Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F and P450nor co-factors, with their reduced Ni- and Fe-containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature.

Competing magnetic states and-loop splitting in core-shell NiO nanoparticles.

Magnetic relaxation in a nanoparticles system depends on the intra-particle interactions, reversal mechanism, the anisotropy field, easy axis distribution, particle volume, lattice defects, surface defects, materials composite, etc. Here we report the competing magnetic states between superparamagnetic blocking and Néel transition states in 14 nm core-shell NiO nanoparticles. A crossover temperature of 50 K was observed for both these states from the zero field cooled/field cooled magnetization curves taken at different fields.

Disproportionation of Nitric Oxide at a Surface-Bound Nickel Porphyrinoid.

Uncommon metal oxidation states in porphyrinoid cofactors are responsible for the activity of many enzymes. The F and P450nor co-factors, with their reduced Ni - and Fe -containing tetrapyrrolic cores, are prototypical examples of biological systems involved in methane formation and in the reduction of nitric oxide, respectively. Herein, using a comprehensive range of experimental and theoretical methods, we raise evidence that nickel tetraphenyl porphyrins deposited in vacuo on a copper surface are reactive towards nitric oxide disproportionation at room temperature.

Quantitative comparison of frequency-domain and delay-and-sum optoacoustic image reconstruction including the effect of coherence factor weighting.

Image reconstruction in optoacoustic imaging is often based on a delay-and-sum (DAS) or a frequency domain (FD) algorithm. In this study, we performed a comprehensive comparison of these two algorithms together with coherence factor (CF) weighting using phantom and in-vivo mouse data obtained with optoacoustic microscopy. For this purpose we developed an FD based definition of the CF.

New MRI contrast agents based on silicon nanotubes loaded with superparamagnetic iron oxide nanoparticles.

This article describes the preparation and fundamental properties of a new possible material as a magnetic resonance imaging contrast agent based on the incorporation of preformed iron oxide (FeO) nanocrystals into hollow silicon nanotubes (Si NTs). Specifically, superparamagnetic FeO nanoparticles of two different average sizes (5 nm and 8 nm) were loaded into Si NTs of two different shell thicknesses (40 nm and 70 nm). To achieve proper aqueous solubility, the NTs were functionalized with an outer polyethylene glycol-diacid (600) moiety via an aminopropyl linkage.

Publisher Correction: Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The original version of this Article contained an error in the spelling of the author Claus Michael Schneider, which was incorrectly given as Claus Michael Schneidery. This has now been corrected in both the PDF and HTML versions of the Article.

Multi-orbital charge transfer at highly oriented organic/metal interfaces.

The molecule-substrate interaction plays a key role in charge injection organic-based devices. Charge transfer at molecule-metal interfaces strongly affects the overall physical and magnetic properties of the system, and ultimately the device performance. Here, we report theoretical and experimental evidence of a pronounced charge transfer involving nickel tetraphenyl porphyrin molecules adsorbed on Cu(100).

Decomposition of Methanol on Mixed CuO-CuWO Surfaces.

Mixed CuO(2 × 1)-CuWO layers on a Cu(110) surface have been prepared by the on-surface reaction of the CuO(2 × 1) surface oxide with adsorbed (WO) clusters. The adsorption and decomposition of methanol on these well-defined CuO-CuWO surfaces has been followed by high-resolution X-ray photoelectron spectroscopy (XPS), high-resolution electron energy loss spectroscopy (HREELS), and temperature-programmed desorption (TPD) to assess the molecular surface species and their concentration, while the state of the surface oxide phases before and after methanol decomposition has been characterized by scanning tunneling microscopy (STM), low energy electron diffraction (LEED), and XPS. Surface methoxy species form the primary methanol decomposition products, which desorb partly by recombination as methanol at 200-300 K or decompose into CH and possibly CO.

Phase behaviour of 2D MnWO and FeWO ternary oxide layers on Pd(1 0 0).

The structure and properties of ternary oxide materials at the nanoscale are poorly explored both on experimental and theoretical levels. With this work we demonstrate the successful on-surface synthesis of two-dimensional (2D) ternary oxide, MnWO and FeWO , nanolayers on a Pd(1 0 0) surface and the understanding of their new structure and phase behaviour with the help of state-of-art surface structure and spectroscopy techniques. We find that the 2D MnWO and FeWO phases, prepared under identical thermodynamic conditions, exhibit similar structural properties, reflecting the similarity of the bulk MnWO and FeWO phases with the wolframite structure.

Direct-Write 3D Nanoprinting of Plasmonic Structures.

During the past decade, significant progress has been made in the field of resonant optics ranging from fundamental aspects to concrete applications. While several techniques have been introduced for the fabrication of highly defined metallic nanostructures, the synthesis of complex, free-standing three-dimensional (3D) structures is still an intriguing, but so far intractable, challenge. In this study, we demonstrate a 3D direct-write synthesis approach that addresses this challenge.

Epitaxy of highly ordered organic semiconductor crystallite networks supported by hexagonal boron nitride.

This study focuses on hexagonal boron nitride as an ultra-thin van der Waals dielectric substrate for the epitaxial growth of highly ordered crystalline networks of the organic semiconductor parahexaphenyl. Atomic force microscopy based morphology analysis combined with density functional theory simulations reveal their epitaxial relation. As a consequence, needle-like crystallites of parahexaphenyl grow with their long axes oriented five degrees off the hexagonal boron nitride zigzag directions.

Transient surface photovoltage studies of bare and Ni-filled porous silicon performed in different ambients.

Unlabelled: Mesoporous silicon and porous silicon/Ni nanocomposites have been investigated in this work employing light-dark surface photovoltage (SPV) transients to monitor the response of surface charge dynamics to illumination changes. The samples were prepared by anodization of a highly n-doped silicon wafer and a subsequent electrodepositing of Ni into the pores. The resulting pores were oriented towards the surface with an average pore diameter of 60 nm and the thickness of the porous layer of approximately 40 μm.

Magnetic interactions between metal nanostructures within porous silicon.

Unlabelled: Electrochemically deposited magnetic nanostructures arranged in a three-dimensional system are investigated with respect to their cross-talk between each other. The nanostructures are embedded in porous silicon templates with different morphologies which means pores offering dendritic growth of different strengths. An increase of the uniformity of the pores is concomitant with an increase of the smoothness of the metal deposits which strongly influences the magnetic behavior of the system.

Magnetic properties of superparamagnetic nanoparticles loaded into silicon nanotubes.

Unlabelled: In this work, the magnetic properties of silicon nanotubes (SiNTs) filled with Fe3O4 nanoparticles (NPs) are investigated. SiNTs with different wall thicknesses of 10 and 70 nm and an inner diameter of approximately 50 nm are prepared and filled with superparamagnetic iron oxide nanoparticles of 4 and 10 nm in diameter. The infiltration process of the NPs into the tubes and dependence on the wall-thickness is described.

Spectral modifications and polarization dependent coupling in tailored assemblies of quantum dots and plasmonic nanowires.

The coupling of optical emitters with a nanostructured environment is at the heart of nano- and quantum optics. We control this coupling by the lithographic positioning of a few (1-3) quantum dots (QDs) along plasmonic silver nanowires with nanoscale resolution. The fluorescence emission from the QD-nanowire systems is probed spectroscopically, by microscopic imaging and decay time measurements.

Template-assisted deposition of CTAB-functionalized gold nanoparticles with nanoscale resolution.

In this paper, we demonstrate the template-assisted deposition of cetyltrimethylammonium bromide (CTAB) stabilized gold nanorods at lithographically defined positions on a substrate. Overcoating of the nanoparticles with polystyrenesulfonate allows to switch the original nanoparticles positive surface charge to negative and to apply the template-assisted deposition technique developed for citrate-capped gold nanoparticles also to CTAB stabilized nanoparticles. The successful, selective deposition of gold nanorods in trenches with widths down to 50 nm is demonstrated.

Variable blocking temperature of a porous silicon/Fe3O4 composite due to different interactions of the magnetic nanoparticles.

In the frame of this work, the aim was to create a superparamagnetic nanocomposite system with a maximized magnetic moment when magnetized by an external field and a blocking temperature far below room temperature. For this purpose, iron oxide nanoparticles of 3.8-, 5- and 8-nm size have been infiltrated into the pores of porous silicon.

Porous silicon/Ni composites of high coercivity due to magnetic field-assisted etching.

Ferromagnetic nanostructures have been electrodeposited within the pores of porous silicon templates with average pore diameters between 25 and 60 nm. In this diameter regime, the pore formation in general is accompanied by dendritic growth resulting in rough pore walls, which involves metal deposits also offering a branched structure. These side branches influence the magnetic properties of the composite system not only due to modified and peculiar stray fields but also because of a reduced interpore spacing by the approaching of adjacent side pores.

Magnetically interacting low dimensional Ni-nanostructures within porous silicon.

Electrodeposition of ferromagnetic metals, a common method to fabricate magnetic nanostructures, is used for the incorporation of Ni structures into the pores of porous silicon templates. The porous silicon is fabricated in various morphologies with average pore-diameters between 40 and 95 nm and concomitant pore-distances between 60 and 40 nm. The metal nanostructures are deposited with different geometries as spheres, ellipsoids or wires influenced by the deposition process parameters.

Surface plasmon leakage radiation microscopy at the diffraction limit.

This paper describes the image formation process in optical leakage radiation microscopy of surface plasmon-polaritons with diffraction limited spatial resolution. The comparison of experimentally recorded images with simulations of point-like surface plasmon-polariton emitters allows for an assignment of the observed fringe patterns. A simple formula for the prediction of the fringe periodicity is presented and practically relevant effects of abberations in the imaging system are discussed.

Measurement and reduction of damping in plasmonic nanowires.

We report on a spectroscopic study of surface plasmon damping and group velocity in polycrystalline silver and gold nanowires. By comparing to single-crystalline wires and by using different substrates, we quantitatively deduce the relative damping contributions due to metal crystallinity and absorption in the substrate. Compared to absorbing substrates, we find strongly reduced plasmonic damping for polycrystalline nanowires on quartz substrates, enabling the application of such wires for plasmonic waveguide networks.

Attenuation of ultrasound in severely plastically deformed nickel.

Ultrasound attenuation was measured in nickel specimens of about 30 mm diameter prepared using the high pressure torsion technique. The cold working process produced an equivalent shear strain increasing from zero at the center up to 1000% at the edge of the specimen. The fragmentation of the grains due to multiple dislocations led to an ultrafine microstructure with large angle grain boundaries.

Design and Optical Properties of Active Polymer-Coated Plasmonic Nanostructures.

The grafting of stimuli-responsive polymer brushes on plasmonic structures provides a perfectly controlled two-dimensional active device with optical properties that can be modified through external stimuli. Herein, we demonstrate thermally induced modifications of the plasmonic response of lithographic gold nanoparticles functionalized by thermosensitive polymer brushes of (poly(N-isopropylacrylamide), PNIPAM). Optical modifications result from refractive local index changes due to a phase transition from a hydrophilic state (swollen regime) to a hydrophobic state (collapsed regime) of the polymer chains occurring in a very small range of temperatures.