Electron microscopy approach to the wetting dynamics of single organosilanized mesopores.

Columnar mesoporous silicon (PSi) with hydrophobic vs. hydrophilic chemistries was chosen as a model for the local (pore-by-pore) study of water-pore interactions. Tomographic reconstructions provided a 3D view of the ramified pore structure. An in situ study of PSi wetting was conducted for categorized pore diameters by environmental scanning TEM. An appropriate setting of the contrast allows for the normalization of the gray scale in the images as a function of relative humidity (RH). This allows constructing an isotherm for each single pore and a subsequent averaging provides an isotherm for each pore size range. The isotherms systematically point to an initial adsorption through the formation of water adlayers, followed by a capillary filling process at higher RH. The local isotherms correlate with (global) gravimetric determination of wetting. Our results point at the validation of a technique for the study of aging and stability of single-pore nanoscale devices.

Real-space observation of ultraconfined in-plane anisotropic acoustic terahertz plasmon polaritons.

Thin layers of in-plane anisotropic materials can support ultraconfined polaritons, whose wavelengths depend on the propagation direction. Such polaritons hold potential for the exploration of fundamental material properties and the development of novel nanophotonic devices. However, the real-space observation of ultraconfined in-plane anisotropic plasmon polaritons (PPs)-which exist in much broader spectral ranges than phonon polaritons-has been elusive. Here we apply terahertz nanoscopy to image in-plane anisotropic low-energy PPs in monoclinic Ag2Te platelets. The hybridization of the PPs with their mirror image-by placing the platelets above a Au layer-increases the direction-dependent relative polariton propagation length and the directional polariton confinement. This allows for verifying a linear dispersion and elliptical isofrequency contour in momentum space, revealing in-plane anisotropic acoustic terahertz PPs. Our work shows high-symmetry (elliptical) polaritons on low-symmetry (monoclinic) crystals and demonstrates the use of terahertz PPs for local measurements of anisotropic charge carrier masses and damping.

Mechanical properties of friction induced nanocrystalline pearlitic steel.

Nanocrystalline structured variants of commercially available alloys have shown potential for boosting the mechanical properties of these materials, leading to a reduction in waste and thereby retaining feasible supply chains. One approach towards achieving these nanostructures resides in frictional treatments on manufactured parts, leading to differential refinement of the surface structure as compared to the bulk material. In this work the machining method is considered to be a testing platform for the formation and study of frictional nanostructured steel, assembly of which is stabilized by fast cooling of the produced chip. Analysis of the mechanical properties has shown extraordinary results at the surface, over 2000 MPa of strength on AISI1045 steel, more than three times the strength of the base material, demonstrating at the same time a reduction of 15% in the elastic modulus. The microscopic analysis suggests a reassembly of the elements in a new lattice of carbon supersaturated nano-ferrite.

"Missing" One-Dimensional Red-Phosphorus Chains Encapsulated within Single-Walled Carbon Nanotubes.

We identify the "missing" 1D-phosphorus allotrope, red phosphorus chains, formed in the interior of tip-opened single-walled carbon nanotubes (SWCNTs). Via a comprehensive experimental and theoretical study we show that in intermediate diameter cavities (1.6-2.9 nm), phosphorus vapor condenses into linear P8]P2 chains and fibrous red-phosphorus type cross-linked double-chains. Thermogravimetric and X-ray photoelectron spectroscopy analysis estimates ∼7 atom % of elemental phosphorus in the sample, while high-resolution energy dispersive X-ray spectroscopy mapping reveals that phosphorus fills the SWCNTs. High-resolution transmission electron microscopy (HRTEM) shows long chains inside the nanotubes with varying arrangement and packing density. A detailed match is obtained between density functional theory (DFT) simulations, HRTEM, and low-frequency Raman spectroscopy. Notably, a signature spectroscopic signal for phosphorus chain cross-linking is identified. When coupled with reinterpretation of literature data and wide-ranging DFT calculations, these results reveal a comprehensive picture of the diameter dependence of confined 1D-phosphorus allotropes.

Impact of Symmetry on Anisotropic Magnetoresistance in Textured Ferromagnetic Thin Films.

We report on the magnetoresistance of textured films consisting of 3d-ferromagnetic layers sandwiched by Pt. While the conventional cos^{2}φ behavior of the anisotropic magnetoresistance (AMR) is found when the magnetization M is varied in the film plane, cos^{2n}θ contributions (2n≤6) exist for rotating M in the plane perpendicular to the current. This finding is explained by the symmetry-adapted modeling of AMR of textured films demonstrating that the cos^{2}θ behavior cannot be used as a fingerprint for the presence of spin Hall magnetoresistance (SMR). Further, the interfacial MR contributions for Pt/Ni/Pt contradict the SMR behavior confirming the dominant role of AMR in all-metallic systems.

Films of filled single-wall carbon nanotubes as a new material for high-performance air-sustainable transparent conductive electrodes operating in a wide spectral range.

In this paper we show the advantages of transparent high conductive films based on filled single-wall carbon nanotubes. The nanotubes with internal channels filled with acceptor molecules (copper chloride or iodine) form networks demonstrating significantly improved characteristics. Due to the charge transfer between the nanotubes and filler, the doped-nanotube films exhibit a drop in electrical sheet resistance of an order of magnitude together with a noticeable increase of film transparency in the visible and near-infrared spectral range. The thermoelectric power measurements show a significant improvement of air-stability of the nanotube network in the course of the filling procedure. For the nanotube films with an initial transparency of 87% at 514 nm and electrical sheet resistance of 862 Ohm sq-1 we observed an improvement of transparency up to 91% and a decrease of sheet resistance down to 98 Ohm sq-1. The combination of the nanotube synthesis technique and molecules for encapsulation has been optimized for applications in optoelectronics.

Creation of nanosized holes in graphene planes for improvement of rate capability of lithium-ion batteries.

Holes with an average size of 2-5 nm have been created in graphene layers by heating of graphite oxide (GO) in concentrated sulfuric acid followed by annealing in an argon flow. The hot mineral acid acts simultaneously as a defunctionalizing and etching agent, removing a part of oxygen-containing groups and lattice carbon atoms from the layers. Annealing of the holey reduced GO at 800 °C-1000 °C causes a decrease of the content of residual oxygen and the interlayer spacing thus producing thin compact stacks from holey graphene layers. Electrochemical tests of the obtained materials in half-cells showed that the removal of oxygen and creation of basal holes lowers the capacity loss in the first cycle and facilitates intercalation-deintercalation of lithium ions. This was attributed to minimization of electrolyte decomposition reactions, easier desolvation of lithium ions near the hole boundaries and appearance of multiple entrances for the naked ions into graphene stacks.

Cobalt oxide as a selective co-catalyst for water oxidation in the presence of an organic dye.

In photobiocatalytical processes involving the simultaneous oxidation of water and reduction of specific organic molecules (e.g., cofactors), the lack of physical separation of the redox half-reactions adversely affects the product stability. This is largely because organic molecules are generally less stable within harsh oxidative environments. In general, surface co-catalysts are able to improve the selectivity of photocatalysts towards water oxidation. However, harsh oxidative environments reduce the chemical stability of the organic molecules. Herein, we show that the use of Co3O4 as a surface co-catalyst on silver orthophosphate improve water photo-oxidation in the presence of organic dye molecules, such as methylene blue, that typically exhibits susceptibility toward photodegradation. The presence of Co3O4 on the photocatalyst surface prevents the adsorption of the organic dye, thus reducing its degradation rate. These findings provide a promising scenario for the visible light-driven reduction of organic molecules using water as an electron donor.

An approach to growth of Fe-Si multilayers with controlled composition profile-a way to exchange coupled thin films.

The growth, composition and structure of sandwich structures (Fe-rich layer/Si-rich layer/Fe-rich silicide layer) grown on a Si(111) surface were studied by a few complementary microscopic and spectroscopic techniques with high spatial resolution. Intermixing at the Fe/Si and Si/Fe interfaces is demonstrated. Fe-rich layers grown directly on the Si(111) surface are crystalline and have abrupt but rough interfaces at both sides. The succeeding layers are disordered and their interfaces are fuzzy. The distributions of Fe and Si within the layers are laterally non-uniform. The reproducible fabrication of thin non-magnetic silicide spacers of predetermined thickness is demonstrated. Sandwich structures with such spacers exhibit exchange coupling between ferromagnetic Fe-rich layers.

Segregation of materials in double precursor electron-beam-induced-deposition: a route to functional magnetic nanostructures.

Here we report an observation of the phenomenon of spatial segregation of two materials in double precursor electron beam induced deposition. Segregation occurs under proper deposition conditions in a single spot illumination due to generic variation of electron current density within an electron beam. Combining precursors for magnetic (dicobaltoctacarbonyl) and non-magnetic (tetraethyl orthosilicate) properties we demonstrate a one-step fabrication process for magnetic tubules at the scale of 100 nm. Electron holography applied on the cross-section of thus prepared tubules reveals the concentration of the magnetic field in the cobalt rich shell, corroborating spatially distributed functionality. We elaborate the numerical model describing the observed phenomenon and defining the conditions for its practical achievement.

Colloidal synthesis and optical properties of type-II CdSe-CdTe and inverted CdTe-CdSe core-wing heteronanoplatelets.

We developed colloidal synthesis to investigate the structural and electronic properties of CdSe-CdTe and inverted CdTe-CdSe heteronanoplatelets and experimentally demonstrate that the overgrowth of cadmium selenide or cadmium telluride core nanoplatelets with counterpartner chalcogenide wings leads to type-II heteronanoplatelets with emission energies defined by the bandgaps of the CdSe and CdTe platelets and the characteristic band offsets. The observed conduction and valence band offsets of 0.36 eV and 0.56 eV are in line with theoretical predictions. The presented type-II heteronanoplatelets exhibit efficient spatially indirect radiative exciton recombination with a quantum yield as high as 23%. While the exciton lifetime is strongly prolonged in the investigated type-II 2D systems with respect to 2D type-I systems, the occurring 2D giant oscillator strength (GOST) effect still leads to a fast and efficient exciton recombination. This makes type-II heteronanoplatelets interesting candidates for low threshold lasing applications and photovoltaics.

Crystallographically driven magnetic behaviour of arrays of monocrystalline Co nanowires.

Cobalt nanowires, 40 nm in diameter and several micrometers long, have been grown by controlled electrodeposition into ordered anodic alumina templates. The hcp crystal symmetry is tuned by a suitable choice of the electrolyte pH (between 3.5 and 6.0) during growth. Systematic high resolution transmission electron microscopy imaging and analysis of the electron diffraction patterns reveals a dependence of crystal orientation from electrolyte pH. The tailored modification of the crystalline signature results in the reorientation of the magnetocrystalline anisotropy and increasing experimental coercivity and squareness with decreasing polar angle of the 'c' growth axis. Micromagnetic modeling of the demagnetization process and its angular dependence is in agreement with the experiment and allows us to establish the change in the character of the magnetization reversal: from quasi-curling to vortex domain wall propagation modes when the crystal 'c' axis tilts more than 75° in respect to the nanowire axis.

Crystallography-driven positive exchange bias in Co/CoO bilayers.

We have studied the temperature dependence of the exchange bias effect in epitaxial Co/CoO bilayer structures with in-plane uniaxial magnetocrystalline anisotropy. We have measured the anisotropic positive exchange bias, which is independent from the initial cooling field value. Synchronous with the occurrence of positive exchange bias, distinct changes in the magnetization reversal process indicate a temperature-dependent rotation of the effective anisotropy and exchange bias axis. Model calculations based upon the electron microscopy-determined epitaxial Co/CoO-interface structure corroborate this interpretation.

Correlative infrared-electron nanoscopy reveals the local structure-conductivity relationship in zinc oxide nanowires.

High-resolution characterization methods play a key role in the development, analysis and optimization of nanoscale materials and devices. Because of the various material properties, only a combination of different characterization techniques provides a comprehensive understanding of complex functional materials. Here we introduce correlative infrared-electron nanoscopy, a novel method yielding transmission electron microscope and infrared near-field images of one and the same nanostructure. While transmission electron microscopy provides structural information up to the atomic level, infrared near-field imaging yields nanoscale maps of chemical composition and conductivity. We demonstrate the method's potential by studying the relation between conductivity and crystal structure in ZnO nanowire cross-sections. The combination of infrared conductivity maps and the local crystal structure reveals a radial free-carrier gradient, which inversely correlates to the density of extended crystalline defects. Our method opens new avenues for studying the local interplay between structure, conductivity and chemical composition in widely different material systems.

Self-assembly of a sulphur-terminated graphene nanoribbon within a single-walled carbon nanotube.

The ability to tune the properties of graphene nanoribbons (GNRs) through modification of the nanoribbon's width and edge structure widens the potential applications of graphene in electronic devices. Although assembly of GNRs has been recently possible, current methods suffer from limited control of their atomic structure, or require the careful organization of precursors on atomically flat surfaces under ultra-high vacuum conditions. Here we demonstrate that a GNR can self-assemble from a random mixture of molecular precursors within a single-walled carbon nanotube, which ensures propagation of the nanoribbon in one dimension and determines its width. The sulphur-terminated dangling bonds of the GNR make these otherwise unstable nanoribbons thermodynamically viable over other forms of carbon. Electron microscopy reveals elliptical distortion of the nanotube, as well as helical twist and screw-like motion of the nanoribbon. These effects suggest novel ways of controlling the properties of these nanomaterials, such as the electronic band gap and the concentration of charge carriers.

Synthesis and properties of hydroxyapatite-containing porous titania coating on ultrafine-grained titanium by micro-arc oxidation.

Equal channel angular pressing results in ultrafine-grained (approximately 200-500 nm) Ti with superior mechanical properties without harmful alloying elements, which benefits medical implants. To further improve the bioactivity of Ti surfaces, Ca/P-containing porous titania coatings were prepared on ultrafine-grained and coarse-grained Ti by micro-arc oxidation (MAO). The phase identification, composition, morphology and microstructure of the coatings and the thermal stability of ultrafine-grained Ti during MAO were investigated subsequently. The amounts of Ca, P and the Ca/P ratio of the coatings formed on ultrafine-grained Ti were greater than those on coarse-grained Ti. Nanocrystalline hydroxyapatite and alpha-Ca(3)(PO(4))(2) phases appeared in the MAO coating formed on ultrafine-grained Ti for 20 min (E20). Incubated in a simulated body fluid, bone-like apatite was completely formed on the surface of E20 after 2 days, thus evidencing preferable bioactivity. Compared with initial ultrafine-grained Ti, the microhardness of the E20 substrate was reduced by 8% to 2.9 GPa, which is considerably more than that of coarse-grained Ti (approximately 1.5 GPa).

Byproduct with altered fluorescent properties is formed during standard deprotection step of hexachlorofluorescein labeled oligonucleotides.

HEX-labeled oligonucleotides obtained via typical synthetic protocols may contain more than 15% of material with altered spectral characteristics. We discovered hexachlorofluorescein residue transformation unknown earlier for standard DNA ammonolysis step. HEX residue reacts with ammonium hydroxide yielding acridine derivative, which has differed UV-VIS and fluorescent properties compared to HEX. Therefore, for critical bioassays where sensitivity and/or fluorescent signal differentiation (e.g., in quantitative or multiplexed assays) are essential, the careful RP-HPLC purification step is required.

Significance of methods for purification of oligodeoxyribonucleotide probes for the efficiency of gene diagnosis by real-time PCR.

Analysis of the use of real-time PCR with fluorescent registration of results for gene diagnosis of infectious diseases showed that the sensitivity and reliability of quantitative evaluation of DNA targets directly depended on the method of purification of oligonucleotide probes. Chromatographic behavior of synthetic probes carrying various fluorophores and fluorescence quenchers was analyzed. Approaches to optimization of purification methods are proposed enabling elimination of previously undetectable admixtures. The importance of these studies is explained by the need in extending the armory of methods for the development and production of diagnosticums for detection of infectious and hereditary diseases, identification of genetically modified organisms, and for a wide spectrum of research in molecular biology and medicine.

[Telomeric oligonucleotide complexes with PGEk protein vector: internalization by target cells and antiproliferative properties].

The recombinant protein PGEk, containing residual of the human epidermal factor (hEGF) bearing DNA binding sequence, retains ability of hEGF to bind with hEGF receptor and to induce cell proliferation was shown. On an example of PGEk complexes with telomeric mimic-oligodeoxyribonucleotide d(TTAGGG)4 and with its thio-analogue we had found such systems can be effectively and selectively internalized by hEGF receptors super expressing cells. The association of this process with a protein/oligonucleotide ratio in complexes was investigated. The intracellular localization of oligonucleotides was explored. We had shown that PGEk not only promotes intensive delivery of oligonucleotides, but also protects them from degradation by nucleases. The oligonucleotides in composition of complexes have considerably more expressed cytotoxic activity in comparison with free oligonucleotides.

Principles of creation of protein carriers of DNA new derivatives of human epidermal growth factor for gene therapy.

We formulated a new approach to the creation of transport proteins for the delivery of foreign DNA to target cells and used it for obtaining a polypeptide PGEk. Structural and functional analysis of PGEk--DNA complexes demonstrated good prospects for the creation of a wide spectrum of targeted preparations for gene therapy. These approaches and regularities are necessary for construction of new DNA carriers selective for various cell types.