Two-Dimensional Crystals as a Buffer Layer for High Work Function Applications: The Case of Monolayer MoO3.

We propose that the crystallinity of two-dimensional (2D) materials is a crucial factor for achieving highly effective work function (WF) modification. A crystalline 2D MoO3 monolayer enhances substrate WF up to 6.4 eV for thicknesses as low as 0.7 nm. Such a high WF makes 2D MoO3 a great candidate for tuning properties of anode materials and for the future design of organic electronic devices, where accurate evaluation of the WF is crucial. We provide a detailed investigation of WF of 2D α-MoO3 directly grown on highly ordered pyrolytic graphite, by means of Kelvin probe force microscopy (KPFM) and ultraviolet photoemission spectroscopy (UPS). This study underlines the importance of a controlled environment and the resulting crystallinity to achieve high WF in MoO3. UPS is proved to be suitable for determining higher WF attributed to 2D islands on a substrate with lower WF, yet only in particular cases of sufficient coverage. KPFM remains a method of choice for nanoscale investigations, especially when conducted under ultrahigh vacuum conditions. Our experimental results are supported by density functional theory calculations of electrostatic potential, which indicate that oxygen vacancies result in anisotropy of WF at the sides of the MoO3 monolayer. These novel insights into the electronic properties of 2D-MoO3 are promising for the design of electronic devices with high WF monolayer films, preserving the transparency and flexibility of the systems.

Bioderived, chiral and stable 1-dimensional light-responsive nanostructures: Interconversion between tubules and twisted ribbons.

HYPOTHESIS: Self-assembling molecular structures responding to light stimulus are appealing for applications as sensing and drug delivery. Supramolecular nanotubes have a relevant potential in nanotechnology as they can be used to encapsulate different loads like drugs, biological macromolecules, and nanomaterials. In addition, they are suitable elements for novel supracolloidal materials. Structural responses of supramolecular nanotubes to non-invasive stimuli are very much desired to enable controlled release of the encapsulated guests and to provide these recently developed new materials with an external trigger. Here, we describe the formation of well-defined, single wall tubules that interconvert into twisted ribbons upon UV-light exposure in aqueous environment. The structures are provided by self-assembly of an azobenzene substituted cholic acid, a biological surfactant belonging to the family of bile acids. The azobenzene group allows for the light responsiveness of the molecular packing. Concurrently the steroidal moieties assure both chiral features and extensive hydrophobic interactions for time and temperature resistant aggregates. EXPERIMENTS: The molecular packing interconversion was followed by circular dichroism. Microscopy, small angle X-ray scattering and light scattering measurements demonstrated the drastic morphological variation upon irradiation. A model of the molecular arrangement within the tubular walls was suggested based on the circular dichroism spectra simulation. FINDINGS: Innovatively, the molecular design reported in our work allows for encoding in the same light responsive system multiple desirable features (e.g. bio-origin, temperature resistance and chirality of the aggregates). Such combination of properties, never reported before for a single molecule, might be relevant for the realization of robust, stimuli-responsive bio-vectors.

Condensed Supramolecular Helices: The Twisted Sisters of DNA.

Condensation of DNA helices into hexagonally packed bundles and toroids represents an intriguing example of functional organization of biological macromolecules at the nanoscale. The condensation models are based on the unique polyelectrolyte features of DNA, however here we could reproduce a DNA-like condensation with supramolecular helices of small chiral molecules, thereby demonstrating that it is a more general phenomenon. We show that the bile salt sodium deoxycholate can form supramolecular helices upon interaction with oppositely charged polyelectrolytes of homopolymer or block copolymers. At higher order, a controlled hexagonal packing of the helices into DNA-like bundles and toroids could be accomplished. The results disclose unknown similarities between covalent and supramolecular non-covalent helical polyelectrolytes, which inspire visionary ideas of constructing supramolecular versions of biological macromolecules. As drug nanocarriers the polymer-bile salt superstructures would get advantage of a complex chirality at molecular and supramolecular levels, whose effect on the nanocarrier assisted drug efficiency is a still unexplored fascinating issue.

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.

Supracolloidal Atomium.

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.

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.

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 ß -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.

ZnO@TiO2 Core Shell Nanorod Arrays with Tailored Structural, Electrical, and Optical Properties for Photovoltaic Application.

ZnO has prominent electron transport and optical properties, beneficial for photovoltaic application, but its surface is prone to the formation of defects. To overcome this problem, we deposited nanostructured TiO2 thin film on ZnO nanorods to form a stable shell. ZnO nanorods synthesized by wet-chemistry are single crystals. Three different procedures for deposition of TiO2 were applied. The influence of preparation methods and parameters on the structure, morphology, electrical and optical properties were studied. Nanostructured TiO2 shells show different morphologies dependent on deposition methods: (1) separated nanoparticles (by pulsed laser deposition (PLD) in Ar), (2) a layer with nonhomogeneous thickness (by PLD in vacuum or DC reactive magnetron sputtering), and (3) a homogenous thin layer along the nanorods (by chemical deposition). Based on the structural study, we chose the preparation parameters to obtain an anatase structure of the TiO2 shell. Impedance spectroscopy shows pure electron conductivity that was considerably better in all the ZnO@TiO2 than in bare ZnO nanorods or TiO2 layers. The best conductivity among the studied samples and the lowest activation energy was observed for the sample with a chemically deposited TiO2 shell. Higher transparency in the visible part of spectrum was achieved for the sample with a homogenous TiO2 layer along the nanorods, then in the samples with a layer of varying thickness.

Electrodeposition of Gold Nanostructures at the Interface of a Pickering Emulsion.

The controlled electrodeposition of nanoparticles at the surface of an emulsion droplet offers enticing possibilities in regards to the formation of intricate structures or fine control over the locus or duration of nanoparticle growth. In this work we develop electrochemical control over the spontaneous reduction of aqueous phase Au(III) by heterogeneous electron transfer from decamethylferrocene present in an emulsion droplet - resulting in the growth of nanoparticles. As gold is a highly effective conduit for the passage of electrical current, even on the nanoscale, the deposition significantly enhances the current response for the single electron transfer of decamethylferrocene when acting as a redox indicator. The nanostructures formed at the surface of the emulsion droplets were imaged by cryo-TEM, providing an insight into the types of structures that may form when stabilised by the interface alone, and how the structures are able to conduct electrons.

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.

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.

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.

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.

Direct-write deposition and focused-electron-beam-induced purification of gold nanostructures.

Three-dimensional gold (Au) nanostructures offer promise in nanoplasmonics, biomedical applications, electrochemical sensing and as contacts for carbon-based electronics. Direct-write techniques such as focused-electron-beam-induced deposition (FEBID) can provide such precisely patterned nanostructures. Unfortunately, FEBID Au traditionally suffers from a high nonmetallic content and cannot meet the purity requirements for these applications. Here we report exceptionally pure pristine FEBID Au nanostructures comprising submicrometer-large monocrystalline Au sections. On the basis of high-resolution transmission electron microscopy results and Monte Carlo simulations of electron trajectories in the deposited nanostructures, we propose a curing mechanism that elucidates the observed phenomena. The in situ focused-electron-beam-induced curing mechanism was supported by postdeposition ex situ curing and, in combination with oxygen plasma cleaning, is utilized as a straightforward purification method for planar FEBID structures. This work paves the way for the application of FEBID Au nanostructures in a new generation of biosensors and plasmonic nanodevices.

Synthesis of individually tuned nanomagnets for Nanomagnet Logic by direct write focused electron beam induced deposition.

Nanomagnet Logic (NML) is a promising new technology for future logic which exploits interactions among magnetic nanoelements in order to encode and compute binary information. This approach overcomes the well-known limits of CMOS-based microelectronics by drastically reducing the power consumption of computational systems and by offering nonvolatility. An actual key challenge is the nanofabrication of such systems that, up to date, are prepared by complex multistep processes in planar technology. Here, we report the single-step synthesis of NML key elements by focused electron beam induced deposition (FEBID) using iron pentacarbonyl as a gas precursor. The resulting nanomagnets feature an inner iron part and a 3 nm iron oxide cover (core-shell structure). Full functionality of conventional NML gates from FEBID-nanowires was achieved. An advanced structure maintaining the gate functionality based on bended nanowires was realized. The unique design obtained by direct-writing reduces the error probability and may merge several NWs in future NML elements.