfaces
We present a systematic survey of unprotected Ag-Au nanoclusters prepared by inert gas aggregation. The clusters are initially fully and homogeneously alloyed, exhibiting icosahedral and decahedral structural motifs. Imaging using scanning transmission electron microscopy indicates that over a period of up to 2 yr, the nanoclusters undergo structural transitions into phase-segregated core-shell and Janus particles with Ag-Au cores and AgxO shells. Larger Janus particles undergo a ripening process which results in division into separate Ag-Au-rich and Ag2O-rich particles. We propose that oxidation of the Ag component and subsequent diffusion of AgxO are responsible for the observed phenomena.
We present evidence that ultra-thin Bi(110) nanostructures oxidise from the edges, and that their top surfaces remain unoxidised. Even after prolonged oxidation, clean (unoxidised) bismuth is present in nanostructures that are less than 5 monolayers thick. Since the (110) surface of bulk bismuth is known to be readily oxidised, this is strong evidence for a thin film allotrope of bismuth. We present a comparison with calculated structures and the structures of polymeric nitrogen, which suggests that the allotrope is one of several complex or hybrid paired-layer structures.
Nature suggests that complex materials result from a hierarchical organization of matter at different length scales. At the nano- and micrometer scale, macromolecules and supramolecular aggregates spontaneously assemble into supracolloidal structures whose complexity is given by the coexistence of various colloidal entities and the specific interactions between them. Here, we demonstrate how such control can be implemented by engineering specially customized bile salt derivative-based supramolecular tubules that exhibit a highly specific interaction with polymeric microgel spheres at their extremities thanks to their scroll-like structure. This design allows for hierarchical supracolloidal self-assembly of microgels and supramolecular scrolls into a regular framework of “nodes” and “linkers”. The supramolecular assembly into scrolls can be triggered by pH and temperature, thereby providing the whole supracolloidal system with interesting stimuli-responsive properties. A colloidal smart assembly is embodied with features of center-linker frameworks as those found in molecular metal–organic frameworks and in structures engineered at human scale, masterfully represented by the Atomium in Bruxelles.