Constructing a library of metal and metal-oxide nanoparticle heterodimers through colloidal assembly.

Nanoparticle dimers composed of different metals or metal oxides, as well as different shapes and sizes, are of wide interest for applications ranging from nanoplasmonic sensing to nanooptics to biomedical engineering. Shaped nanoparticles, like triangles and nanorods, can be particularly useful in applications due to the strong localized plasmonic hot-spot that forms at the tips or corners. By placing catalytic, but traditionally weakly- or non-plasmonic nanoparticles, such as metal oxides and metals like palladium, in these hot-spots, an enhanced function for sensing, photocatalysis or optical use is predicted. Here, we present an electrostatic colloidal assembly strategy for nanoparticles, incorporating different sizes, shapes and metal or metal oxide compositions into heterodimers with smaller gaps than are achievable using nanofabrication techniques. This versatile method is demonstrated on 14 combinations, including a variety of shaped gold nanoparticles as well as palladium, iron oxide, and titanium oxide nanoparticles. These colloidal nanoparticles are stabilized with traditional surfactants, such as citrate, CTAB, PVP and oleic acid/oleylamines, indicating the wide applicability of our approach. Heterodimers of gold and palladium are further analyzed using cathodoluminescence to demonstrate the tunability of these "plasmonic molecules". Since systematically altering the absorption and emission of the plasmonic nanoparticles dimers is crucial to extending their functionality, and small gap sizes produce the strongest hot-spots, this method indicates that the electrostatic approach to heterodimer assembly can be useful in creating new nanoparticle dimers for many applications.

Parallel Fabrication of Self-Assembled Nanogaps for Molecular Electronic Devices.

Single molecule electronics might be a way to add additional function to nanoscale devices and continue miniaturization beyond current state of the art. Here, a combined top-down and bottom-up strategy is employed to assemble single molecules onto prefabricated electrodes. Protodevices, which are self-assembled nanogaps composed by two gold nanoparticles linked by a single or a few molecules, are guided onto top-down prefabricated nanosized nickel electrodes with sandwiched palladium layers. It is shown that an optimized geometry of multilayered metallic (top-down) electrodes facilitates the assembly of (bottom-up) nanostructures by surface charge interactions. Moreover, such assembly process results in an electrode-nanoparticle interface free from linking molecules that enable electrical measurements to probe electron transport properties of the nanoparticle-molecule-nanoparticle protodevices.

Controlling deposition of nanoparticles by tuning surface charge of SiO2 by surface modifications.

The self-assembly of nanoparticles on substrates is relevant for a variety of applications such as plasmonics, sensing devices and nanometer-sized electronics. We investigate the deposition of 60 nm spherical Au nanoparticles onto silicon dioxide (SiO2) substrates by changing the chemical treatment of the substrate and by that altering the surface charge. The deposition is characterized by scanning electron microscopy (SEM). Kelvin probe force microscopy (KPFM) was used to characterize the surface workfunction. The underlying physics involved in the deposition of nanoparticles was described by a model based on Derjaguin-Landau-Verwey-Overbeek (DLVO) theory combined with random sequential adsorption (RSA). The spatial statistical method Ripley's K-function was used to verify the DLVO-RSA model (ERSA). The statistical results also showed that the adhered particles exhibit a short-range order at distances below ~300 nm. This method can be used in future research to predict the deposition densities of charged nanoparticles onto charged surfaces.

Hydride formation thermodynamics and hysteresis in individual Pd nanocrystals with different size and shape.

Physicochemical properties of nanoparticles may depend on their size and shape and are traditionally assessed in ensemble-level experiments, which accordingly may be plagued by averaging effects. These effects can be eliminated in single-nanoparticle experiments. Using plasmonic nanospectroscopy, we present a comprehensive study of hydride formation thermodynamics in individual Pd nanocrystals of different size and shape, and find corresponding enthalpies and entropies to be nearly size- and shape-independent. The hysteresis observed is significantly wider than in bulk, with details depending on the specifics of individual nanoparticles. Generally, the absorption branch of the hysteresis loop is size-dependent in the sub-30 nm regime, whereas desorption is size- and shape-independent. The former is consistent with a coherent phase transition during hydride formation, influenced kinetically by the specifics of nucleation, whereas the latter implies that hydride decomposition either occurs incoherently or via different kinetic pathways.

Being two is better than one-catalytic reductions with dendrimer encapsulated copper- and copper-cobalt-subnanoparticles.

Copper and copper-cobalt subnanoparticles have been synthesized using 4-carbomethoxypyrrolidone terminated PAMAM-dendrimers as templates. The metal particles were applied in catalytic reduction reactions. While Cu subnanoparticles were only capable of reducing conjugated double bonds, enhancing the Cu particles with Co led to a surprising increase in catalytic activity, reducing also isolated carbon double and triple bonds.

Monofunctionalization and dimerization of nanoparticles using coordination chemistry.

This paper describes a strategy for controlled nanoparticle dimerization by using a solid support approach. Two types of nanoparticles have been linked by using a 5-([2,2':6',2″-terpyridine]-4'-yloxy)pentan-1-amine (terpy-amine) iron complex. The strategy includes two major steps: first, the monofunctionalization of individual nanoparticles with terpy-amine ligand molecules on a solid support, followed by release of monofunctionalized particles and subsequent dimerization. The versatility of the approach was demonstrated by dimerizing two different types of nanoparticles: spherical gold and cube-shaped iron oxide nanoparticles.

The conquest of middle-earth: combining top-down and bottom-up nanofabrication for constructing nanoparticle based devices.

The development of top-down nanofabrication techniques has opened many possibilities for the design and realization of complex devices based on single molecule phenomena such as e.g. single molecule electronic devices. These impressive achievements have been complemented by the fundamental understanding of self-assembly phenomena, leading to bottom-up strategies to obtain hybrid nanomaterials that can be used as building blocks for more complex structures. In this feature article we highlight some relevant published work as well as present new experimental results, illustrating the versatility of self-assembly methods combined with top-down fabrication techniques for solving relevant challenges in modern nanotechnology. We present recent developments on the use of hierarchical self-assembly methods to bridge the gap between sub-nanometer and micrometer length scales. By the use of non-covalent self-assembly methods, we show that we are able to control the positioning of nanoparticles on surfaces, and to address the deterministic assembly of nano-devices with potential applications in plasmonic sensing and single-molecule electronics experiments.

Single-molecule electronics: from chemical design to functional devices.

The use of single molecules in electronics represents the next limit of miniaturisation of electronic devices, which would enable us to continue the trend of aggressive downscaling of silicon-based electronic devices. More significantly, the fabrication, understanding and control of fully functional circuits at the single-molecule level could also open up the possibility of using molecules as devices with novel, not-foreseen functionalities beyond complementary metal-oxide semiconductor technology (CMOS). This review aims at highlighting the chemical design and synthesis of single molecule devices as well as their electrical and structural characterization, including a historical overview and the developments during the last 5 years. We discuss experimental techniques for fabrication of single-molecule junctions, the potential application of single-molecule junctions as molecular switches, and general physical phenomena in single-molecule electronic devices.

A versatile self-assembly strategy for the synthesis of shape-selected colloidal noble metal nanoparticle heterodimers.

The self-assembly of individual nanoparticles into dimers-so-called heterodimers-is relevant for a broad range of applications, in particular in the vibrant field of nanoplasmonics and nanooptics. In this paper we report the synthesis and characterization of material- and shape-selected nanoparticle heterodimers assembled from individual particles via electrostatic interaction. The versatility of the synthetic strategy is shown by assembling combinations of metal particles of different shapes, sizes, and metal compositions like a gold sphere (90 nm) with either a gold cube (35 nm), gold rhombic dodecahedron (50 nm), palladium truncated cube (120 nm), palladium rhombic dodecahedron (110 nm), palladium octahedron (130 nm), or palladium cubes (25 and 70 nm) as well as a silver sphere (90 nm) with palladium cubes (25 and 70 nm). The obtained heterodimer combinations are characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), scanning transmission electron microscopy-energy dispersive X-ray spectroscopy (STEM-EDX), dynamic light scattering (DLS), and zeta-potential measurements. We describe the optimal experimental conditions to achieve the highest yield of heterodimers compared to other aggregates. The experimental results have been rationalized using theoretical modeling. A proof-of-principle experiment where individual Au-Pd heterodimers are exploited for indirect plasmonic sensing of hydrogen finally illustrates the potential of these structures to probe catalytic processes at the single particle level.

Direct measurement and modulation of single-molecule coordinative bonding forces in a transition metal complex.

Coordination chemistry has been a consistently active branch of chemistry since Werner's seminal theory of coordination compounds inaugurated in 1893, with the central focus on transition metal complexes. However, control and measurement of metal-ligand interactions at the single-molecule level remain a daunting challenge. Here we demonstrate an interdisciplinary and systematic approach that enables measurement and modulation of the coordinative bonding forces in a transition metal complex. Terpyridine is derived with a thiol linker, facilitating covalent attachment of this ligand on both gold substrate surfaces and gold-coated atomic force microscopy tips. The coordination and bond breaking between terpyridine and osmium are followed in situ by electrochemically controlled atomic force microscopy at the single-molecule level. The redox state of the central metal atom is found to have a significant impact on the metal-ligand interactions. The present approach represents a major advancement in unravelling the nature of metal-ligand interactions and could have broad implications in coordination chemistry.

Ultrafast spinning of gold nanoparticles in water using circularly polarized light.

Controlling the position and movement of small objects with light is an appealing way to manipulate delicate samples, such as living cells or nanoparticles. It is well-known that optical gradient and radiation pressure forces caused by a focused laser beam enables trapping and manipulation of objects with strength that is dependent on the particle's optical properties. Furthermore, by utilizing transfer of photon spin angular momentum, it is also possible to set objects into rotational motion simply by targeting them with a beam of circularly polarized light. Here we show that this effect can set ∼200 nm radii gold particles trapped in water in 2D by a laser tweezers into rotation at frequencies that reach several kilohertz, much higher than any previously reported light driven rotation of a microscopic object. We derive a theory for the fluctuations in light scattering from a rotating particle, and we argue that the high rotation frequencies observed experimentally is the combined result of favorable optical particle properties and a low local viscosity due to substantial heating of the particles surface layer. The high rotation speed suggests possible applications in nanofluidics, optical sensing, and microtooling of soft matter.

Lanthanide-based luminescent probes for selective time-gated detection of hydrogen peroxide in water and in living cells.

Lanthanide-based luminescent probes TPR1 and TPR2 were developed for the detection of hydrogen peroxide (H(2)O(2)) in living systems. The chemoselective reaction of these boronate-protected probes with H(2)O(2) resulted in an enhanced lanthanide sensitization and a 6-fold increase in luminescent intensity. TPR2 was utilized to measure the endogenous production of H(2)O(2) in RAW 264.7 macrophages using time-gated luminescent spectroscopy.