Crown Ether-Capped Gold Nanoclusters as a Multimodal Platform for Bioimaging

The distinct polarity of biomolecule surfaces plays a pivotal role in their biochemistry and functions as it is involved in numerous processes, such as folding, aggregation, or denaturation. Therefore, there is a need to image both hydrophilic and hydrophobic bio-interfaces with markers of distinct responses to hydrophobic and hydrophilic environments. In this work, we present a synthesis, characterization, and application of ultrasmall gold nanoclusters capped with a 12-crown-4 ligand. The nanoclusters present an amphiphilic character and can be successfully transferred between aqueous and organic solvents and have their physicochemical integrity retained. They can serve as probes for multimodal bioimaging with light (as they emit near-infrared luminescence) and electron microscopy (due to the high electron density of gold). In this work, we used protein superstructures, namely, amyloid spherulites, as a hydrophobic surface model and individual amyloid fibrils with a mixed hydrophobicity profile. Our nanoclusters spontaneously stained densely packed amyloid spherulites as observed under fluorescence microscopy, which is limited for hydrophilic markers. Moreover, our clusters revealed structural features of individual amyloid fibrils at a nanoscale as observed under a transmission electron microscope. We show the potential of crown ether-capped gold nanoclusters in multimodal structural characterization of bio-interfaces where the amphiphilic character of the supramolecular ligand is required.publishedVersionPeer reviewe

Design of artificial membrane transporters from gold nanoparticles with controllable hydrophobicity

Gold nanoparticles with variable hydrophobicity have been prepared in three different size regimes following established methods. The control of hydrophobicity was achieved by complexation of the 18-crown-6-CH2-thiolate ligand shell with potassium ions. Potassium dependent phase transfer of these particles from dispersion in water to chloroform was demonstrated, and the equilibrium partitioning of the particles in water–chloroform liquid/liquid systems was quantified by optical spectroscopy. The gradual complexation of the ligand shell with potassium ions was further monitored by zeta potential measurements. Potassium dependent insertion of nanoparticles into the phospholipid bilayer membrane of vesicles in aqueous dispersion has been demonstrated by cryogenic transmission electron microscopy (cryo-TEM). Nanoparticle-dependent potassium ion transport across the vesicle membrane has been established by monitoring the membrane potential with fluorescence spectroscopy using a potential sensitive dye.</p

Ion Transport across Biological Membranes by Carborane-Capped Gold Nanoparticles

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

Humidity-Dependent Reversible Transitions in Gold Nanoparticle Superlattices

The changes in interparticle spacing upon hydration and dehydration of drop-cast films of hydrophilic gold nanoparticles (GNP) have been measured <i>in situ</i> 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

Ion shuttling between emulsion droplets by crown ether modified gold nanoparticles

Selective unidirectional transport of barium ions between droplets in a water-in-chloroform emulsion is demonstrated. Gold nanoparticles (GNPs) modified with a thiolated crown ether act as barium ion complexing shuttles that carry the ions from one population of droplets (source) to another (target). This process is driven by a steep barium ion concentration gradient between source and target droplets. The concentration of barium ions in the target droplets is kept low at all times by the precipitation of insoluble barium sulfate. A potential role of electrostatically coupled secondary processes that maintain the electroneutrality of the emulsion droplets is discussed. Charging of the GNP metal cores by electron transfer in the presence of the Fe(ii)/Fe(iii) redox couple appears to affect the partitioning of the GNPs between the water droplets and the chloroform phase. Processes have been monitored and studied by optical microscopy, Raman spectroscopy, cryogenic scanning electron microscopy (cryo-SEM) and zeta potential. The shuttle action of the GNPs has further been demonstrated electrochemically in a model system

Optical Response of Individual Au–Ag@SiO₂ Heterodimers

The optical extinction response of individual Au–Ag@SiO₂ heterodimers whose individual morphologies are determined by transmission electron microscopy (TEM) is investigated using spatial modulation spectroscopy. The extinction spectra show two resonances spectrally close to the surface plasmon resonances of the constituting Au and Ag@SiO₂ core–shell particles. The interparticle electromagnetic coupling is demonstrated to induce a large increase of the optical extinction of the dimer around its Au-like surface plasmon resonance for light polarized along its axis, as compared to that for perpendicular polarization and to that of an isolated Au nanoparticle. For spherical particles, this interaction also leads to comparable shifts with light polarization of the two dimer resonances, an effect masked or even reversed for particles significantly deviating from sphericity. Both amplitude and spectral effects are found to be in excellent quantitative agreement with numerical simulations when using the TEM-measured dimer morphology (<i>i</i>.<i>e</i>., size, shape, and orientation of the individual dimers), stressing the importance of individual morphology characterization for interpreting heterodimer optical response