Monitoring pattern formation in drying and wetting dispersions of gold nanoparticles by ESEM

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.</p

Physicochemical Characterisation of KEIF-The Intrinsically Disordered N-Terminal Region of Magnesium Transporter A

Magnesium transporter A (MgtA) is an active transporter responsible for importing magnesium ions into the cytoplasm of prokaryotic cells. This study focuses on the peptide corresponding to the intrinsically disordered N-terminal region of MgtA, referred to as KEIF. Primary-structure and bioinformatic analyses were performed, followed by studies of the undisturbed single chain using a combination of techniques including small-angle X-ray scattering, circular dichroism spectroscopy, and atomistic molecular-dynamics simulations. Moreover, interactions with large unilamellar vesicles were investigated by using dynamic light scattering, laser Doppler velocimetry, cryogenic transmission electron microscopy, and circular dichroism spectroscopy. KEIF was confirmed to be intrinsically disordered in aqueous solution, although extended and containing little β-structure and possibly PPII structure. An increase of helical content was observed in organic solvent, and a similar effect was also seen in aqueous solution containing anionic vesicles. Interactions of cationic KEIF with anionic vesicles led to the hypothesis that KEIF adsorbs to the vesicle surface through electrostatic and entropic driving forces. Considering this, there is a possibility that the biological role of KEIF is to anchor MgtA in the cell membrane, although further investigation is needed to confirm this hypothesis

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

Studies of Alloy Nanoclusters and Their Influence on Growth of Carbon Nanotubes

In this work we examine Ag-Au and Ni-Cu nanoclusters: their structural,compositional, and morphological characteristics are investigated in detail. The clusters are produced by the inert gas aggregation (IGA) method from magnetron sputtered alloy targets, in an UHV compatible system. The design of the system is optimized for production and deposition of the clusters with size in the range 5 nm < D < 10 nm. In order to increase the flux of sub-5 nm clusters in the system, we conducted modeling and experimental studies of cluster motion: the simulations showed that skimmers with wider internal angles might significantly improve the flux of smaller nanoclusters; however, the experimental study revealed a major influence of the background gas on scattering of such nanoclusters which consequently led to the loss of their flux. A comprehensive study of Ag0:85Au0:15 nanoclusters was conducted over a period of more than 2 years. Nanoclusters with sizes in the range 3 nm < D < 10 nm were deposited onto a-C films at various surface coverages and systematically investigated by transmission electron microscopy. We found that Ag-Au nanoclusters initially exhibited icosahedral and decahedral structural motifs, with a very small fraction of face centered cubic nanoclusters present. This may suggest that the source conditions used in the experiments (primarily Ar flow) left Ag-Au nanoclusters kinetically trapped in structures which correspond to local thermodynamic minima, rather than global energetically favoured atomic configurations. When left exposed to ambient conditions, over time Ag-Au nanoclusters exhibited structural, morphological, and compositional changes: core-shell and Janus nanoclusters were observed in aged samples, as well as fragmentation of bigger particles. We attribute these changes to oxidation of the Ag component and increased diffusion of Ag₂O over the substrates. The final morphology of aged nanocluster-based thin films is governed by a combination of diffusion, Ostwald ripening, and the Plateau-Rayleigh instability. High resolution transmission electron microscopy confirmed the presence of fivefold symmetric structures in Ni-Cu nanoclusters; however, their higher oxidation rate may have influenced the structures from the outset. In addition, when these nanoclusters were exposed to the electron beam, crystalline artifacts (nanochimneys)started to grown on them, with a structure corresponding to the NiO structure. Ni-Cu nanoclusters are subsequently used as catalysts in a pilot study of carbon nanotube synthesis which confirmed that such alloy nanoclusters are catalytically active for single-wall and multi-wall carbon nanotube growth

Nanoplatelet interactions in the presence of multivalent ions: The effect of overcharging and stability

Hypothesis: The stability of colloidal dispersions in the presence of multivalent ions depends strongly on the electrostatic interactions between the suspended particles. Of particular interest are colloidal particles having dimensions in the nanometric range and with an anisotropic shape due to its high surface area per unit mass, for example clay, which has the key characteristic of a negatively charged surface, surrounded by an oppositely charged rim. Experiments: In this study, we investigate the interactions in nanoplatelet dispersions for the model system of Laponite® clay with addition of mono- and multivalent salt. Molecular dynamics simulations with enhanced umbrella sampling have been utilised in combination with the experimental techniques of zeta-potential measurements, dynamic light scattering, and transmission electron microscopy. Findings: It was observed that tactoid formation and tactoidal dissolution due to overcharging occur upon the addition of trivalent salt. The overcharging effect was captured from calculated potential of mean force and confirmed from the zeta-potential, which changed sign from negative to positive when increasing the stoichiometric charge-ratio between the positive salt ions and the clay. Consequently, the gained information could provide useful physical insight of nanoplatelet interactions in the presence of multivalent ions

Direct writing of gold nanostructures with an electron beam: On the way to pure nanostructures by combining optimized deposition with oxygen-plasma treatment

This work presents a highly effective approach for the chemical purification of directly written 2D and 3D gold nanostructures suitable for plasmonics, biomolecule immobilisation, and nanoelectronics. Gold nano- and microstructures can be fabricated by one-step direct-write lithography process using focused electron beam induced deposition (FEBID). Typically, as-deposited gold nanostructures suffer from a low Au content and unacceptably high carbon contamination. We show that the undesirable carbon contamination can be diminished using a two-step process – a combination of optimized deposition followed by appropriate postdeposition cleaning. Starting from the common metal-organic precursor Me2-Au-tfac, it is demonstrated that the Au content in pristine FEBID nanostructures can be increased from 30 atom % to as much as 72 atom %, depending on the sustained electron beam dose. As a second step, oxygen-plasma treatment is established to further enhance the Au content in the structures, while preserving their morphology to a high degree. This two-step process represents a simple, feasible and high-throughput method for direct writing of purer gold nanostructures that can enable their future use for demanding applications