Single-shell carbon-encapsulated iron nanoparticles: synthesis and high electrocatalytic activity for hydrogen evolution reaction.

Efficient hydrogen evolution reaction (HER) through effective and inexpensive electrocatalysts is a valuable approach for clean and renewable energy systems. Here, single-shell carbon-encapsulated iron nanoparticles (SCEINs) decorated on single-walled carbon nanotubes (SWNTs) are introduced as a novel highly active and durable non-noble-metal catalyst for the HER. This catalyst exhibits catalytic properties superior to previously studied nonprecious materials and comparable to those of platinum. The SCEIN/SWNT is synthesized by a novel fast and low-cost aerosol chemical vapor deposition method in a one-step synthesis. In SCEINs the single carbon layer does not prevent desired access of the reactants to the vicinity of the iron nanoparticles but protects the active metallic core from oxidation. This finding opens new avenues for utilizing active transition metals such as iron in a wide range of applications.

Ferromagnetic resonance in ϵ-Co magnetic composites.

We investigate the electromagnetic properties of assemblies of nanoscale ϵ-cobalt crystals with size range between 5 to 35 nm, embedded in a polystyrene matrix, at microwave (1-12 GHz) frequencies. We investigate the samples by transmission electron microscopy imaging, demonstrating that the particles aggregate and form chains and clusters. By using a broadband coaxial-line method, we extract the magnetic permeability in the frequency range from 1 to 12 GHz, and we study the shift of the ferromagnetic resonance (FMR) with respect to an externally applied magnetic field. We find that the zero-magnetic field ferromagnetic resonant peak shifts towards higher frequencies at finite magnetic fields, and the magnitude of complex permeability is reduced. At fields larger than 2.5 kOe the resonant frequency changes linearly with the applied magnetic field, demonstrating the transition to a state in which the nanoparticles become dynamically decoupled. In this regime, the particles inside clusters can be treated as non-interacting, and the peak position can be predicted from Kittel's FMR theory for non-interacting uniaxial spherical particles combined with the Landau-Lifshitz-Gilbert equation. In contrast, at low magnetic fields this magnetic order breaks down and the resonant frequency in zero magnetic field reaches a saturation value reflecting the interparticle interactions as resulting from aggregation. Our results show that the electromagnetic properties of these composite materials can be tuned by external magnetic fields and by changes in the aggregation structure.

Potential determining salts in microemulsions: interfacial distribution and effect on the phase behavior.

In this work we consider potential determining salts, also referred to as phase transfer agents for a future objective of electrochemistry at the oil-water interface in microemulsions. We have studied these salts, composed of a hydrophilic and a hydrophobic ion, in microemulsion stabilized by nonionic surfactants with an oligo ethylene oxide headgroup. NMR measurements show that the salts preferentially dissociate across the surfactant interface between the oil and water domains, and hence create a potential drop across the surfactant film, and back to back diffuse double layers in the oil and water phases. These observations are also supported by Poisson-Boltzmann calculations. This adsorption like event stabilizes the microemulsion. Repulsive long-range interactions between thin lamellae of surfactant and water lamellae in oil were observed using SAXS, thus confirming the presence of electrostatic forces mediated through the oil domain. We also observed that reversing the charges on the potential determining salts had opposite effects on the phase inversion temperature.

Electrochemically controlled proton-transfer-catalyzed reactions at liquid-liquid interfaces: nucleophilic substitution on ferrocene methanol.

The generation of α-ferrocenyl carbocations from ferrocenyl alcohols for S(N)1 substitution at the water-organic solvent interface is initiated by the transfer of protons into the organic phase. The proton flux, and hence the reaction rate, can be controlled by addition of a suitable "phase-transfer catalyst" anion or by external polarization with a potentiostat, providing a new method for the synthesis of ferrocene derivatives.

Anomalous dependence of particle size on supersaturation in the preparation of iron nanoparticles from iron pentacarbonyl.

Iron nanoparticles were prepared by decomposing iron pentacarbonyl (Fe(CO)(5)) at 170-220°C in the presence of amine surfactant and alkane solvent and under 1-12 bar carbon monoxide (CO) pressure. It was found that the amine not only acted as a stabilizer for the growing particles but also had a critical role as a promotor in the decomposition reaction. Relatively small changes in the CO pressure had anomalous effects on the particle size distribution. Typically, monodisperse particles were obtained at 1 bar, while pressures in the 2-6 bar range led to wider and even bimodal size distributions due to an emergence of smaller particles. At still higher pressures, the larger particle size disappeared leaving the distribution monodisperse again. The CO pressure, at which the bimodal transition took place, increased with the reaction temperature. Polycrystalline particles were formed at lower pressures and monocrystalline particles at higher pressures. This indicates that increased CO pressure inhibits aggregation.

A facile template-free approach to magnetodriven, multifunctional artificial cilia.

Flexible and magnetic artificial cilia were grown on various substrates by a facile bottom-up approach based on template-free magnetic assembly. The magnetic cilia formed spontaneously from a suspension of micrometer-sized ferromagnetic particles and elastomeric polymer in a liquid solvent when dried in an external magnetic field. The cilia mimics were mechanically stable even in the absence of an external magnetic field and a solvent due to the polymer, which acted as "glue" holding the particles together and connecting the cilia to the substrate. The length of the magnetic cilia was in the millimeter range, that is, two to three orders of magnitude times the length of typical biological cilia. The aspect ratio reached values over 100 and was tunable with the magnetic field gradient and the size of the ferromagnetic particles. The cilia mimics responded to an external magnetic field by reversibly bending along the field. The bending actuation was sufficiently powerful to allow two functions: to translate macroscopic nonmagnetic objects placed over the cilia mimics and to mix liquids of even high viscosity. The mechanical properties of the magnetic cilia could be easily tuned by changing the impregnating polymer. The particularly simple template-free construction and fixation on various surfaces suggest applications as an externally controllable surface.

Cobalt nanoparticle Langmuir-Schaefer films on ethylene glycol subphase.

The Langmuir-Schaefer (LS) technique was applied to prepare two-dimensional films of tridodecylamine (TDA)-stabilized Co nanoparticles. Ethylene glycol was used as the subphase because the Co nanoparticles spread better on it than on water. Surface pressure-area isotherms provided very little information on the floating films, and Brewster angle microscopy (BAM) was needed to characterize the film formation in situ. In addition to the subphase, various other experimental factors were tested in the LS film preparation, including solvent and presence of free TDA ligands and poly(styrene-b-ethylene oxide) (PS-b-PEO) in the nanoparticle dispersion. LS films deposited from dispersions from which the excess TDA ligands had been removed by washing the Co nanoparticles with 2-propanol consisted of hexagonally organized particles in rafts that were organized in necklace structures. The addition of PS-b-PEO to the deposition dispersion resulted in small nanoparticle rafts evenly distributed over the substrate surface. The best Co-nanoparticle-PS-b-PEO films were obtained with a mass ratio of 20:1 between Co (9 nm) and block copolymer (38 200 g/mol, PEO content 22 mass %). These films were successfully transferred onto Formvar-coated TEM grids and characterized by transmission electron microscopy (TEM) and a superconducting quantum interference device (SQUID) magnetometer. At room temperature the films showed superparamagnetic behavior with a saturation magnetization M(s) of 100 emu/g (Co). Our work indicates that it is possible to obtain thin superparamagnetic LS films of TDA-stabilized Co nanoparticles. This is an important result as the TDA-stabilized Co nanoparticles show a very good resistance to corrosion.

Directing oxidation of cobalt nanoparticles with the capping ligand.

The oxidation of Co nanoparticles stabilized with various ligands has been studied in an autoclave. Tridodecylamine stabilized Co nanoparticles with different sizes (8 nm, 22 nm and 36 nm) were prepared by thermal decomposition of Co(2)(CO)(8) in dodecane. The oxidation of the particles was studied by introducing oxygen into the autoclave and following the oxygen consumption with a pressure meter. Tridodecylamine capped particles were initially oxidized at a high rate, however, the oxidation layer quickly inhibited further oxidation. The thickness of the oxide layer estimated from the oxygen consumption was 0.8 nm for all three particle sizes showing that the oxidation is size independent in the studied particle size range. The tridodecylamine ligand was exchanged for various long chain carboxylic acids and the oxidation was studied. While the carboxylic acids give a slower initial oxidation rate, the formed oxide layer does not inhibit further oxidation as effectively as in the case of tridodecylamine. TEM studies show that tridodecylamine capping leads to particles with a metal core surrounded by an oxide layer, while particles capped with long chain carboxylic acids form hollow cobalt oxide shells.

Evolution of size distribution in pressure drop induced decomposition synthesis of cobalt nanoparticles.

Cobalt nanoparticles with average diameters of 8.8 nm and a standard deviation of 8% were obtained in a pressure drop induced decomposition synthesis in an autoclave. Samples were taken during the experiment and characterized with TEM. A significant narrowing of the size distribution coincident with particle growth was observed. The standard deviation decreased from 31% to 8% while the average size increased from 5.5 nm to 8.8 nm. In order to explain the experimentally observed narrowing of the size distribution, a model that accounts for the influence of the capping layer on the growth rate was developed. The transfer of the reacting monomer into the capping layer was considered to be similar to an adsorption process. A rate constant of 4x10(-5) cm(4) mol(-1) s(-1) was obtained for the growth reaction, and it was thus concluded that the growth reaction proceeds under kinetic control rather than under diffusion control.

Influence of ligand structure on the stability and oxidation of copper nanoparticles.

The stability and oxidation of copper nanoparticles stabilized with various ligands have been studied. Lauric acid-capped copper nanoparticles were prepared by a modified Brust-Schiffrin method. Then, ligand exchange with an excess of different capping agents was performed. Oxidation and stability were studied by UV-vis, XRD, and TEM. Alkanethiols and oleic acid were found to improve air stability. The oxidation resistance of thiol-capped copper nanoparticles was found to increase with the chain length of the thiol. However, excess thiol caused etching of the particles under nitrogen. With oleic acid no etching was observed under nitrogen. After oxidation, no traces of the ligand-exchanged particles were found, suggesting their dissolution due to excess ligand. Oleic acid protected the particles against oxidation better than the tested thiols at large excess (ligand-copper ratio 20:1).

Gold nanoparticles enable selective light-induced contents release from liposomes.

A novel proof of principle demonstration for contents release from liposomes that can be selectively activated by light irradiation is presented. The content release temperature was adjusted to slightly above body temperature, and hydrophobic or hydrophilic gold nanoparticles were incorporated into the lipid bilayer or the core of the liposomes, respectively. The release of a fluorescent marker was monitored upon exposure of the liposomes to UV light. Gold nanoparticle-containing liposomes remained intact at 37 degrees C but contents release was triggered by UV light-induced heating of the gold nanoparticles. This light-induced release is mediated by heat transfer from the gold nanoparticles to the lipids and subsequent phase transition. Heating is highly localized in the liposomes and the gold nanoparticles act as energy collectors that sensitize the liposomes to the light signal. This kind of selectivity is very advantageous as it can potentially make the drug delivery mechanism biologically more compatible. The triggered contents release could also be extended to other applications where local contents release is needed.

Stability and electrostatics of mercaptoundecanoic acid-capped gold nanoparticles with varying counterion size.

The solubility of charged nanoparticles is critically dependent on pH. However, the concentration range available with bases such as NaOH is quite narrow, since the particles precipitate due to compression of the electric double layer when the ionic strength is increased. The stability of mercaptoundecanoic acid-capped Au nanoparticles is studied at a set pH using the hydroxide as base and different cations of various sizes. The counterions used are sodium (Na(+)), tetramethylammonium (TMA(+)), tetraethylammonium (TEA(+)), and tetrabutylammonium (TBA(+)). The particles precipitate in the 70-90 mM range with Na(+) as the counterion, but with quaternary ammonium hydroxides the particles are stable even in concentrations exceeding 1 M. The change in solubility is linked to a strongly adsorbed layer on the surface of the ligand shell of the nanoparticles. The increased concentration range obtained with TEAOH is further used to facilitate thiol exchange which occurs at a greater extent than would be achieved in NaOH solution.

Modification of permeability transition pore arginine(s) by phenylglyoxal derivatives in isolated mitochondria and mammalian cells. Structure-function relationship of arginine ligands.

Methylglyoxal and synthetic glyoxal derivatives react covalently with arginine residue(s) on the mitochondrial permeability transition pore (PTP). In this study, we have investigated how the binding of a panel of synthetic phenylglyoxal derivatives influences the opening and closing of the PTP. Using both isolated mitochondria and mammalian cells, we demonstrate that the resulting arginine-phenylglyoxal adduct can lead to either suppression or induction of permeability transition, depending on the net charge and hydrogen bonding capacity of the adduct. We report that phenylglyoxal derivatives that possess a net negative charge and/or are capable of forming hydrogen bonds induced permeability transition. Derivatives that were overall electroneutral and cannot form hydrogen bonds suppressed permeability transition. When mammalian cells were incubated with low concentrations of negatively charged phenylglyoxal derivatives, the addition of oligomycin caused a depolarization of the mitochondrial membrane potential. This depolarization was completely blocked by cyclosporin A, a PTP opening inhibitor, indicating that the depolarization was due to PTP opening. Collectively, these findings highlight that the target arginine(s) is functionally linked with the opening/closing mechanism of the PTP and that the electric charge and hydrogen bonding of the resulting arginine adduct influences the conformation of the PTP. These results are consistent with a model where the target arginine plays a role as a voltage sensor.

Surface activity profiling of drugs applied to the prediction of blood-brain barrier permeability.

The present study describes a novel in vitro platform for physicochemical profiling of compounds, based on their impact on the air/water interfacial tension. Interfacial partitioning coefficient, cross-sectional area, and critical micelle concentration were derived from the Gibbs adsorption isotherms recorded for 76 structurally diverse drugs. An approximation for the membrane partitioning coefficient, K(memb), is introduced and calculated for the measured compounds. This methodology provides a fully automatic, high-throughput screening technique for compound characterization, yielding precise thermodynamic information on the partitioning behavior of molecules at air/water interfaces, which can be directly related to their anisotropic interaction with lipid bilayers in biological membranes. The latter represents the barrier for the passive entry of compounds into cells. The surface activity profiles are shown to correlate to the ability of the compounds to pass passively through the blood-brain barrier.

Influence of the presence of a gel in the water phase on the electrochemical transfer of ionic forms of beta-blockers across a large water 1,2-dichloroethane interface.

The transfer of ionic species of three beta-blockers (propranolol, sotalol and timolol) has been studied by cyclic voltammetry at a macroscopic water 1,2-dichloroethane (1,2-DCE) interface. The aqueous solution has been gellified in order to study the effect of the gel on the transport properties of the drugs. The gelling agent also stabilizes the interface overcoming mechanical instability. The standard potential and standard Gibbs energy of transfer across the interface, the partition coefficient and the diffusion coefficient of each drug were determined in the presence of a gelled interface. The diffusion coefficients were shifted relative to those obtained at normal water 1,2-DCE interfaces (free of gel).

Disk-generation/ring-collection scanning electrochemical microscopy: theory and application.

The potential of ring-disk ultramicroelectrodes (RD UMEs) as probes for scanning electrochemical microscopy (SECM) was investigated both theoretically and experimentally. In particular, the disk-generation/ring-collection (DG/RC) mode of operation was considered. In this case, the interaction of two species with the substrate under investigation can be followed simultaneously from single tip current-distance measurement (approach curve) to the substrate. Theoretical approach curves for DG/RC were calculated by numerical methods. Such approach curves to both insulating and conducting substrates indicate a strong tip response dependence on the ring radius while the response was relatively insensitive to ring thickness and overall tip radius. The RD tip was characterized by fitting experimental approach curves recorded at insulating and conducting substrates to simulated curves for a given tip geometry. DG/RC SECM was then applied to investigate the partitioning of iodine across a liquid-liquid interface.