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.
The changes in interparticle
spacing upon hydration and dehydration
of drop-cast films of hydrophilic gold nanoparticles (GNP) have been
measured in situ with nanometer resolution using
WetSTEM and ESEM. These subtle variations correlate well with the
corresponding changes in the optical spectra and perceived color as
well as changes in the electrical conductivity of the films. AC impedance
analysis allows us to differentiate between resistive and capacitive
components and to evaluate how these depend on average particle spacing
and the water content of the matrix, respectively. Thin films of this
type are well-known structures used for development of sensors and
diagnostics.
We report an investigation of the self-assembly of patterns from functionalized gold nanoparticles (GNPs) by monitoring the process in situ by environmental scanning electron microscopy (ESEM) during both evaporation and condensation of the dispersant. As this method limits the choice of dispersants to water, GNPs functionalized with hydrophilic thiol ligands, containing poly(ethylene)glycol (PEG) groups, were used on a variety of substrates including pre-patterned ones. Particular emphasis was given to early stage deposition of GNPs, as well as redispersion and lift-off upon condensation of water droplets. ESEM presents a unique opportunity of directly imaging such events in situ. It was found that attractive interactions between the substrate and the GNPs are often stronger than expected once the particles have been deposited. The role of nickel perchlorate as a highly water-soluble additive was studied. It was found that entropically driven deposition of particles and decoration of surface features was enhanced in its presence, as expected.
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