Characterization of Self-Assembled Monolayers on a Ruthenium Surface

PubMed Central

2017-01-01

We have modified and stabilized the ruthenium surface by depositing a self-assembled monolayer (SAM) of 1-hexadecanethiol on a polycrystalline ruthenium thin film. The growth mechanism, dynamics, and stability of these monolayers were studied. SAMs, deposited under ambient conditions, on piranha-cleaned and piranha + H2SO4 cleaned substrates were compared to monolayers formed on H-radical-cleaned Ru surfaces. We found that alkanethiols on H-radical-cleaned Ru formed densely packed monolayers that remained stable when kept in a nitrogen atmosphere. X-ray photoelectron spectroscopy (XPS) shows a distinct sulfur peak (BE = 162.3 eV), corresponding to metal–sulfur bonding. When exposed to ambient conditions, the SAM decayed over a period of hours. PMID:28585831

Plasma-assisted oxide removal from ruthenium-coated EUV optics

NASA Astrophysics Data System (ADS)

Dolgov, A.; Lee, C. J.; Bijkerk, F.; Abrikosov, A.; Krivtsun, V. M.; Lopaev, D.; Yakushev, O.; van Kampen, M.

2018-04-01

An experimental study of oxide reduction at the surface of ruthenium layers on top of multilayer mirrors and thin Ru/Si films is presented. Oxidation and reduction processes were observed under conditions close to those relevant for extreme ultraviolet lithography. The oxidized ruthenium surface was exposed to a low-temperature hydrogen plasma, similar to the plasma induced by extreme ultraviolet radiation. The experiments show that hydrogen ions are the main reducing agent. Furthermore, the addition of hydrogen radicals increases the reduction rate beyond that expected from simple flux calculations. We show that low-temperature hydrogen plasmas can be effective for reducing oxidized top surfaces. Our proof-of-concept experiments show that an in situ, EUV-generated plasma cleaning technology is feasible.

Application of maximum-likelihood estimation in optical coherence tomography for nanometer-class thickness estimation

NASA Astrophysics Data System (ADS)

Huang, Jinxin; Yuan, Qun; Tankam, Patrice; Clarkson, Eric; Kupinski, Matthew; Hindman, Holly B.; Aquavella, James V.; Rolland, Jannick P.

2015-03-01

In biophotonics imaging, one important and quantitative task is layer-thickness estimation. In this study, we investigate the approach of combining optical coherence tomography and a maximum-likelihood (ML) estimator for layer thickness estimation in the context of tear film imaging. The motivation of this study is to extend our understanding of tear film dynamics, which is the prerequisite to advance the management of Dry Eye Disease, through the simultaneous estimation of the thickness of the tear film lipid and aqueous layers. The estimator takes into account the different statistical processes associated with the imaging chain. We theoretically investigated the impact of key system parameters, such as the axial point spread functions (PSF) and various sources of noise on measurement uncertainty. Simulations show that an OCT system with a 1 μm axial PSF (FWHM) allows unbiased estimates down to nanometers with nanometer precision. In implementation, we built a customized Fourier domain OCT system that operates in the 600 to 1000 nm spectral window and achieves 0.93 micron axial PSF in corneal epithelium. We then validated the theoretical framework with physical phantoms made of custom optical coatings, with layer thicknesses from tens of nanometers to microns. Results demonstrate unbiased nanometer-class thickness estimates in three different physical phantoms.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Callis, C.F.; Moore, R.L.

1959-09-01

>The separation of ruthenium from aqueous solutions containing uranium plutonium, ruthenium, and fission products is described. The separation is accomplished by providing a nitric acid solution of plutonium, uranium, ruthenium, and fission products, oxidizing plutonium to the hexavalent state with sodium dichromate, contacting the solution with a water-immiscible organic solvent, such as hexone, to extract plutonyl, uranyl, ruthenium, and fission products, reducing with sodium ferrite the plutonyl in the solvent phase to trivalent plutonium, reextracting from the solvent phase the trivalent plutonium, ruthenium, and some fission products with an aqueous solution containing a salting out agent, introducing ozone into the aqueous acid solution to oxidize plutonium to the hexavalent state and ruthenium to ruthenium tetraoxide, and volatizing off the ruthenium tetraoxide.

Low pressure hand made PVD system for high crystalline metal thin film preparation in micro-nanometer scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Rosikhin, Ahmad, E-mail: a.rosikhin86@yahoo.co.id; Hidayat, Aulia Fikri; Marimpul, Rinaldo

High crystalline metal thin film preparation in application both for catalyst substrate or electrode in any electronic devices always to be considered in material functional material research and development. As a substrate catalyst, this metal take a role as guidance for material growth in order to resulted in proper surface structure although at the end it will be removed via etching process. Meanwhile as electrodes, it will dragging charges to be collected inside. This brief discussion will elaborate general fundamental principle of physical vapor deposition (PVD) system for metal thin film preparation in micro-nanometer scale. The influence of thermodynamic parametersmore » and metal characteristic such as melting point and particle size will be elucidated. Physical description of deposition process in the chamber can be simplified by schematic evaporation phenomena which is supported by experimental measurement such as SEM and XRD.« less

Ruthenium films by digital chemical vapor deposition: Selectivity, nanostructure, and work function

NASA Astrophysics Data System (ADS)

Dey, Sandwip K.; Goswami, Jaydeb; Gu, Diefeng; de Waard, Henk; Marcus, Steve; Werkhoven, Chris

2004-03-01

Ruthenium electrodes were selectively deposited on photoresist-patterned HfO2 surface [deposited on a SiOx/Si wafer by atomic layer deposition (ALD)] by a manufacturable, digital chemical vapor deposition (DCVD) technique. DCVD of Ru was carried out at 280-320 °C using an alternate delivery of Bis (2,2,6,6-tetramethyl-3,5-heptanedionato)(1,5-cyclooctadiene)Ru (dissolved in tetrahydrofuran) and oxygen. The as-deposited Ru films were polycrystalline, dense, and conducting (resistivity ˜20.6 μΩ cm). However, Rutherford backscattering spectroscopy, x-ray photoelectron spectroscopy, and high-resolution electron microscopy results indicate the presence of an amorphous RuOx at the Ru grain boundaries and at the DCVD-Ru/ALD-HfO2 interface. The estimated work function of DCVD-Ru on ALD-HfO2 was ˜5.1 eV. Moreover, the equivalent oxide thickness, hysteresis in capacitance-voltage, and leakage current density at -2 V of the HfO2/SiOx dielectric, after forming gas (95% N2+5% H2) annealing at 450 °C for 30 min, were 1.4 nm, 20 mV, and 7.4×10-7 A cm-2, respectively.

Ruthenium(ii)-polypyridyl zirconium(iv) metal–organic frameworks as a new class of sensitized solar cells

DOE PAGES

Maza, W. A.; Haring, A. J.; Ahrenholtz, S. R.; ...

2015-10-16

Ruthenium(ii) polypyridyl-doped metal–organic framework sensitized films on TiO 2 for photovoltaics reveal that the preparative method of dye doping/incorporation into the MOF is integral to the total solar cell efficiency.

SEPARATION OF RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Beederman, M.; Vogler, S.; Hyman, H.H.

1959-07-14

The separation of rathenium from a rathenium containing aqueous solution is described. The separation is accomplished by adding sodium nitrite, silver nitrate and ozone to the ruthenium containing aqueous solution to form ruthenium tetroxide and ihen volatilizing off the ruthenium tetroxide.

Chemical Mechanical Polishing of Ruthenium, Cobalt, and Black Diamond Films

NASA Astrophysics Data System (ADS)

Peethala, Brown Cornelius

Ta/TaN bilayer serves as the diffusion barrier as well as the adhesion promoter between Cu and the dielectric in 32 nm technology devices. A key concern of future technology devices (<32 nm) for Cu interconnects is the extendibility of TaN/Ta/Cu-seed to sustain the diffusion barrier performance without forming voids and meeting the requirements of low resistivity. These are very challenging requirements for the Ta/TaN bilayer at a thickness of < 5 nm. Hence, ruthenium (Ru) and cobalt (Co), among these, are being considered for replacing Ta/TaN as barrier materials for Cu interconnects in future technology devices. Both are very attractive for reasons such as the capability of direct electroplating of Cu, lower resistivity and for a single layer (vs. a bilayer of Ta/TaN) to act as a barrier. During patterning, they need to be planarized using conventional chemical mechanical polishing (CMP) to achieve a planar surface. However, CMP of these new barrier materials requires novel slurry compositions that provide adequate selectivity towards Cu and dielectric films, and minimize galvanic corrosion. Apart from the application as a barrier, Ru also has been proposed as a lower electrode material in metal-insulator-metal capacitors where high (> 50 nm/min) Ru removal rates (RRs) are required and as a stop layer in magnetic recording head fabrication where low (< 1 nm/min) Ru RRs are desired. A Ru removal rate of ˜60 nm/min was achieved with a colloidal silica-based slurry at pH 9 using potassium periodate (KIO4) as the oxidizer. At this pH, toxic RuO4 does not form eliminating a major challenge in Ru CMP. This removal rate was obtained by increasing the solubility of KIO4 by adding potassium hydroxide (KOH). It was also determined that increased the ionic strength is not responsible for the observed increase in Ru removal rate. Benzotirazole (BTA) and ascorbic acid were added to the slurry to reduce the open circuit potential (Eoc) difference between Cu and Ru to ˜20 m

Titanium and Ruthenium Phthalocyanines for NO2 Sensors: A Mini-Review

PubMed Central

Paoletti, Anna Maria; Pennesi, Giovanna; Rossi, Gentilina; Generosi, Amanda; Paci, Barbara; Albertini, Valerio Rossi

2009-01-01

This review presents studies devoted to the description and comprehension of phenomena connected with the sensing behaviour towards NO2 of films of two phthalocyanines, titanium bis-phthalocyanine and ruthenium phthalocyanine. Spectroscopic, conductometric, and morphological features recorded during exposure to the gas are explained and the mechanisms of gas-molecule interaction are also elucidated. The review also shows how X-ray reflectivity can be a useful tool for monitoring morphological parameters such as thickness and roughness that are demonstrated to be sensitive variables for monitoring the exposure of thin films of sensor materials to NO2 gas. PMID:22346697

IR-doped ruthenium oxide catalyst for oxygen evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I. (Inventor); Narayanan, Sekharipuram R. (Inventor)

2012-01-01

A method for preparing a metal-doped ruthenium oxide material by heating a mixture of a doping metal and a source of ruthenium under an inert atmosphere. In some embodiments, the doping metal is in the form of iridium black or lead powder, and the source of ruthenium is a powdered ruthenium oxide. An iridium-doped or lead-doped ruthenium oxide material can perform as an oxygen evolution catalyst and can be fabricated into electrodes for electrolysis cells.

Sensitive SERS detection at the single-particle level based on nanometer-separated mushroom-shaped plasmonic dimers

NASA Astrophysics Data System (ADS)

Xiang, Quan; Li, Zhiqin; Zheng, Mengjie; Liu, Qing; Chen, Yiqin; Yang, Lan; Jiang, Tian; Duan, Huigao

2018-03-01

Elevated metallic nanostructures with nanogaps (<10 nm) possess advantages for surface enhanced Raman scattering (SERS) via the synergic effects of nanogaps and efficient decoupling from the substrate through an elevated three-dimensional (3D) design. In this work, we demonstrate a pattern-transfer-free process to reliably define elevated nanometer-separated mushroom-shaped dimers directly from 3D resist patterns based on the gap-narrowing effect during the metallic film deposition. By controlling the initial size of nanogaps in resist structures and the following deposited film thickness, metallic nanogaps could be tuned at the sub-10 nm scale with single-digit nanometer precision. Both experimental and simulated results revealed that gold dimer on mushroom-shaped pillars have the capability to achieve higher SERS enhancement factor comparing to those plasmonic dimers on cylindrical pillars or on a common SiO2/Si substrate, implying that the nanometer-gapped elevated dimer is an ideal platform to achieve the highest possible field enhancement for various plasmonic applications.

Mechanical Properties of Materials with Nanometer Scale Microstructures

DOE Office of Scientific and Technical Information (OSTI.GOV)

William D. Nix

2004-10-31

We have been engaged in research on the mechanical properties of materials with nanometer-scale microstructural dimensions. Our attention has been focused on studying the mechanical properties of thin films and interfaces and very small volumes of material. Because the dimensions of thin film samples are small (typically 1 mm in thickness, or less), specialized mechanical testing techniques based on nanoindentation, microbeam bending and dynamic vibration of micromachined structures have been developed and used. Here we report briefly on some of the results we have obtained over the past three years. We also give a summary of all of the dissertations,more » talks and publications completed on this grant during the past 15 years.« less

Characterization And Dissolution Properties Of Ruthenium Oxides

EPA Science Inventory

Ruthenium oxides (RuO₂•1.10H₂O and RuO₂) have been synthesized by forced hydrolysis and oxidation of ruthenium chloride. The resulting materials were extensively characterized to determine the crystallinity, surface area, and ruthenium oxidation ...

XPS study of ruthenium tris-bipyridine electrografted from diazonium salt derivative on microcrystalline boron doped diamond.

PubMed

Agnès, Charles; Arnault, Jean-Charles; Omnès, Franck; Jousselme, Bruno; Billon, Martial; Bidan, Gérard; Mailley, Pascal

2009-12-28

Boron doped diamond (BDD) functionalization has received an increasing interest during the last few years. Such an infatuation comes from the original properties of BDD, including chemical stability or an electrochemical window, that opens the way for the design of (bio)sensors or smart interfaces. In such a context, diazonium salts appear to be well suited for BDD functionalization as they enable covalent immobilization of functional entities such as enzymes or DNA. In this study we report microcrystalline BDD functionalization with a metallic complex, ruthenium tris(bipyridine), using the p-(tris(bipyridine)Ru(2+))phenyl diazonium salt. Electrografting using cyclic voltammetry (CV) allowed the formation of a ruthenium complex film that was finely characterized using electrochemistry and X-ray photoelectron spectroscopy (XPS). Moreover, we showed that chronopotentiometry (CP) is a convenient tool to monitor Ru complex film deposition through the control of the electrochemical pulse parameters (i.e. current density and pulse duration). Finally, such a control was demonstrated through the correlation between electrochemical and XPS characterizations.

Metal substrates with nanometer scale surface roughness for flexible electronics

NASA Astrophysics Data System (ADS)

Lee, Jong-Lam; Kim, Kisoo

2012-09-01

In this work, we present a novel way in fabricating a metal substrate with nanometer scale in surface roughness (Ra < 1 nm) using a surface roughness transfer method without any polishing or planarization process. Ag film (8 inch, Ra = 0.57 nm) and an INVAR (Invariable alloy) one (20 cm × 20 cm, Ra = 1.40 nm) were demonstrated. The INVAR film was used as a substrate for fabricating organic light emitting diodes (OLED) and organic photovoltaic (OPV). The optical and electrical characteristics of OLEDs and OPVs using the INVAR were comparable to those using a conventional ITO glass substrate.

TEM Study of Intergranular Fluid Distributions in Rocks at a Nanometer Scale

NASA Astrophysics Data System (ADS)

Hiraga, T.; Anderson, I. M.; Kohlstedt, D. L.

2002-12-01

The distribution of intergranular fluids in rocks plays an essential role in fluid migration and rock rheology. Structural and chemical analyses with sub-nanometer resolution is possible with transmission and scanning-transmission electron microscopy; therefore, it is possible to perform the fine-scale structural analyses required to determine the presence or absence of very thin fluid films along grain boundaries. For aqueous fluids in crustal rocks, Hiraga et al. (2001) observed a fluid morphology controlled by the relative values of the solid-solid and solid-fluid interfacial energies, which resulted in well-defined dihedral angles. Their high-resolution transmission electron microscopy (TEM) observations demonstrate that grain boundaries are tight even at a nanometer scale, consistent with the absence of aqueous fluid films. For partially molten ultra-mafic rocks, two conflicting conclusions have been reached: nanometer-thick melt films wet grain boundaries (Drury and Fitz Gerald 1996; De Kloe et al. 2000) versus essentially all grain boundaries are melt-free (Vaughan et al. 1982; Kohlstedt 1990). To resolve this conflict, Hiraga et al. (2002) examined grain boundaries in quenched partially molten peridotites. Their observations demonstrate the following: (i) Although a small fraction of the grains are separated by relatively thick (~1 μm) layers of melt, lattice fringe images obtained with a high-resolution TEM reveal that most of the remaining boundaries do not contain a thin amorphous phase. (ii) In addition, the composition of olivine-olivine grain boundaries was analyzed with a nano-beam analytical scanning TEM with a probe size of <2 nm. Although the grain boundaries contained no melt film, the concentration of Ca, Al and Ti were enhanced near the boundaries. The segregation of these elements to the grain boundaries formed enriched regions <7 nm wide. A similar pattern of chemical segregation was detected in subsolidus systems. Creep experiments on the

SOLVENT EXTRACTION OF RUTHENIUM

DOEpatents

Hyman, H.H.; Leader, G.R.

1959-07-14

The separation of rathenium from aqueous solutions by solvent extraction is described. According to the invention, a nitrite selected from the group consisting of alkali nitrite and alkaline earth nitrite in an equimolecular quantity with regard to the quantity of rathenium present is added to an aqueous solution containing ruthenium tetrantrate to form a ruthenium complex. Adding an organic solvent such as ethyl ether to the resulting mixture selectively extracts the rathenium complex.

Platinum-ruthenium-palladium fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2006-02-07

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum at a concentration that is between about 20 and about 60 atomic percent, ruthenium at a concentration that is between about 20 and about 60 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having an atomic ratio of platinum to ruthenium that is between about 0.7 and about 1.2. Alternatively, the catalyst may contain platinum at a concentration that is between about 25 and about 50 atomic percent, ruthenium at a concentration that is between about 25 and about 55 atomic percent, palladium at a concentration that is between about 5 and about 45 atomic percent, and having a difference between the concentrations of ruthenium and platinum that is no greater than about 20 atomic percent.

Ruthenium red-induced bundling of bacterial cell division protein, FtsZ.

PubMed

Santra, Manas Kumar; Beuria, Tushar K; Banerjee, Abhijit; Panda, Dulal

2004-06-18

The assembly of FtsZ plays a major role in bacterial cell division, and it is thought that the assembly dynamics of FtsZ is a finely regulated process. Here, we show that ruthenium red is able to modulate FtsZ assembly in vitro. In contrast to the inhibitory effects of ruthenium red on microtubule polymerization, we found that a substoichiometric concentration of ruthenium red strongly increased the light-scattering signal of FtsZ assembly. Further, sedimentable polymer mass was increased by 1.5- and 2-fold in the presence of 2 and 10 microm ruthenium red, respectively. In addition, ruthenium red strongly reduced the GTPase activity and prevented dilution-induced disassembly of FtsZ polymers. Electron microscopic analysis showed that 4-10 microm of ruthenium red produced thick bundles of FtsZ polymers. The significant increase in the light-scattering signal and pelletable polymer mass in the presence of ruthenium red seemed to be due to the bundling of FtsZ protofilaments into larger polymers rather than the actual increase in the level of polymeric FtsZ. Furthermore, ruthenium red was found to copolymerize with FtsZ, and the copolymerization of substoichiometric amounts of ruthenium red with FtsZ polymers promoted cooperative assembly of FtsZ that produced large bundles. Calcium inhibited the binding of ruthenium red to FtsZ. However, a concentration of calcium 1000-fold higher than that of ruthenium red was required to produce similar effects on FtsZ assembly. Ruthenium red strongly modulated FtsZ polymerization, suggesting the presence of an important regulatory site on FtsZ and suggesting that a natural ligand, which mimics the action of ruthenium red, may regulate the assembly of FtsZ in bacteria.

Highly sensitive catalytic spectrophotometric determination of ruthenium

NASA Astrophysics Data System (ADS)

Naik, Radhey M.; Srivastava, Abhishek; Prasad, Surendra

2008-01-01

A new and highly sensitive catalytic kinetic method (CKM) for the determination of ruthenium(III) has been established based on its catalytic effect on the oxidation of L-phenylalanine ( L-Pheala) by KMnO 4 in highly alkaline medium. The reaction has been followed spectrophotometrically by measuring the decrease in the absorbance at 526 nm. The proposed CKM is based on the fixed time procedure under optimum reaction conditions. It relies on the linear relationship where the change in the absorbance (Δ At) versus added Ru(III) amounts in the range of 0.101-2.526 ng ml -1 is plotted. Under the optimum conditions, the sensitivity of the proposed method, i.e. the limit of detection corresponding to 5 min is 0.08 ng ml -1, and decreases with increased time of analysis. The method is featured with good accuracy and reproducibility for ruthenium(III) determination. The ruthenium(III) has also been determined in presence of several interfering and non-interfering cations, anions and polyaminocarboxylates. No foreign ions interfered in the determination ruthenium(III) up to 20-fold higher concentration of foreign ions. In addition to standard solutions analysis, this method was successfully applied for the quantitative determination of ruthenium(III) in drinking water samples. The method is highly sensitive, selective and very stable. A review of recently published catalytic spectrophotometric methods for the determination of ruthenium(III) has also been presented for comparison.

Superconductor-Insulator transition in sputtered amorphous MoRu and MoRuN thin films

NASA Astrophysics Data System (ADS)

Makise, K.; Shinozaki, B.; Ichikawa, F.

2018-03-01

This work shows the experimental results of the superconductor-insulator (S-I) transition for amorphous molybdenum ruthenium (MoRu) and molybdenum ruthenium nitride (MoRuN) films. These amorphous films onto c-plane sapphire substrates have been interpreted to be homogeneous by XRD and AFM measurements. Electrical and superconducting properties measurements were carried out on MoRu and MoRuN thin films deposited by reactive sputtering technique. We have analysed the data on R sq (T) based on excess conductivity of superconducting films by the AL and MT term and weak localization and electron-electron interaction for the conductance. MoRu films which offer the most homogeneous film morphology, showed a critical sheet resistance of transition, Rc, of ∼ 2 kΩ. This values is smaller than those previously our reported for quench-condensed MoRu films on SiO underlayer held at liquid He temperature.

Growth of strontium ruthenate films by hybrid molecular beam epitaxy

DOE PAGES

Marshall, Patrick B.; Kim, Honggyu; Ahadi, Kaveh; ...

2017-09-01

We report on the growth of epitaxial Sr 2RuO 4 films using a hybrid molecular beam epitaxy approach in which a volatile precursor containing RuO 4 is used to supply ruthenium and oxygen. The use of the precursor overcomes a number of issues encountered in traditional molecular beam epitaxy that uses elemental metal sources. Phase-pure, epitaxial thin films of Sr 2RuO 4 are obtained. At high substrate temperatures, growth proceeds in a layer-by-layer mode with intensity oscillations observed in reflection high-energy electron diffraction. Films are of high structural quality, as documented by x-ray diffraction, atomic force microscopy, and transmission electronmore » microscopy. In conclusion, the method should be suitable for the growth of other complex oxides containing ruthenium, opening up opportunities to investigate thin films that host rich exotic ground states.« less

METABOLISM OF RUTHENIUM IN THE RAT. Technical Documentary Report

DOE Office of Scientific and Technical Information (OSTI.GOV)

Traynor, J.E.; Leeper, S.W.

1961-12-01

Seventeen Sprague-Dawley rats were injected intramuscularly and intraperitoneally with ruthenium-106. The amount of this isotope was determined daily for 5 weeks in the urine and feces. Animals were sacrificed at intervals and the various organs were analyzed for ruthenium. It was noted from this experiment that the pathways of absorption, metabolism, and excretion are dependent on the route of administration of ruthenium. (auth)

Iridium-Doped Ruthenium Oxide Catalyst for Oxygen Evolution

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Narayan, Sri R.; Billings, Keith J.

2011-01-01

NASA requires a durable and efficient catalyst for the electrolysis of water in a polymer-electrolyte-membrane (PEM) cell. Ruthenium oxide in a slightly reduced form is known to be a very efficient catalyst for the anodic oxidation of water to oxygen, but it degrades rapidly, reducing efficiency. To combat this tendency of ruthenium oxide to change oxidation states, it is combined with iridium, which has a tendency to stabilize ruthenium oxide at oxygen evolution potentials. The novel oxygen evolution catalyst was fabricated under flowing argon in order to allow the iridium to preferentially react with oxygen from the ruthenium oxide, and not oxygen from the environment. Nanoparticulate iridium black and anhydrous ruthenium oxide are weighed out and mixed to 5 18 atomic percent. They are then heat treated at 300 C under flowing argon (in order to create an inert environment) for a minimum of 14 hours. This temperature was chosen because it is approximately the creep temperature of ruthenium oxide, and is below the sintering temperature of both materials. In general, the temperature should always be below the sintering temperature of both materials. The iridium- doped ruthenium oxide catalyst is then fabricated into a PEM-based membrane- electrode assembly (MEA), and then mounted into test cells. The result is an electrolyzer system that can sustain electrolysis at twice the current density, and at the same efficiency as commercial catalysts in the range of 100-200 mA/sq cm. At 200 mA/sq cm, this new system operates at an efficiency of 85 percent, which is 2 percent greater than commercially available catalysts. Testing has shown that this material is as stable as commercially available oxygen evolution catalysts. This means that this new catalyst can be used to regenerate fuel cell systems in space, and as a hydrogen generator on Earth.

Imaging Nanometer Phase Coexistence at Defects During the Insulator-Metal Phase Transformation in VO2 Thin Films by Resonant Soft X-ray Holography.

PubMed

Vidas, Luciana; Günther, Christian M; Miller, Timothy A; Pfau, Bastian; Perez-Salinas, Daniel; Martínez, Elías; Schneider, Michael; Gührs, Erik; Gargiani, Pierluigi; Valvidares, Manuel; Marvel, Robert E; Hallman, Kent A; Haglund, Richard F; Eisebitt, Stefan; Wall, Simon

2018-05-18

We use resonant soft X-ray holography to image the insulator-metal phase transition in vanadium dioxide with element and polarization specificity and nanometer spatial resolution. We observe that nanoscale inhomogeneity in the film results in spatial-dependent transition pathways between the insulating and metallic states. Additional nanoscale phases form in the vicinity of defects which are not apparent in the initial or final states of the system, which would be missed in area-integrated X-ray absorption measurements. These intermediate phases are vital to understand the phase transition in VO 2 , and our results demonstrate how resonant imaging can be used to understand the electronic properties of phase-separated correlated materials obtained by X-ray absorption.

Electrochemistry at Nanometer-Scaled Electrodes

ERIC Educational Resources Information Center

Watkins, John J.; Bo Zhang; White, Henry S.

2005-01-01

Electrochemical studies using nanometer-scaled electrodes are leading to better insights into electrochemical kinetics, interfacial structure, and chemical analysis. Various methods of preparing electrodes of nanometer dimensions are discussed and a few examples of their behavior and applications in relatively simple electrochemical experiments…

Nanometer-scale oxide thin film transistor with potential for high-density image sensor applications.

PubMed

Jeon, Sanghun; Park, Sungho; Song, Ihun; Hur, Ji-Hyun; Park, Jaechul; Kim, Hojung; Kim, Sunil; Kim, Sangwook; Yin, Huaxiang; Chung, U-In; Lee, Eunha; Kim, Changjung

2011-01-01

The integration of electronically active oxide components onto silicon circuits represents an innovative approach to improving the functionality of novel devices. Like most semiconductor devices, complementary-metal-oxide-semiconductor image sensors (CISs) have physical limitations when progressively scaled down to extremely small dimensions. In this paper, we propose a novel hybrid CIS architecture that is based on the combination of nanometer-scale amorphous In-Ga-Zn-O (a-IGZO) thin-film transistors (TFTs) and a conventional Si photo diode (PD). With this approach, we aim to overcome the loss of quantum efficiency and image quality due to the continuous miniaturization of PDs. Specifically, the a-IGZO TFT with 180 nm gate length is probed to exhibit remarkable performance including low 1/f noise and high output gain, despite fabrication temperatures as low as 200 °C. In particular, excellent device performance is achieved using a double-layer gate dielectric (Al₂O₃/SiO₂) combined with a trapezoidal active region formed by a tailored etching process. A self-aligned top gate structure is adopted to ensure low parasitic capacitance. Lastly, three-dimensional (3D) process simulation tools are employed to optimize the four-pixel CIS structure. The results demonstrate how our stacked hybrid device could be the starting point for new device strategies in image sensor architectures. Furthermore, we expect the proposed approach to be applicable to a wide range of micro- and nanoelectronic devices and systems.

Hydronium ion motion in nanometer 3-methyl-pentane films

NASA Astrophysics Data System (ADS)

Bell, Richard C.; Wu, Kai; Iedema, Martin J.; Cowin, James P.

2007-07-01

An ion soft-landing approach was applied to study the motion of hydronium (D3O+) and cesium (Cs+) ions from 84to104K in glassy 3-methyl-pentane (3MP) films vapor deposited on Pt(111). Both ions were found to have very similar mobilities in 3MP. The span of ion mobilities probed is from ˜10-18to˜10-13m2V-1s-1. Ion transport in these films was studied as a function of film thickness and electric field strength. The drift velocity was found to be linear with applied field below about 2×108V/m and deviated from linearity above this. To a large extent, D3O+ and Cs+ motion in 3MP was well predicted by a simple continuum-based ion mobility model in films from 25 to 20 000 ML thick (including pronounced perturbations 7 ML from both the vacuum and Pt interfaces). The mobility varied with temperature more slowly than predicted by Stokes' law, which may be due to extended inhomogeneous structures in the 3MP near its glass transition at 77K.

Three-dimensional single-molecule localization with nanometer accuracy using Metal-Induced Energy Transfer (MIET) imaging

NASA Astrophysics Data System (ADS)

Karedla, Narain; Chizhik, Anna M.; Stein, Simon C.; Ruhlandt, Daja; Gregor, Ingo; Chizhik, Alexey I.; Enderlein, Jörg

2018-05-01

Our paper presents the first theoretical and experimental study using single-molecule Metal-Induced Energy Transfer (smMIET) for localizing single fluorescent molecules in three dimensions. Metal-Induced Energy Transfer describes the resonant energy transfer from the excited state of a fluorescent emitter to surface plasmons in a metal nanostructure. This energy transfer is strongly distance-dependent and can be used to localize an emitter along one dimension. We have used Metal-Induced Energy Transfer in the past for localizing fluorescent emitters with nanometer accuracy along the optical axis of a microscope. The combination of smMIET with single-molecule localization based super-resolution microscopy that provides nanometer lateral localization accuracy offers the prospect of achieving isotropic nanometer localization accuracy in all three spatial dimensions. We give a thorough theoretical explanation and analysis of smMIET, describe its experimental requirements, also in its combination with lateral single-molecule localization techniques, and present first proof-of-principle experiments using dye molecules immobilized on top of a silica spacer, and of dye molecules embedded in thin polymer films.

Thermodynamic properties of gaseous ruthenium species.

PubMed

Miradji, Faoulat; Souvi, Sidi; Cantrel, Laurent; Louis, Florent; Vallet, Valérie

2015-05-21

The review of thermodynamic data of ruthenium oxides reveals large uncertainties in some of the standard enthalpies of formation, motivating the use of high-level relativistic correlated quantum chemical methods to reduce the level of discrepancies. The reaction energies leading to the formation of ruthenium oxides RuO, RuO2, RuO3, and RuO4 have been calculated for a series of reactions. The combination of different quantum chemical methods has been investigated [DFT, CASSCF, MRCI, CASPT2, CCSD(T)] in order to predict the geometrical parameters, the energetics including electronic correlation and spin-orbit coupling. The most suitable method for ruthenium compounds is the use of TPSSh-5%HF for geometry optimization, followed by CCSD(T) with complete basis set (CBS) extrapolations for the calculation of the total electronic energies. SO-CASSCF seems to be accurate enough to estimate spin-orbit coupling contributions to the ground-state electronic energies. This methodology yields very accurate standard enthalpies of formations of all species, which are either in excellent agreement with the most reliable experimental data or provide an improved estimate for the others. These new data will be implemented in the thermodynamical databases that are used by the ASTEC code (accident source term evaluation code) to build models of ruthenium chemistry behavior in severe nuclear accident conditions. The paper also discusses the nature of the chemical bonds both from molecular orbital and topological view points.

Ferromagnetic thin films

DOEpatents

Krishnan, K.M.

1994-12-20

A ferromagnetic [delta]-Mn[sub 1[minus]x]Ga[sub x] thin film having perpendicular anisotropy is described which comprises: (a) a GaAs substrate, (b) a layer of undoped GaAs overlying said substrate and bonded thereto having a thickness ranging from about 50 to about 100 nanometers, (c) a layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] overlying said layer of undoped GaAs and bonded thereto having a thickness ranging from about 20 to about 30 nanometers, and (d) a layer of GaAs overlying said layer of [delta]-Mn[sub 1[minus]x]Ga[sub x] and bonded thereto having a thickness ranging from about 2 to about 5 nanometers, wherein x is 0.4[+-]0.05. 7 figures.

Synthesis of PVP-stabilized ruthenium colloids with low boiling point alcohols.

PubMed

Zhang, Yuqing; Yu, Jiulong; Niu, Haijun; Liu, Hanfan

2007-09-15

A route to the preparation of poly(N-vinyl-2-pyrrolidone) (PVP)-stabilized ruthenium colloids by refluxing ruthenium(III) chloride in low boiling point alcohols was developed. Deep purple colloids with shuttle-like ruthenium particles were also synthesized. XPS measurement verified the nanoparticles were in the metallic state. The morphology of metal nanoparticles was characterized by UV-visible absorption spectrophotometry, TEM and XRD.

Non-exponential resistive switching in Ag2S memristors: a key to nanometer-scale non-volatile memory devices.

PubMed

Gubicza, Agnes; Csontos, Miklós; Halbritter, András; Mihály, György

2015-03-14

The dynamics of resistive switchings in nanometer-scale metallic junctions formed between an inert metallic tip and an Ag film covered by a thin Ag2S layer are investigated. Our thorough experimental analysis and numerical simulations revealed that the resistance change upon a switching bias voltage pulse exhibits a strongly non-exponential behaviour yielding markedly different response times at different bias levels. Our results demonstrate the merits of Ag2S nanojunctions as nanometer-scale non-volatile memory cells with stable switching ratios, high endurance as well as fast response to write/erase, and an outstanding stability against read operations at technologically optimal bias and current levels.

Using Organic Light-Emitting Electrochemical Thin-Film Devices to Teach Materials Science

ERIC Educational Resources Information Center

Sevian, Hannah; Muller, Sean; Rudmann, Hartmut; Rubner, Michael F.

2004-01-01

Materials science can be taught by applying organic light-emitting electrochemical thin-film devices and in this method students were allowed to make a light-emitting device by spin coating a thin film containing ruthenium (II) complex ions onto a glass slide. Through this laboratory method students are provided with the opportunity to learn about…

Electrochemical Sensing of Casein Based on the Interaction between Its Phosphate Groups and a Ruthenium(III) Complex.

PubMed

Inaba, Iku; Kuramitz, Hideki; Sugawara, Kazuharu

2016-01-01

A reaction to casein, along with β-lactoglobulin, is a main cause of milk allergies, and also is a useful indicator of protein in allergic analyses. In the present study, a simple casein sensor was developed based on the interaction between a phosphate group of casein and electroactive [Ru(NH3)6](3+). We evaluated the voltammetric behavior of a casein-[Ru(NH3)6](3+) complex using a glassy carbon electrode. When the ruthenium(III) complex was combined with the phosphate groups of casein, the structure of the casein was changed. Since the hydrophobicity of casein was increased due to the binding, the casein was adsorbed onto the electrode. Furthermore, we modified an electrode with a ruthenium(III) ions/collagen film. When the sensor was applied to the detection of the casein contained in milk, the values coincided with those indicated by the manufacturer. Accordingly, this electrode could be a powerful sensor for the determination of casein in several foods.

PROCESS FOR DECONTAMINATING THORIUM AND URANIUM WITH RESPECT TO RUTHENIUM

DOEpatents

Meservey, A.A.; Rainey, R.H.

1959-10-20

The control of ruthenium extraction in solvent-extraction processing of neutron-irradiated thorium is presented. Ruthenium is rendered organic-insoluble by the provision of sulfite or bisulfite ions in the aqueous feed solution. As a result the ruthenium remains in the aqueous phase along with other fission product and protactinium values, thorium and uranium values being extracted into the organic phase. This process is particularly applicable to the use of a nitrate-ion-deficient aqueous feed solution and to the use of tributyl phosphate as the organic extractant.

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

NASA Astrophysics Data System (ADS)

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; Sweat, Daniel P.; Wang, Xudong; Gopalan, Padma

2016-06-01

In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. We conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.In this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order-disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns and

Fabrication of a symmetric micro supercapacitor based on tubular ruthenium oxide on silicon 3D microstructures

NASA Astrophysics Data System (ADS)

Wang, Xiaofeng; Yin, Yajiang; Li, Xiangyu; You, Zheng

2014-04-01

A micro-supercapacitor with a three-dimensional configuration has been fabricated using an ICP etching technique. Hydrous ruthenium oxide with a tubular morphology is successfully synthesized using a cathodic deposition technique with a Si micro prominence as a template. The desired tubular RuO2·xH2O architecture facilitates electrolyte penetration and proton exchange/diffusion. A single MEMS electrode is studied using cyclic voltammetry, and a specific capacitance of 99.3 mF cm-2 and 70 F g-1 is presented at 5 mV s-1 in neutral Na2SO4 solution. The accelerated cycle life is tested at 80 mV s-1, and satisfactory cyclability is observed. When placed on a chip, the symmetric cell exhibits good supercapacitor properties, and a specific capacitance as high as 23 mF cm-2 is achieved at 10 mA cm-2. Therefore, 3D MEMS microelectrode arrays with electrochemically deposited ruthenium oxide films are promising candidates for on-chip electrochemical micro-capacitor applications.

Method of synthesizing metal doped diamond-like carbon films

NASA Technical Reports Server (NTRS)

Ueno, Mayumi (Inventor); Sunkara, Mahendra Kumar (Inventor)

2003-01-01

A method of synthesizing metal doped carbon films by placing a substrate in a chamber with a selected amount of a metalorganic compound. An electron cyclotron resonance is applied to the chamber in order to vaporize the metalorganic compound. The resonance is applied to the chamber until a metal doped carbon film is formed. The metalorganic compound is preferably selected from the group consisting of an organic salt of ruthenium, palladium, gold or platinum.

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications

PubMed Central

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-01-01

Ruthenium active species containing Ruthenium Sulphide (RuS2) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS2 on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s−1 is 238 F g−1. This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications. PMID:29301192

Graphene/Ruthenium Active Species Aerogel as Electrode for Supercapacitor Applications.

PubMed

Gigot, Arnaud; Fontana, Marco; Pirri, Candido Fabrizio; Rivolo, Paola

2017-12-30

Ruthenium active species containing Ruthenium Sulphide (RuS₂) is synthesized together with a self-assembled reduced graphene oxide (RGO) aerogel by a one-pot hydrothermal synthesis. Ruthenium Chloride and L-Cysteine are used as reactants. The hydrothermal synthesis of the innovative hybrid material occurs at 180 °C for 12 h, by using water as solvent. The structure and morphology of the hybrid material are fully characterized by Raman, XRD, XPS, FESEM and TEM. The XRD and diffraction pattern obtained by TEM display an amorphous nanostructure of RuS₂ on RGO crystallized flakes. The specific capacitance measured in planar configuration in 1 M NaCl electrolyte at 5 mV s -1 is 238 F g -1 . This supercapacitor electrode also exhibits perfect cyclic stability without loss of the specific capacitance after 15,000 cycles. In summary, the RGO/Ruthenium active species hybrid material demonstrates remarkable properties for use as active material for supercapacitor applications.

Low Temperature, Selective Atomic Layer Deposition of Nickel Metal Thin Films.

PubMed

Kerrigan, Marissa M; Klesko, Joseph P; Blakeney, Kyle J; Winter, Charles H

2018-04-25

We report the growth of nickel metal films by atomic layer deposition (ALD) employing bis(1,4-di- tert-butyl-1,3-diazadienyl)nickel and tert-butylamine as the precursors. A range of metal and insulating substrates were explored. An initial deposition study was carried out on platinum substrates. Deposition temperatures ranged from 160 to 220 °C. Saturation plots demonstrated self-limited growth for both precursors, with a growth rate of 0.60 Å/cycle. A plot of growth rate versus substrate temperature showed an ALD window from 180 to 195 °C. Crystalline nickel metal was observed by X-ray diffraction for a 60 nm thick film deposited at 180 °C. Films with thicknesses of 18 and 60 nm grown at 180 °C showed low root mean square roughnesses (<2.5% of thicknesses) by atomic force microscopy. X-ray photoelectron spectroscopies of 18 and 60 nm thick films deposited on platinum at 180 °C revealed ionizations consistent with nickel metal after sputtering with argon ions. The nickel content in the films was >97%, with low levels of carbon, nitrogen, and oxygen. Films deposited on ruthenium substrates displayed lower growth rates than those observed on platinum substrates. On copper substrates, discontinuous island growth was observed at ≤1000 cycles. Film growth was not observed on insulating substrates under any conditions. The new nickel metal ALD procedure gives inherently selective deposition on ruthenium and platinum from 160 to 220 °C.

Unexpected Rotamerism at the Origin of a Chessboard Supramolecular Assembly of Ruthenium Phthalocyanine.

PubMed

Mattioli, Giuseppe; Larciprete, Rosanna; Alippi, Paola; Bonapasta, Aldo Amore; Filippone, Francesco; Lacovig, Paolo; Lizzit, Silvano; Paoletti, Anna Maria; Pennesi, Giovanna; Ronci, Fabio; Zanotti, Gloria; Colonna, Stefano

2017-11-16

We have investigated the formation and the properties of ultrathin films of ruthenium phthalocyanine (RuPc) 2 vacuum deposited on graphite by scanning tunneling microscopy and synchrotron photoemission spectroscopy measurements, interpreted in close conjunction with ab initio simulations. Thanks to its unique dimeric structure connected by a direct Ru-Ru bond, (RuPc) 2 can be found in two stable rotameric forms separated by a low-energy barrier. Such isomerism leads to a peculiar organization of the molecules in flat, horizontal layers on the graphite surface, characterized by a chessboard-like alternation of the two rotamers. Moreover, the molecules are vertically connected to form π-stacked columnar pillars of akin rotamers, compatible with the high conductivity measured in (RuPc) 2 powders. Such features yield an unprecedented supramolecular assembly of phthalocyanine films, which could open interesting perspectives toward the realization of new architectures of organic electronic devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low temperature rf sputtering deposition of (Ba, Sr) TiO3 thin film with crystallization enhancement by rf power supplied to the substrate

NASA Astrophysics Data System (ADS)

Yoshimaru, Masaki; Takehiro, Shinobu; Abe, Kazuhide; Onoda, Hiroshi

2005-05-01

The (Ba, Sr) TiO3 thin film deposited by radio frequency (rf) sputtering requires a high deposition temperature near 500 °C to realize a high relative dielectric constant over of 300. For example, the film deposited at 330 °C contains an amorphous phase and shows a low relative dielectric constant of less than 100. We found that rf power supplied not only to the (Ba, Sr) TiO3 sputtering target, but also to the substrate during the initial step of film deposition, enhanced the crystallization of the (Ba, Sr) TiO3 film drastically and realized a high dielectric constant of the film even at low deposition temperatures near 300 °C. The 50-nm-thick film with only a 10 nm initial layer deposited with the substrate rf biasing is crystallized completely and shows a high relative dielectric constant of 380 at the deposition temperature of 330 °C. The (Ba, Sr) TiO3 film deposited at higher temperatures (upwards of 400 °C) shows <110> preferred orientation, while the film deposited at 330 °C with the 10 nm initial layer shows a <111> preferred orientation on a <001>-oriented ruthenium electrode. The unit cell of (Ba, Sr) TiO3 (111) plane is similar to that of ruthenium (001) plane. We conclude that the rf power supplied to the substrate causes ion bombardments on the (Ba, Sr) TiO3 film surface, which assists the quasiepitaxial growth of (Ba, Sr) TiO3 film on the ruthenium electrode at low temperatures of less than 400 °C.

Toxicology and pharmacology of some ruthenium compounds: Vascular smooth muscle relaxation by nitrosyl derivatives of ruthenium and iridium.

PubMed

Kruszyna, H; Kruszyna, R; Hurst, J; Smith, R P

1980-07-01

A series of compounds were synthesized from ruthenium trichloride, and their ip LD50s were determined in mice: pentamminenitrosylruthenium(II) chloride, 8.9; chloronitrobis(2,2'-dipyridyl)ruthenium(II), 55;dichlorobis(2,2'-dipyridyl)ruthenium(II), 63; ruthenium trichloride, 108; and potassium pentachloronitrosylruthenate(II), 127 mg/kg. The two bis-bipyridyl complexes produced death in convulsions within minutes, whereas the remaining compounds resulted in long, debilitating courses with death occurring in 4-7d. When given in massive overdoses, however, the compounds with inorganic ligands also produced rapid convulsive death in mice, and when given iv to anesthetized cats, they produced respiratory arrest. The major toxic effects of all the complexes appeared to be due to the metal and not to its associated ligands. Only complexes having nitrosyl ligand specifically relaxed vascular smooth muscle. Potassium pentabromoiridate(III) also relaxed rabbit aortic strips that had been contracted by adrenergic agonists, but potassium pentachloroiridate(III) did not. None of the complexes was as active as nitroprusside in relaxing aortic strips or in decreasing arterial blood pressure in cats. No compound tested was as potent as cisplatin in antitumor activity. The pentamminenitrosylruthenium(II) complex also relaxed guinea pig ileum and frog rectus abdominus when these isolated muscles had been contracted by acetylcho line. It appears that these organoruthenium compounds may produce death in central respiratory arrest, as do the inorganic complexes when given iv or ip in massive overdoses. In minimally lethal doses, the complexes with inorganic ligands may affect a variety of contractile tissues, perhaps by a general mechanism involving Ca. These complexes are apt to be generally cytotoxic as well.

The nature of the Fe–graphene interface at the nanometer level

DOE PAGES

Cattelan, M.; Peng, G. W.; Cavaliere, E.; ...

2014-12-22

The emerging fields of graphene-based magnetic and spintronic devices require a deep understanding of the interface between graphene and ferromagnetic metals. This paper reports a detailed investigation at the nanometer level of the Fe–graphene interface carried out by angle-resolved photoemission, high-resolution photoemission from core levels, near edge X-ray absorption fine structure, scanning tunnelling microscopy and spin polarized density functional theory calculations. Quasi-free-standing graphene was grown on Pt(111), and the iron film was either deposited atop or intercalated beneath graphene. Here, calculations and experimental results show that iron strongly modifies the graphene band structure and lifts its π band spin degeneracy.

Photoisomerization of ruthenium(ii) aquo complexes: mechanistic insights and application development.

PubMed

Hirahara, Masanari; Yagi, Masayuki

2017-03-21

Ruthenium(ii) complexes with polypyridyl ligands have been extensively studied as promising functional molecules due to their unique photochemical and photophysical properties as well as redox properties. In this context, we report the photoisomerization of distal-[Ru(tpy)(pynp)OH 2 ] 2+ (d-1) (tpy = 2,2';6',2''-terpyridine, pynp = 2-(2-pyridyl)-1,8-naphthyridine) to proximal-[Ru(tpy)(pynp)OH 2 ] 2+ (p-1), which has not been previously characterized for polypyridyl ruthenium(ii) aquo complexes. Herein, we review recent progress made by our group on the mechanistic insights and application developments related to the photoisomerization of polypyridyl ruthenium(ii) aquo complexes. We report a new strategic synthesis of dinuclear ruthenium(ii) complexes that can act as an active water oxidation catalyst, as well as the development of unique visible-light-responsive giant vesicles, both of which were achieved based on photoisomerization.

The inhibition of mitochondrial calcium transport by lanthanides and Ruthenium Red

PubMed Central

Reed, Ken C.; Bygrave, Fyfe L.

1974-01-01

An EGTA (ethanedioxybis(ethylamine)tetra-acetic acid)-quench technique was developed for measuring initial rates of 45Ca2+ transport by rat liver mitochondria. This method was used in conjunction with studies of Ca2+-stimulated respiration to examine the mechanisms of inhibition of Ca2+ transport by the lanthanides and Ruthenium Red. Ruthenium Red inhibits Ca2+ transport non-competitively with Ki 3×10−8m; there are 0.08nmol of carrier-specific binding sites/mg of protein. The inhibition by La3+ is competitive (Ki=2×10−8m); the concentration of lanthanide-sensitive sites is less than 0.001nmol/mg of protein. A further difference between their modes of action is that lanthanide inhibition diminishes with time whereas that by Ruthenium Red does not. Binding studies showed that both classes of inhibitor bind to a relatively large number of external sites (probably identical with the `low-affinity' Ca2+-binding sites). La3+ competes with Ruthenium Red for most of these sites, but a small fraction of the bound Ruthenium Red (less than 2nmol/mg of protein) is not displaced by La3+. The results are discussed briefly in relation to possible models for a Ca2+ carrier. PMID:4375957

Ruthenium-Catalyzed Aerobic Oxidation of Amines.

PubMed

Ray, Ritwika; Hazari, Arijit Singha; Lahiri, Goutam Kumar; Maiti, Debabrata

2018-01-18

Amine oxidation is one of the fundamental reactions in organic synthesis as it leads to a variety of value-added products such as oximes, nitriles, imines, and amides among many others. These products comprise the key N-containing building blocks in the modern chemical industry, and such transformations, when achieved in the presence of molecular oxygen without using stoichiometric oxidants, are much preferred as they circumvent the production of unwanted wastes. In parallel, the versatility of ruthenium catalysts in various oxidative transformations is well-documented. Herein, this review focuses on aerobic oxidation of amines specifically by using ruthenium catalysts and highlights the major achievements in this direction and challenges that still need to be addressed. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Recommendation of ruthenium source for sludge batch flowsheet studies

DOE Office of Scientific and Technical Information (OSTI.GOV)

Woodham, W.

Included herein is a preliminary analysis of previously-generated data from sludge batches 7a, 7b, 8, and 9 sludge simulant and real-waste testing, performed to recommend a form of ruthenium for future sludge batch simulant testing under the nitric-formic flowsheet. Focus is given to reactions present in the Sludge Receipt and Adjustment Tank cycle, given that this cycle historically produces the most changes in chemical composition during Chemical Process Cell processing. Data is presented and analyzed for several runs performed under the nitric-formic flowsheet, with consideration given to effects on the production of hydrogen gas, nitrous oxide gas, consumption of formate,more » conversion of nitrite to nitrate, and the removal and recovery of mercury during processing. Additionally, a brief discussion is given to the effect of ruthenium source selection under the nitric-glycolic flowsheet. An analysis of data generated from scaled demonstration testing, sludge batch 9 qualification testing, and antifoam degradation testing under the nitric-glycolic flowsheet is presented. Experimental parameters of interest under the nitric-glycolic flowsheet include N2O production, glycolate destruction, conversion of glycolate to formate and oxalate, and the conversion of nitrite to nitrate. To date, the number of real-waste experiments that have been performed under the nitric-glycolic flowsheet is insufficient to provide a complete understanding of the effects of ruthenium source selection in simulant experiments with regard to fidelity to real-waste testing. Therefore, a determination of comparability between the two ruthenium sources as employed under the nitric-glycolic flowsheet is made based on available data in order to inform ruthenium source selection for future testing under the nitric-glycolic flowsheet.« less

C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex.

PubMed

Man, Wai-Lun; Xie, Jianhui; Pan, Yi; Lam, William W Y; Kwong, Hoi-Ki; Ip, Kwok-Wa; Yiu, Shek-Man; Lau, Kai-Chung; Lau, Tai-Chu

2013-04-17

We report experimental and computational studies of the facile oxidative C-N bond cleavage of anilines by a (salen)ruthenium(VI) nitrido complex. We provide evidence that the initial step involves nucleophilic attack of aniline at the nitrido ligand of the ruthenium complex, which is followed by proton and electron transfer to afford a (salen)ruthenium(II) diazonium intermediate. This intermediate then undergoes unimolecular decomposition to generate benzene and N2.

Glass ceramic ZERODUR enabling nanometer precision

NASA Astrophysics Data System (ADS)

Jedamzik, Ralf; Kunisch, Clemens; Nieder, Johannes; Westerhoff, Thomas

2014-03-01

The IC Lithography roadmap foresees manufacturing of devices with critical dimension of < 20 nm. Overlay specification of single digit nanometer asking for nanometer positioning accuracy requiring sub nanometer position measurement accuracy. The glass ceramic ZERODUR® is a well-established material in critical components of microlithography wafer stepper and offered with an extremely low coefficient of thermal expansion (CTE), the tightest tolerance available on market. SCHOTT is continuously improving manufacturing processes and it's method to measure and characterize the CTE behavior of ZERODUR® to full fill the ever tighter CTE specification for wafer stepper components. In this paper we present the ZERODUR® Lithography Roadmap on the CTE metrology and tolerance. Additionally, simulation calculations based on a physical model are presented predicting the long term CTE behavior of ZERODUR® components to optimize dimensional stability of precision positioning devices. CTE data of several low thermal expansion materials are compared regarding their temperature dependence between - 50°C and + 100°C. ZERODUR® TAILORED 22°C is full filling the tight CTE tolerance of +/- 10 ppb / K within the broadest temperature interval compared to all other materials of this investigation. The data presented in this paper explicitly demonstrates the capability of ZERODUR® to enable the nanometer precision required for future generation of lithography equipment and processes.

Nonproductive events in ring-closing metathesis using ruthenium catalysts.

PubMed

Stewart, Ian C; Keitz, Benjamin K; Kuhn, Kevin M; Thomas, Renee M; Grubbs, Robert H

2010-06-30

The relative TONs of productive and nonproductive metathesis reactions of diethyl diallylmalonate are compared for eight different ruthenium-based catalysts. Nonproductive cross metathesis is proposed to involve a chain-carrying ruthenium methylidene. A second more-challenging substrate (dimethyl allylmethylallylmalonate) that forms a trisubstituted olefin product is used to further delineate the effect of catalyst structure on the relative efficiencies of these processes. A steric model is proposed to explain the observed trends.

Synthesis and characterization of Copper/Cobalt/Copper/Iron nanostructurated films with magnetoresistive properties

NASA Astrophysics Data System (ADS)

Ciupinǎ, Victor; Prioteasa, Iulian; Ilie, Daniela; Manu, Radu; Petrǎşescu, Lucian; Tutun, Ştefan Gabriel; Dincǎ, Paul; MustaÅ£ǎ, Ion; Lungu, Cristian Petricǎ; Jepu, IonuÅ£; Vasile, Eugeniu; Nicolescu, Virginia; Vladoiu, Rodica

2017-02-01

Copper/Cobalt/Copper/Iron thin films were synthesized in order to obtain nanostructured materials with special magnetoresistive properties. The multilayer films were deposited on silicon substrates. In this respect we used Thermionic Vacuum Arc Discharge Method (TVA). The benefit of this deposition technique is the ability to have a controlled range of thicknesses starting from few nanometers to hundreds of nanometers. The purity of the thin films was insured by a high vacuum pressure and a lack of any kind of buffer gas inside the coating chamber. The morphology and structure of the thin films were analyzed using Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) Techniques and Energy Dispersive X-ray Spectroscopy (EDXS). Magnetoresistive measurement results depict that thin films possess Giant Magneto-Resistance Effect (GMR). Magneto-Optic-Kerr Effect (MOKE) studies were performed to characterize the magnetic properties of these thin films.

Electronic transport properties of nano-scale Si films: an ab initio study

NASA Astrophysics Data System (ADS)

Maassen, Jesse; Ke, Youqi; Zahid, Ferdows; Guo, Hong

2010-03-01

Using a recently developed first principles transport package, we study the electronic transport properties of Si films contacted to heavily doped n-type Si leads. The quantum transport analysis is carried out using density functional theory (DFT) combined with nonequilibrium Green's functions (NEGF). This particular combination of NEGF-DFT allows the investigation of Si films with thicknesses in the range of a few nanometers and lengths up to tens of nanometers. We calculate the conductance, the momentum resolved transmission, the potential profile and the screening length as a function of length, thickness, orientation and surface structure. Moreover, we compare the properties of Si films with and without a top surface passivation by hydrogen.

Ruthenium Grubbs' catalyst nanostructures grown by UV-excimer-laser ablation for self-healing applications

NASA Astrophysics Data System (ADS)

Aïssa, B.; Nechache, R.; Haddad, E.; Jamroz, W.; Merle, P. G.; Rosei, F.

2012-10-01

A self healing composite material consisting of 5-Ethylidene-2-Norbornene (5E2N) monomer reacted with Ruthenium Grubbs' Catalyst (RGC) was prepared. First, the kinetics of the 5E2N ring opening metathesis polymerization (ROMP) reaction RGC was studied as a function of temperature. We show that the polymerization reaction is still effective in a large temperature range (-15 to 45 °C), occurring at short time scales (less than 1 min at 40 °C). Second, the amount of RGC required for ROMP reaction significantly decreased through its nanostructuration by means of a UV-excimer laser ablation process. RGC nanostructures of few nanometers in size where successfully obtained directly on silicon substrates. The X-ray photoelectron spectroscopy data strongly suggest that the RGC still keep its original stoichiometry after nanostructuration. More importantly, the associated ROMP reaction was successfully achieved at an extreme low RGC concentration equivalent to (11.16 ± 1.28) × 10-4 Vol.%, occurring at very short time reaction. This approach opens new prospects for using healing agent nanocomposite materials for self-repair functionality, thereby obtaining a higher catalytic efficiency per unit mass.

Laser damage of free-standing nanometer membranes

NASA Astrophysics Data System (ADS)

Morimoto, Yuya; Roland, Iännis; Rennesson, Stéphanie; Semond, Fabrice; Boucaud, Philippe; Baum, Peter

2017-12-01

Many high-field/attosecond and ultrafast electron diffraction/microscopy experiments on condensed matter require samples in the form of free-standing membranes with nanometer thickness. Here, we report the measurement of the laser-induced damage threshold of 11 different free-standing nanometer-thin membranes of metallic, semiconducting, and insulating materials for 1-ps, 1030-nm laser pulses at 50 kHz repetition rate. We find a laser damage threshold that is very similar to each corresponding bulk material. The measurements also reveal a band gap dependence of the damage threshold as a consequence of different ionization rates. These results establish the suitability of free-standing nanometer membranes for high-field pump-probe experiments.

Using ruthenium sawhorse based decarboxylation to produce industrial materials from oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium catalyzed isomerization and decarboxylation of 9-cis-octadecenoic acid are reported as part of the effort to produce valuable industrial materials from biobased sources. Initial studies have demonstrated the efficacy of ruthenium sawhorse materials and further mechanistic studies uncovered...

High-throughput characterization of film thickness in thin film materials libraries by digital holographic microscopy.

PubMed

Lai, Yiu Wai; Krause, Michael; Savan, Alan; Thienhaus, Sigurd; Koukourakis, Nektarios; Hofmann, Martin R; Ludwig, Alfred

2011-10-01

A high-throughput characterization technique based on digital holography for mapping film thickness in thin-film materials libraries was developed. Digital holographic microscopy is used for fully automatic measurements of the thickness of patterned films with nanometer resolution. The method has several significant advantages over conventional stylus profilometry: it is contactless and fast, substrate bending is compensated, and the experimental setup is simple. Patterned films prepared by different combinatorial thin-film approaches were characterized to investigate and demonstrate this method. The results show that this technique is valuable for the quick, reliable and high-throughput determination of the film thickness distribution in combinatorial materials research. Importantly, it can also be applied to thin films that have been structured by shadow masking.

Optical field enhancement of nanometer-sized gaps at near-infrared frequencies.

PubMed

Ahn, Jae Sung; Kang, Taehee; Singh, Dilip K; Bahk, Young-Mi; Lee, Hyunhwa; Choi, Soo Bong; Kim, Dai-Sik

2015-02-23

We report near-field and far-field measurements of transmission through nanometer-sized gaps at near-infrared frequencies with varying the gap size from 1 nm to 10 nm. In the far-field measurements, we excluded direct transmission on the metal film surface via interferometric method. Kirchhoff integral formalism was used to relate the far-field intensity to the electric field at the nanogaps. In near-field measurements, field enhancement factors of the nanogaps were quantified by measuring transmission of the nanogaps using near-field scanning optical microscopy. All the measurements produce similar field enhancements of about ten, which we put in the context of comparing with the giant field enhancements in the terahertz regime.

Platinum-ruthenium-nickel fuel cell electrocatalyst

DOEpatents

Gorer, Alexander

2005-07-26

A catalyst suitable for use in a fuel cell, especially as an anode catalyst, that contains platinum, ruthenium, and nickel, wherein the nickel is at a concentration that is less than about 10 atomic percent.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

ERIC Educational Resources Information Center

Rapp, Teresa L.; Phillips, Susan R.; Dmochowski, Ivan J.

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, lightdriven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes…

Metal-assisted exfoliation (MAE): green process for transferring graphene to flexible substrates and templating of sub-nanometer plasmonic gaps (Presentation Recording)

NASA Astrophysics Data System (ADS)

Zaretski, Aliaksandr V.; Marin, Brandon C.; Moetazedi, Herad; Dill, Tyler J.; Jibril, Liban; Kong, Casey; Tao, Andrea R.; Lipomi, Darren J.

2015-09-01

This paper describes a new technique, termed "metal-assisted exfoliation," for the scalable transfer of graphene from catalytic copper foils to flexible polymeric supports. The process is amenable to roll-to-roll manufacturing, and the copper substrate can be recycled. We then demonstrate the use of single-layer graphene as a template for the formation of sub-nanometer plasmonic gaps using a scalable fabrication process called "nanoskiving." These gaps are formed between parallel gold nanowires in a process that first produces three-layer thin films with the architecture gold/single-layer graphene/gold, and then sections the composite films with an ultramicrotome. The structures produced can be treated as two gold nanowires separated along their entire lengths by an atomically thin graphene nanoribbon. Oxygen plasma etches the sandwiched graphene to a finite depth; this action produces a sub-nanometer gap near the top surface of the junction between the wires that is capable of supporting highly confined optical fields. The confinement of light is confirmed by surface-enhanced Raman spectroscopy measurements, which indicate that the enhancement of the electric field arises from the junction between the gold nanowires. These experiments demonstrate nanoskiving as a unique and easy-to-implement fabrication technique that is capable of forming sub-nanometer plasmonic gaps between parallel metallic nanostructures over long, macroscopic distances. These structures could be valuable for fundamental investigations as well as applications in plasmonics and molecular electronics.

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

DOE PAGES

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.; ...

2016-05-04

Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

Patterning at the 10 nanometer length scale using a strongly segregating block copolymer thin film and vapor phase infiltration of inorganic precursors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Choi, Jonathan W.; Li, Zhaodong; Black, Charles T.

Here in this work, we demonstrate the use of self-assembled thin films of the cylinder-forming block copolymer poly(4-tert-butylstyrene-block-2-vinylpyridine) to pattern high density features at the 10 nm length scale. This material's large interaction parameter facilitates pattern formation in single-digit nanometer dimensions. This block copolymer's accessible order–disorder transition temperature allows thermal annealing to drive the assembly of ordered 2-vinylpyridine cylinders that can be selectively complexed with the organometallic precursor trimethylaluminum. This unique chemistry converts organic 2-vinylpyridine cylinders into alumina nanowires with diameters ranging from 8 to 11 nm, depending on the copolymer molecular weight. Graphoepitaxy of this block copolymer aligns andmore » registers sub-12 nm diameter nanowires to larger-scale rectangular, curved, and circular features patterned by optical lithography. The alumina nanowires function as a robust hard mask to withstand the conditions required for patterning the underlying silicon by plasma etching. Lastly, we conclude with a discussion of some of the challenges that arise with using block copolymers for patterning at sub-10 nm feature sizes.« less

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, Douglas C.; Sealock, John L.

1998-01-01

A method of hydrogenation using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions.

Simulation and measurement of nanometer-scale resistivity of copper films for interconnect applications

NASA Astrophysics Data System (ADS)

Yarimbiyik, Arif Emre

2007-12-01

A highly versatile simulation program is developed and used to examine how the resistivity of thin metal films and lines increases as their dimensions approach and become smaller than the mean fee path of electrons in metals such as copper (size effect). The simulation program: (1) provides a more accurate calculation of surface scattering effects than that obtained from the usual formulation of Fuchs' theory, (2) calculates grain-boundary effects that are consistent with the theory of Mayadas and Shatzkes, (3) includes the effects of surface and grain-boundary scattering either separately or together, and (4) simulates the effect on resistivity if a surface of a film or line has a different value for the scattering parameter. The increase in resistivity with decreasing thickness of thin, evaporated copper films (approximately 10 nm to 150 nm thick) was determined from sheet resistance and film thickness measurements. Good agreement between the experimental results with those of the simulation program was obtained when the measured mean grain sizes were used by the simulation program. The mean of the grain sizes tend to decrease with decreasing film thickness and thereby increase the impact of grain-boundary scattering on the effective resistivity of the film. Estimates of the mean grain size for each film were determined from using, in combination, the electron backscatter diffraction (EBSD) and the X-ray diffraction (XRD) methods. With values for the measured change in sheet resistance with temperature of these films, it is shown that measurements of the electrical film thickness, using Matthiessen's rule, agreed to within 3 nm of the physical measurements (profilometer) of these films. Hence, Matthiessen's rule can continue to be used to measure the thickness of a copper film and, by inference, the cross-sectional area of a copper line for dimensions well below the mean free path of electrons in copper at room temperature (39 nm).

Metal-metal interactions in linear tri-, penta-, hepta-, and nona-nuclear ruthenium string complexes.

PubMed

Niskanen, Mika; Hirva, Pipsa; Haukka, Matti

2012-05-01

Density functional theory (DFT) methodology was used to examine the structural properties of linear metal string complexes: [Ru(3)(dpa)(4)X(2)] (X = Cl(-), CN(-), NCS(-), dpa = dipyridylamine(-)), [Ru(5)(tpda)(4)Cl(2)], and hypothetical, not yet synthesized complexes [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] (tpda = tri-α-pyridyldiamine(2-), tpta = tetra-α-pyridyltriamine(3-), ppta = penta-α-pyridyltetraamine(4-)). Our specific focus was on the two longest structures and on comparison of the string complexes and unsupported ruthenium backboned chain complexes, which have weaker ruthenium-ruthenium interactions. The electronic structures were studied with the aid of visualized frontier molecular orbitals, and Bader's quantum theory of atoms in molecules (QTAIM) was used to study the interactions between ruthenium atoms. The electron density was found to be highest and distributed most evenly between the ruthenium atoms in the hypothetical [Ru(7)(tpta)(4)Cl(2)] and [Ru(9)(ppta)(4)Cl(2)] string complexes.

Recent advances in ruthenium complex-based light-driven water oxidation catalysts.

PubMed

Xue, Long-Xin; Meng, Ting-Ting; Yang, Wei; Wang, Ke-Zhi

2015-11-01

The light driven splitting of water is one of the most attractive approaches for direct conversion of solar energy into chemical energy in the future. Ruthenium complexes as the water oxidation catalysts (WOCs) and light sensitizers have attracted increasing attention, and have made a great progress. This mini-review highlights recent progress on ruthenium complex-based photochemical and photoelectrochemical water oxidation catalysts. The recent representative examples of these ruthenium complexes that are in homogeneous solution or immobilized on solid electrodes, are surveyed. In particular, special attention has been paid on the supramolecular dyads with photosensitizer and WOC being covalently hold together, and grafted onto the solid electrode. Copyright © 2015 Elsevier B.V. All rights reserved.

Nickel/ruthenium catalyst and method for aqueous phase reactions

DOEpatents

Elliott, D.C.; Sealock, J.L.

1998-09-29

A method of hydrogenation is described using a catalyst in the form of a plurality of porous particles wherein each particle is a support having nickel metal catalytic phase or reduced nickel deposited thereon in a first dispersed phase and an additional ruthenium metal deposited onto the support in a second dispersed phase. The additional ruthenium metal is effective in retarding or reducing agglomeration or sintering of the nickel metal catalytic phase thereby increasing the life time of the catalyst during hydrogenation reactions. 2 figs.

Tin-decorated ruthenium nanoparticles: a way to tune selectivity in hydrogenation reaction

NASA Astrophysics Data System (ADS)

Bonnefille, Eric; Novio, Fernando; Gutmann, Torsten; Poteau, Romuald; Lecante, Pierre; Jumas, Jean-Claude; Philippot, Karine; Chaudret, Bruno

2014-07-01

Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity.Two series of ruthenium nanoparticles stabilized either by a polymer (polyvinylpyrrolidone; Ru/PVP) or a ligand (bisdiphenylphosphinobutane; Ru/dppb) were reacted with tributyltin hydride [(n-C4H9)3SnH] leading to tin-decorated ruthenium nanoparticles, Ru/PVP/Sn and Ru/dppb/Sn. The Sn/Ru molar ratio was varied in order to study the influence of the surface tin content on the properties of these new nanoparticles, by comparison with Ru/PVP and Ru/dppb. Besides HRTEM and WAXS analyses, spectroscopic techniques (IR, NMR and Mössbauer) combined with theoretical calculations and a simple catalytic test (styrene hydrogenation) allowed us to evidence the formation of μ3-bridging ``SnR'' groups on the ruthenium surface as well as to rationalize their influence on surface chemistry and catalytic activity. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr00791c

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, Powell; Srivastava, Suresh C.; Meinken, George E.

1984-05-15

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40.degree. C. for about 2 hours, and purifying said complex by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Steric and Electronic Effects of Bidentate Phosphine Ligands on Ruthenium(II)-Catalyzed Hydrogenation of Carbon Dioxide.

PubMed

Zhang, Pan; Ni, Shao-Fei; Dang, Li

2016-09-20

The reactivity difference between the hydrogenation of CO2 catalyzed by various ruthenium bidentate phosphine complexes was explored by DFT. In addition to the ligand dmpe (Me2 PCH2 CH2 PMe2 ), which was studied experimentally previously, a more bulky diphosphine ligand, dmpp (Me2 PCH2 CH2 CH2 PMe2 ), together with a more electron-withdrawing diphosphine ligand, PN(Me) P (Me2 PCH2 N(Me) CH2 PMe2 ), have been studied theoretically to analyze the steric and electronic effects on these catalyzed reactions. Results show that all of the most favorable pathways for the hydrogenation of CO2 catalyzed by bidentate phosphine ruthenium dihydride complexes undergo three major steps: cis-trans isomerization of ruthenium dihydride complex, CO2 insertion into the Ru-H bond, and H2 insertion into the ruthenium formate ion. Of these steps, CO2 insertion into the Ru-H bond has the lowest barrier compared with the other two steps in each preferred pathway. For the hydrogenation of CO2 catalyzed by ruthenium complexes of dmpe and dmpp, cis-trans isomerization of ruthenium dihydride complex has a similar barrier to that of H2 insertion into the ruthenium formate ion. However, in the reaction catalyzed by the PN(Me) PRu complex, cis-trans isomerization of the ruthenium dihydride complex has a lower barrier than H2 insertion into the ruthenium formate ion. These results suggest that the steric effect caused by the change of the outer sphere of the diphosphine ligand on the reaction is not clear, although the electronic effect is significant to cis-trans isomerization and H2 insertion. This finding refreshes understanding of the mechanism and provides necessary insights for ligand design in transition-metal-catalyzed CO2 transformation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Artificial submicron or nanometer speckle fabricating technique and electron microscope speckle photography

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu Zhanwei; Xie Huimin; Fang Daining

2007-03-15

In this article, a novel artificial submicro- or nanometer speckle fabricating technique is proposed by taking advantage of submicro or nanometer particles. In the technique, submicron or nanometer particles were adhered to an object surface by using ultrasonic dispersing technique. The particles on the object surface can be regarded as submicro or nanometer speckle by using a scanning electronic microscope at a special magnification. In addition, an electron microscope speckle photography (EMSP) method is developed to measure in-plane submicron or nanometer deformation of the object coated with the artificial submicro or nanometer speckles. The principle of artificial submicro or nanometermore » speckle fabricating technique and the EMSP method are discussed in detail in this article. Some typical applications of this method are offered. The experimental results verified that the artificial submicro or nanometer speckle fabricating technique and EMSP method is feasible.« less

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility.

PubMed

Li, H F; Zhou, F Y; Li, L; Zheng, Y F

2016-04-19

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co-Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10(-6) cm(3)·g(-1)-1.29 × 10(-6) cm(3)·g(-1) for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti-6Al-4V, ~3.5 × 10(-6) cm(3)·g(-1), CP Ti and Ti-6Al-7Nb, ~3.0 × 10(-6) cm(3)·g(-1)), and one-sixth that of Co-Cr alloys (Co-Cr-Mo, ~7.7 × 10(-6) cm(3)·g(-1)). Among the Zr-Ru alloy series, Zr-1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr-Ru alloy system as therapeutic devices under MRI diagnostics environments.

Design and development of novel MRI compatible zirconium- ruthenium alloys with ultralow magnetic susceptibility

PubMed Central

Li, H.F.; Zhou, F.Y.; Li, L.; Zheng, Y.F.

2016-01-01

In the present study, novel MRI compatible zirconium-ruthenium alloys with ultralow magnetic susceptibility were developed for biomedical and therapeutic devices under MRI diagnostics environments. The results demonstrated that alloying with ruthenium into pure zirconium would significantly increase the strength and hardness properties. The corrosion resistance of zirconium-ruthenium alloys increased significantly. High cell viability could be found and healthy cell morphology observed when culturing MG 63 osteoblast-like cells and L-929 fibroblast cells with zirconium-ruthenium alloys, whereas the hemolysis rates of zirconium-ruthenium alloys are <1%, much lower than 5%, the safe value for biomaterials according to ISO 10993-4 standard. Compared with conventional biomedical 316L stainless steel, Co–Cr alloys and Ti-based alloys, the magnetic susceptibilities of the zirconium-ruthenium alloys (1.25 × 10−6 cm3·g−1–1.29 × 10−6 cm3·g−1 for zirconium-ruthenium alloys) are ultralow, about one-third that of Ti-based alloys (Ti–6Al–4V, ~3.5 × 10−6 cm3·g−1, CP Ti and Ti–6Al–7Nb, ~3.0 × 10−6 cm3·g−1), and one-sixth that of Co–Cr alloys (Co–Cr–Mo, ~7.7 × 10−6 cm3·g−1). Among the Zr–Ru alloy series, Zr–1Ru demonstrates enhanced mechanical properties, excellent corrosion resistance and cell viability with lowest magnetic susceptibility, and thus is the optimal Zr–Ru alloy system as therapeutic devices under MRI diagnostics environments. PMID:27090955

A new approach to synthesize supported ruthenium phosphides for hydrodesulfurization

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Qingfang; Key Laboratory of Advanced Energy Materials Chemistry; Wang, Zhiqiang

2016-02-15

Highlights: • We bring out a new method to synthesize noble metal phosphides at low temperature. • Both RuP and Ru{sub 2}P were synthesized using triphenylphosphine as phosphorus sources. • Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. • RuP/SiO{sub 2} prepared by new method had better HDS activity to that by TPR method. - Abstract: Supported noble metal ruthenium phosphides were synthesized by one-step H{sub 2}-thermal treatment method using triphenylphosphine (TPP) as phosphorus sources at low temperatures. Two phosphides RuP and Ru{sub 2}P can be prepared by this method via varying the molarmore » ratio of metal salt and TPP. The as-prepared phosphides were characterized by X-ray powder diffraction (XRD), low-temperature N{sub 2} adsorption, CO chemisorption and transmission electronic microscopy (TEM). The supported ruthenium phosphides prepared by new method and conventional method together with contradistinctive metallic ruthenium were evaluated in hydrodesulfurization (HDS) of dibenzothiophene (DBT). The catalytic results showed that metal-rich Ru{sub 2}P was the better active phase for HDS than RuP and metal Ru. Besides this, ruthenium phosphide catalyst prepared by new method exhibited superior HDS activity to that prepared by conventional method.« less

Ruthenium nanoparticles in ionic liquids: structural and stability effects of polar solutes.

PubMed

Salas, Gorka; Podgoršek, Ajda; Campbell, Paul S; Santini, Catherine C; Pádua, Agílio A H; Costa Gomes, Margarida F; Philippot, Karine; Chaudret, Bruno; Turmine, Mireille

2011-08-14

Ionic liquids are a stabilizing medium for the in situ synthesis of ruthenium nanoparticles. Herein we show that the addition of molecular polar solutes to the ionic liquid, even in low concentrations, eliminates the role of the ionic liquid 3D structure in controlling the size of ruthenium nanoparticles, and can induce their aggregation. We have performed the synthesis of ruthenium nanoparticles by decomposition of [Ru(COD)(COT)] in 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, [C(1)C(4)Im][NTf(2)], under H(2) in the presence of varying amounts of water or 1-octylamine. For water added during the synthesis of metallic nanoparticles, a decrease of the solubility in the ionic liquid was observed, showed by nanoparticles located at the interface between aqueous and ionic phases. When 1-octylamine is present during the synthesis, stable nanoparticles of a constant size are obtained. When 1-octylamine is added after the synthesis, aggregation of the ruthenium nanoparticles is observed. In order to explain these phenomena, we have explored the molecular interactions between the different species using (13)C-NMR and DOSY (Diffusional Order Spectroscopy) experiments, mixing calorimetry, surface tension measurements and molecular simulations. We conclude that the behaviour of the ruthenium nanoparticles in [C(1)C(4)Im][NTf(2)] in the presence of 1-octylamine depends on the interaction between the ligand and the nanoparticles in terms of the energetics but also of the structural arrangement of the amine at the nanoparticle's surface.

Complex of transferrin with ruthenium for medical applications

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1984-05-15

A novel ruthenium-transferrin complex is disclosed which is prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40 C for about 2 hours. The complex is purified by means of gel chromotography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparative results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex. No Drawings

Ruthenium-Catalyzed Cascade C—H Functionalization of Phenylacetophenones**

PubMed Central

Mehta, Vaibhav P; García-López, José-Antonio; Greaney, Michael F

2014-01-01

Three orthogonal cascade C—H functionalization processes are described, based on ruthenium-catalyzed C—H alkenylation. 1-Indanones, indeno indenes, and indeno furanones were accessed through cascade pathways by using arylacetophenones as substrates under conditions of catalytic [{Ru(p-cymene)Cl2}2] and stoichiometric Cu(OAc)2. Each transformation uses C—H functionalization methods to form C—C bonds sequentially, with the indeno furanone synthesis featuring a C—O bond formation as the terminating step. This work demonstrates the power of ruthenium-catalyzed alkenylation as a platform reaction to develop more complex transformations, with multiple C—H functionalization steps taking place in a single operation to access novel carbocyclic structures. PMID:24453063

Ruthenium-Catalyzed Cascade Annulation of Indole with Propargyl Alcohols.

PubMed

Kaufmann, Julia; Jäckel, Elisabeth; Haak, Edgar

2018-05-14

Cascade transformations forming multiple bonds and one-pot procedures provide rapid access to natural-product-like scaffolds from simple precursors. These atom-economic processes are valuable tools in organic synthesis and drug discovery. Herein, we report on ruthenium-catalyzed cascade annulations of indole with readily available propargyl alcohols. These provide rapid access to diverse carbazoles, cyclohepta[b]indoles, and further fused polycycles with high selectivity. A bifunctional ruthenium complex featuring a redox-coupled cyclopentadienone ligand acts as a common catalyst for the different cascade processes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Preparation and characterization of conductive and transparent ruthenium dioxide sol-gel films.

PubMed

Allhusen, John S; Conboy, John C

2013-11-27

RuO2 conductive thin films were synthesized using the sol-gel method and deposited onto transparent insulating substrates. The optical transmission, film thickness, surface morphology and composition, resistivity, and spectroelectrochemical performance have been characterized. The optical transmission values of these films ranged from 70 to 89% in the visible region and from 56 to 88% in the infrared region. Resistivity values of the RuO2 sol-gel films varied from 1.02 × 10(-3) to 1.13 Ω cm and are highly dependent on the initial solution concentration of RuO2 in the sol-gel. The RuO2 sol-gel films were used as electrodes for the electrochemical oxidation and reduction of ferrocenemethanol. The electrochemical behavior of our novel RuO2 sol-gel films was compared to that of a standard platinum disk electrode and showed no appreciable differences in the half-wave potential (E1/2). The mechanical and chemical stability of the coatings was tested by physical abrasion and exposure to highly acidic, oxidizing Piranha solution. Repeated exposure to these extreme conditions did not result in any appreciable decline in electrochemical performance. Finally, the use of the novel RuO2 sol-gel conductive and transparent films was demonstrated in a spectroelectrochemistry experiment in which the oxidation and reduction of ferrocenemethanol was monitored via UV-vis spectroscopy as the applied potential was cycled.

Formation of thin-film resistors on silicon substrates

DOEpatents

Schnable, George L.; Wu, Chung P.

1988-11-01

The formation of thin-film resistors by the ion implantation of a metallic conductive layer in the surface of a layer of phosphosilicate glass or borophosphosilicate glass which is deposited on a silicon substrate. The metallic conductive layer materials comprise one of the group consisting of tantalum, ruthenium, rhodium, platinum and chromium silicide. The resistor is formed and annealed prior to deposition of metal, e.g. aluminum, on the substrate.

Effective thermal and mechanical properties of polycrystalline diamond films

NASA Astrophysics Data System (ADS)

Cheng, Hao-Yu; Yang, Chi-Yuan; Yang, Li-Chueh; Peng, Kun-Cheng; Chia, Chih-Ta; Liu, Shiu-Jen; Lin, I.-Nan; Lin, Kung-Hsuan

2018-04-01

Polycrystalline diamond films were demonstrated as good candidates for electron field emitters, and their mechanical/thermal properties should thus be considered for real devices. We utilized ultrafast optical techniques to investigate the phonon dynamics of several polycrystalline diamond films, prepared by microwave plasma enhanced chemical vapor deposition. The mechanical properties (longitudinal acoustic velocity) and thermal conductivities of diamond films were evaluated from the coherent and incoherent phonon dynamics, respectively. Ultrananocrystalline diamond films were grown using a CH4 (2%)/Ar plasma, while microcrystalline diamond films were grown using a CH4 (2%)/H2 plasma. The ultrananocrystalline diamond film (with a grain size of several nanometers) possesses low acoustic velocity (14.5 nm/ps) and low thermal conductivity (3.17 W/m K) compared with other kinds of diamond films. The acoustic velocity of diamond films increased abruptly to nearly the same as that of natural diamond and remained there when the rod-shaped diamond grains were induced due to the incorporation of H2 in the growth plasma (CH4/Ar). The thermal conductivities of the materials increased monotonously with increasing incorporation of H2 in the growth plasma (CH4/Ar). The thermal conductivity of 25.6 W/m K was attained for nanocrystalline diamond films containing spherical diamond grains (with a size of several tens of nanometers). Compared with single crystalline diamond, the low thermal conductivity of polycrystalline films results from phonon scattering at the interfaces of grains and amorphous carbon in the boundary phases.

Digital image processing of nanometer-size metal particles on amorphous substrates

NASA Technical Reports Server (NTRS)

Soria, F.; Artal, P.; Bescos, J.; Heinemann, K.

1989-01-01

The task of differentiating very small metal aggregates supported on amorphous films from the phase contrast image features inherently stemming from the support is extremely difficult in the nanometer particle size range. Digital image processing was employed to overcome some of the ambiguities in evaluating such micrographs. It was demonstrated that such processing allowed positive particle detection and a limited degree of statistical size analysis even for micrographs where by bare eye examination the distribution between particles and erroneous substrate features would seem highly ambiguous. The smallest size class detected for Pd/C samples peaks at 0.8 nm. This size class was found in various samples prepared under different evaporation conditions and it is concluded that these particles consist of 'a magic number' of 13 atoms and have cubooctahedral or icosahedral crystal structure.

Ruthenium on chitosan: A recyclable heterogeneous catalyst for aqueous hydration of nitriles to amides

EPA Science Inventory

Ruthenium has been immobilized over chitosan by simply stirring an aqueous suspension of chitosan in water with ruthenium chloride and has been utilized for the oxidation of nitriles to amides; the hydration of nitriles occurs in high yield and excellent selectivity, which procee...

Structural, spectral, DFT and biological studies on macrocyclic mononuclear ruthenium (II) complexes

NASA Astrophysics Data System (ADS)

Muthukkumar, M.; Kamal, C.; Venkatesh, G.; Kaya, C.; Kaya, S.; Enoch, Israel V. M. V.; Vennila, P.; Rajavel, R.

2017-11-01

Macrocyclic mononuclear ruthenium (II) complexes have been synthesized by condensation method [Ru (L1, L2, L3) Cl2] L1 = (C36 H31 N9), L2= (C42H36N8), L3= (C32H32 N8)]. These ruthenium complexes have been established by elemental analyses and spectroscopic techniques (Fourier transform infrared spectroscopy (FT-IR), 1H- nuclear magnetic resonance (NMR), 13C- NMR and Electrospray ionization mass spectrometry (ESI-MS)). The coordination mode of the ligand has been confirmed and the octahedral geometry around the ruthenium ion has been revealed. Binding affinity and binding mode of ruthenium (II) complexes with Bovine serum Albumin (BSA) have been characterized by Emission spectra analysis. UV-Visible and fluorescence spectroscopic techniques have also been utilized to examine the interaction between ligand and its complexes L1, L2, & L3 with BSA. Chemical parameters and molecular structure of Ru (II) complexes L1H, L2H, & L3H have been determined by DFT coupled with B3LYP/6-311G** functional in both the gaseous and aqueous phases.

Measurement of contact-line dissipation in a nanometer-thin soap film

NASA Astrophysics Data System (ADS)

Guo, Shuo; Lee, Chun Huen; Sheng, Ping; Tong, Penger

2015-01-01

We report a direct measurement of the friction coefficient ξc of two fluctuating contact lines formed on a fiber surface when a long glass fiber intersects the two water-air interfaces of a thin soap film. The glass fiber of diameter d in the range of 0.4-4 μ m and length 100-300 μ m is glued onto the front end of a rectangular cantilever used for atomic force microscopy. As a sensitive mechanical resonator, the hanging fiber probe can accurately measure a minute change of its viscous damping caused by the soap film. By measuring the broadening of the resonant peak of the hanging fiber probe with varying viscosity η of the soap film and different surface treatments of the glass fiber, we confirm that the contact line dissipation obeys a universal scaling law, ξc=α π d η , where the coefficient α =1.1 ±0.3 is insensitive to the change of liquid-solid contact angle. The experimental result is in good agreement with the numerical result based on the phase field model under the generalized Navier boundary conditions.

Measurement of contact-line dissipation in a nanometer-thin soap film.

PubMed

Guo, Shuo; Lee, Chun Huen; Sheng, Ping; Tong, Penger

2015-01-01

We report a direct measurement of the friction coefficient ξ(c) of two fluctuating contact lines formed on a fiber surface when a long glass fiber intersects the two water-air interfaces of a thin soap film. The glass fiber of diameter d in the range of 0.4-4 μm and length 100-300 μm is glued onto the front end of a rectangular cantilever used for atomic force microscopy. As a sensitive mechanical resonator, the hanging fiber probe can accurately measure a minute change of its viscous damping caused by the soap film. By measuring the broadening of the resonant peak of the hanging fiber probe with varying viscosity η of the soap film and different surface treatments of the glass fiber, we confirm that the contact line dissipation obeys a universal scaling law, ξ(c)=απdη, where the coefficient α=1.1±0.3 is insensitive to the change of liquid-solid contact angle. The experimental result is in good agreement with the numerical result based on the phase field model under the generalized Navier boundary conditions.

The Mystery of the Electronic Spectrum of Ruthenium Monophosphide

NASA Astrophysics Data System (ADS)

Adam, Allan G.; Christensen, Ryan M.; Dore, Jacob M.; Konder, Ricarda M.; Tokaryk, Dennis W.

2016-06-01

Using PH3 as a reactant gas and ruthenium as the target metal in the UNB laser ablation spectrometer, the ruthenium monophosphide molecule (RuP) has been detected. Dispersed fluorescence experiments have been performed to determine ground state vibrational frequencies and the presence of any low-lying electronic states. Rotationally resolved spectra of two vibrational bands at 577nm and 592nm have been taken; the bands have been identified as 1-0 and 0-0 bands based on isotopic shifts. Ruthenium has seven stable isotopes and rotational transitions have been observed for six of the RuP isotopologues. RuP is isoelectronic to RuN so it is expected that RuP will have a 2Σ+ ground state and low resolution spectra indicated a likely 2Σ+ - 2Σ+ electronic transition. Further investigation has led us to believe we are observing a 2Π - 2Σ+ transition but mysteriously some important rotational branches are missing. It is hoped that new data to be recorded on a second electronic system we have observed at 535nm will help shed light on this mystery.

Ruthenium on rutile catalyst, catalytic system, and method for aqueous phase hydrogenations

DOEpatents

Elliot, Douglas C.; Werpy, Todd A.; Wang, Yong; Frye, Jr., John G.

2001-01-01

An essentially nickel- and rhenium-free catalyst is described comprising ruthenium on a titania support where the titania is greater than 75% rutile. A catalytic system containing a nickel-free catalyst comprising ruthenium on a titania support where the titania is greater than 75% rutile, and a method using this catalyst in the hydrogenation of an organic compound in the aqueous phase is also described.

Magnetic Silica-Supported Ruthenium Nanoparticles: An Efficient Catalyst for Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

One-pot synthesis of ruthenium nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium nano particles immobilization; the hydration of nitriles and transfer hydrogenation of carbonyl compounds occurs in hi...

Catalytic water oxidation by ruthenium(II) quaterpyridine (qpy) complexes: evidence for ruthenium(III) qpy-N,N'''-dioxide as the real catalysts.

PubMed

Liu, Yingying; Ng, Siu-Mui; Yiu, Shek-Man; Lam, William W Y; Wei, Xi-Guang; Lau, Kai-Chung; Lau, Tai-Chu

2014-12-22

Polypyridyl and related ligands have been widely used for the development of water oxidation catalysts. Supposedly these ligands are oxidation-resistant and can stabilize high-oxidation-state intermediates. In this work a series of ruthenium(II) complexes [Ru(qpy)(L)2 ](2+) (qpy=2,2':6',2'':6'',2'''-quaterpyridine; L=substituted pyridine) have been synthesized and found to catalyze Ce(IV) -driven water oxidation, with turnover numbers of up to 2100. However, these ruthenium complexes are found to function only as precatalysts; first, they have to be oxidized to the qpy-N,N'''-dioxide (ONNO) complexes [Ru(ONNO)(L)2 ](3+) which are the real catalysts for water oxidation. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thick film magnetic nanoparticulate composites and method of manufacture thereof

NASA Technical Reports Server (NTRS)

Ge, Shihui (Inventor); Yan, Dajing (Inventor); Xiao, Danny T. (Inventor); Ma, Xinqing (Inventor); Zhang, Yide (Inventor); Zhang, Zongtao (Inventor)

2009-01-01

Thick film magnetic/insulating nanocomposite materials, with significantly reduced core loss, and their manufacture are described. The insulator coated magnetic nanocomposite comprises one or more magnetic components, and an insulating component. The magnetic component comprises nanometer scale particles (about 1 to about 100 nanometers) coated by a thin-layered insulating phase. While the intergrain interaction between the immediate neighboring magnetic nanoparticles separated by the insulating phase provides the desired soft magnetic properties, the insulating material provides high resistivity, which reduces eddy current loss.

Pentamethylcyclopentadienyl-ruthenium catalysts for regio- and enantioselective allylation of nucleophiles.

PubMed

Bruneau, Christian; Renaud, Jean-Luc; Demerseman, Bernard

2006-07-05

Ruthenium(II) complexes containing the pentamethylcyclopentadienyl ligand efficiently perform the activation of allylic carbonates and halides to generate cationic and dicationic ruthenium(IV) complexes. This activation has been transferred as a key step to the catalytic allylation of nucleophiles. The structural and electronic properties of the allylic moieties lead to the regioselective formation of chiral products resulting from nucleophilic addition to their most substituted terminus. The catalytic activity of various Ru(Cp*) precatalysts in several allylic substitutions by C and O nucleophiles will be presented. The enantioselective version that has been demonstrated by using optically pure bisoxazoline ligands will also be discussed.

Phase transformation of molecular beam epitaxy-grown nanometer-thick Gd₂O₃ and Y₂O₃ on GaN.

PubMed

Chang, Wen-Hsin; Wu, Shao-Yun; Lee, Chih-Hsun; Lai, Te-Yang; Lee, Yi-Jun; Chang, Pen; Hsu, Chia-Hung; Huang, Tsung-Shiew; Kwo, J Raynien; Hong, Minghwei

2013-02-01

High quality nanometer-thick Gd₂O₃ and Y₂O₃ (rare-earth oxide, R₂O₃) films have been epitaxially grown on GaN (0001) substrate by molecular beam epitaxy (MBE). The R₂O₃ epi-layers exhibit remarkable thermal stability at 1100 °C, uniformity, and highly structural perfection. Structural investigation was carried out by in situ reflection high energy electron diffraction (RHEED) and ex-situ X-ray diffraction (XRD) with synchrotron radiation. In the initial stage of epitaxial growth, the R₂O₃ layers have a hexagonal phase with the epitaxial relationship of R₂O₃ (0001)(H)<1120>(H)//GaN(0001)(H)<1120>(H). With the increase in R₂O₃ film thickness, the structure of the R₂O₃ films changes from single domain hexagonal phase to monoclinic phase with six different rotational domains, following the R₂O₃ (201)(M)[020](M)//GaN(0001)(H)<1120>(H) orientational relationship. The structural details and fingerprints of hexagonal and monoclinic phase Gd₂O₃ films have also been examined by using electron energy loss spectroscopy (EELS). Approximate 3-4 nm is the critical thickness for the structural phase transition depending on the composing rare earth element.

Ru nucleation and thin film smoothness improvement with ammonia during chemical vapor deposition

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liao, Wen; Ekerdt, John G., E-mail: ekerdt@utexas.edu

This study reports the use of ammonia to inhibit the growth of previously nucleated ruthenium islands and force the nucleation of additional islands such that thinner films form as the islands coalesce with continued growth. Ruthenium films are grown at 448 K in a chemical vapor deposition process on SiO{sub 2}/Si(001) using triruthenium dodecacarbonyl, Ru{sub 3}(CO){sub 12}, with and without a constant partial pressure of ammonia. Film growth was performed at a Ru{sub 3}(CO){sub 12}/Ar pressure of 47.2 mTorr. The ammonia partial pressure varied from 0 to 27.8 mTorr. X-ray photoelectron spectroscopy was used to analyze the samples in situ. Exmore » situ characterization included scanning electron microscopy, atomic force microscopy, and x-ray diffraction and x-ray reflectivity. Nucleation studies limited to the first 10 min of growth revealed the maximum nanoparticle (island) density of 8.1 × 10{sup 11 }cm{sup −2} occurred at an intermediate ammonia pressure (5.25 mTorr) compared to a density of 3.1 × 10{sup 11 }cm{sup −2} for no ammonia addition. Extending film growth to 120 min and varying the ammonia partial pressure during the first 10 min followed by 5.25 mTorr ammonia pressure for the final 110 min reveals the importance of nucleation on film smoothness. A model describing the inhibition effects of ammonia during nucleation and growth is presented.« less

A ruthenium anticancer compound interacts with histones and impacts differently on epigenetic and death pathways compared to cisplatin

PubMed Central

Capuozzo, Antonelle; Ali, Moussa; Santamaria, Rita; Armant, Olivier; Delalande, Francois; Dorsselaer, Alain Van; Cianferani, Sarah; Spencer, John; Pfeffer, Michel; Mellitzer, Georg; Gaiddon, Christian

2017-01-01

Ruthenium complexes are considered as potential replacements for platinum compounds in oncotherapy. Their clinical development is handicapped by a lack of consensus on their mode of action. In this study, we identify three histones (H3.1, H2A, H2B) as possible targets for an anticancer redox organoruthenium compound (RDC11). Using purified histones, we confirmed an interaction between the ruthenium complex and histones that impacted on histone complex formation. A comparative study of the ruthenium complex versus cisplatin showed differential epigenetic modifications on histone H3 that correlated with differential expression of histone deacetylase (HDAC) genes. We then characterized the impact of these epigenetic modifications on signaling pathways employing a transcriptomic approach. Clustering analyses showed gene expression signatures specific for cisplatin (42%) and for the ruthenium complex (30%). Signaling pathway analyses pointed to specificities distinguishing the ruthenium complex from cisplatin. For instance, cisplatin triggered preferentially p53 and folate biosynthesis while the ruthenium complex induced endoplasmic reticulum stress and trans-sulfuration pathways. To further understand the role of HDACs in these regulations, we used suberanilohydroxamic acid (SAHA) and showed that it synergized with cisplatin cytotoxicity while antagonizing the ruthenium complex activity. This study provides critical information for the characterization of signaling pathways differentiating both compounds, in particular, by the identification of a non-DNA direct target for an organoruthenium complex. PMID:27935863

Rim instability of bursting thin smectic films

NASA Astrophysics Data System (ADS)

Trittel, Torsten; John, Thomas; Tsuji, Kinko; Stannarius, Ralf

2013-05-01

The rupture of thin smectic bubbles is studied by means of high speed video imaging. Bubbles of centimeter diameter and film thicknesses in the nanometer range are pierced, and the instabilities of the moving rim around the opening hole are described. Scaling laws describe the relation between film thickness and features of the filamentation process of the rim. A flapping motion of the retracting smectic film is assumed as the origin of the observed filamentation instability. A comparison with similar phenomena in soap bubbles is made. The present experiments extend studies on soap films [H. Lhuissier and E. Villermaux, Phys. Rev. Lett. 103, 054501 (2009), 10.1103/PhysRevLett.103.054501] to much thinner, uniform films of thermotropic liquid crystals.

Photoexpulsion of Surface-Grafted Ruthenium Complexes and Subsequent Release of Cytotoxic Cargos to Cancer Cells from Mesoporous Silica Nanoparticles

PubMed Central

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W.; Chen, Xinqi; Botros, Youssry Y.; Cryns, Vincent L.; Sauvage, Jean-Pierre; Stoddart, J. Fraser

2014-01-01

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions. PMID:23815127

Photoexpulsion of surface-grafted ruthenium complexes and subsequent release of cytotoxic cargos to cancer cells from mesoporous silica nanoparticles.

PubMed

Frasconi, Marco; Liu, Zhichang; Lei, Juying; Wu, Yilei; Strekalova, Elena; Malin, Dmitry; Ambrogio, Michael W; Chen, Xinqi; Botros, Youssry Y; Cryns, Vincent L; Sauvage, Jean-Pierre; Stoddart, J Fraser

2013-08-07

Ruthenium(II) polypyridyl complexes have emerged both as promising probes of DNA structure and as anticancer agents because of their unique photophysical and cytotoxic properties. A key consideration in the administration of those therapeutic agents is the optimization of their chemical reactivities to allow facile attack on the target sites, yet avoid unwanted side effects. Here, we present a drug delivery platform technology, obtained by grafting the surface of mesoporous silica nanoparticles (MSNPs) with ruthenium(II) dipyridophenazine (dppz) complexes. This hybrid nanomaterial displays enhanced luminescent properties relative to that of the ruthenium(II) dppz complex in a homogeneous phase. Since the coordination between the ruthenium(II) complex and a monodentate ligand linked covalently to the nanoparticles can be cleaved under irradiation with visible light, the ruthenium complex can be released from the surface of the nanoparticles by selective substitution of this ligand with a water molecule. Indeed, the modified MSNPs undergo rapid cellular uptake, and after activation with light, the release of an aqua ruthenium(II) complex is observed. We have delivered, in combination, the ruthenium(II) complex and paclitaxel, loaded in the mesoporous structure, to breast cancer cells. This hybrid material represents a promising candidate as one of the so-called theranostic agents that possess both diagnostic and therapeutic functions.

Acetate- and thiol-capped monodisperse ruthenium nanoparticles: XPS, XAS, and HRTEM studies.

PubMed

Chakroune, Nassira; Viau, Guillaume; Ammar, Souad; Poul, Laurence; Veautier, Delphine; Chehimi, Mohamed M; Mangeney, Claire; Villain, Françoise; Fiévet, Fernand

2005-07-19

Monodisperse ruthenium nanoparticles were prepared by reduction of RuCl3 in 1,2-propanediol. The mean particle size was controlled by appropriate choice of the reduction temperature and the acetate ion concentration. Colloidal solutions in toluene were obtained by coating the metal particles with dodecanethiol. High-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS), and X-ray absorption spectroscopy (XANES and EXAFS for the Ru K-absorption edge) were performed on particles of two different diameters, 2 and 4 nm, and in different environments, polyol/acetate or thiol. For particles stored in polyol/acetate XPS studies revealed superficial oxidation limited to one monolayer and a surface coating containing mostly acetate ions. Analysis of the EXAFS spectra showed both oxygen and ruthenium atoms around the ruthenium atoms with a Ru-Ru coordination number N smaller than the bulk value, as expected for fine particles. In the case of 2 nm acetate-capped particles N is consistent with particles made up of a metallic core and an oxidized monolayer. For 2 nm thiol-coated particles, a Ru-S bond was evidenced by XPS and XAS. For the 4 nm particles XANES and XPS studies showed that most of the ruthenium atoms are in the zerovalent state. Nevertheless, in both cases, when capped with thiol, the Ru-Ru coordination number inferred from EXAFS is much smaller than for particles of the same size stored in polyol. This is attributed to a structural disorganization of the particles by thiol chemisorption. HRTEM studies confirm the marked dependence of the structural properties of the ruthenium particles on their chemical environment; they show the acetate-coated particles to be single crystals, whereas the thiol-coated particles appear to be polycrystalline.

Oxygen and hydrogen evolution reaction on oriented single crystals of ruthenium dioxide

DOE Office of Scientific and Technical Information (OSTI.GOV)

Berger, L I; Pollak, F H; Canivez, Y

1979-01-01

A novel design for water electrolysis using a solid polymer electrolyte is being developed by General Electric. Ruthenium is one of the best electrocatalysts for the oxygen evolution reaction. There are problems connected with the significant loss in electrocatalytic activity with time. This performance degradation is presumably due to the gradual formation of an RuO/sub 2/ film. We have performed electrochemical measurements on (100), (110) and (111) oriented single crystals of RuO/sub 2/ in order to elucidate the mechanism of the electrocatalytic process. Large single crystals were grown by the vapor transport method. Our investigation has revealed several interesting differencesmore » for the various orientations. This study indicates that RuO/sub 3/ may be an important intermediate species prior to oxygen evolution and that the formation of the RuO/sub 3/ is the rate limiting process. Similar results were previously obtained for IrO/sub 2/.« less

Highly Sensitive, Uniform, and Reproducible Surface-Enhanced Raman Spectroscopy Substrate with Nanometer-Scale Quasi-periodic Nanostructures.

PubMed

Jin, Yuanhao; Wang, Yingcheng; Chen, Mo; Xiao, Xiaoyang; Zhang, Tianfu; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Li, Qunqing

2017-09-20

We introduce a simple and cost-effective approach for fabrication of effective surface-enhanced Raman spectroscopy (SERS) substrates. It is shown that the as-fabricated substrates show excellent SERS effects in various probe molecules with high sensitivity, that is, picomolar level detection, and also good reliability. With a SERS enhancement factor beyond 10 8 and excellent reproducibility (deviation less than 5%) of signal intensity, the fabrication of the SERS substrate is realized on a four-inch wafer and proven to be effective in pesticide residue detection. The SERS substrate is realized first through the fabrication of quasi-periodic nanostructured silicon with dimension features in tens of nanometers using superaligned carbon nanotubes networks as an etching mask, after which a large amount of hot spots with nanometer gaps are formed through deposition of a gold film. With rigorous nanostructure design, the enhanced performance of electromagnetic field distribution for nanostructures is optimized. With the advantage of cost-effective large-area preparation, it is believed that the as-fabricated SERS substrate could be used in a wide variety of actual applications where detection of trace amounts is necessary.

Manganese oxide nanowires, films, and membranes and methods of making

DOEpatents

Suib, Steven Lawrence [Storrs, CT; Yuan, Jikang [Storrs, CT

2008-10-21

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

Giant Faraday Rotation in Metal-Fluoride Nanogranular Films.

PubMed

Kobayashi, N; Ikeda, K; Gu, Bo; Takahashi, S; Masumoto, H; Maekawa, S

2018-03-21

Magneto-optical Faraday effect is widely applied in optical devices and is indispensable for optical communications and advanced information technology. However, the bismuth garnet Bi-YIG is only the Faraday material since 1972. Here we introduce (Fe, FeCo)-(Al-,Y-fluoride) nanogranular films exhibiting giant Faraday effect, 40 times larger than Bi-YIG. These films have a nanocomposite structure, in which nanometer-sized Fe, FeCo ferromagnetic granules are dispersed in a Al,Y-fluoride matrix.

Depositing nanometer-sized particles of metals onto carbon allotropes

NASA Technical Reports Server (NTRS)

Delozier, Donavon M. (Inventor); Fallbach, Michael J. (Inventor); Smith, Joseph G. (Inventor); Watson, Kent A. (Inventor); Ghose, Sayata (Inventor); Connell, John W. (Inventor)

2010-01-01

A process for depositing nanometer-sized metal particles onto a substrate in the absence of aqueous solvents, organic solvents, and reducing agents, and without any required pre-treatment of the substrate, includes preparing an admixture of a metal compound and a substrate by dry mixing a chosen amount of the metal compound with a chosen amount of the substrate; and supplying energy to the admixture in an amount sufficient to deposit zero valance metal particles onto the substrate. This process gives rise to a number of deposited metallic particle sizes which may be controlled. The compositions prepared by this process are used to produce polymer composites by combining them with readily available commodity and engineering plastics. The polymer composites are used as coatings, or they are used to fabricate articles, such as free-standing films, fibers, fabrics, foams, molded and laminated articles, tubes, adhesives, and fiber reinforced articles. These articles are well-suited for many applications requiring thermal conductivity, electrical conductivity, antibacterial activity, catalytic activity, and combinations thereof.

Thickness and surface roughness study of co-sputtered nanostructured alumina/tungsten (Al2O3/W) thin films

NASA Astrophysics Data System (ADS)

Naveen, A.; Krishnamurthy, L.; Shridhar, T. N.

2018-04-01

Tungsten (W) and Alumina (Al2O3) thin films have been developed using co-sputtering technique on SS304, Copper (Cu) and Glass slides using Direct Current magnetron sputtering (DC) and Radio Frequency (RF) magnetron sputtering methods respectively. Central Composite Design (CCD) method approach has been adopted to determine the number of experimental plans for deposition and DC power, RF power and Argon gas flow rate have been input parameters, each at 5 levels for development of thin films. In this research paper, study has been carried out determine the optimized condition of deposition parameters for thickness and surface roughness of the thin films. Thickness and average Surface roughness in terms of nanometer (nm) have been characterized by thickness profilometer and atomic force microscopy respectively. The maximum and minimum average thickness observed to be 445 nm and 130 respectively. The optimum deposition condition for W/Al2O3 thin film growth was determined to be at 1000 watts of DC power and 800 watts of RF power, 20 minutes of deposition time, and almost 300 Standard Cubic Centimeter(SCCM) of Argon gas flow. It was observed that average roughness difference found to be less than one nanometer on SS substrate and one nanometer on copper approximately.

Active Interfacial Shear Microrheology of Aging Protein Films

PubMed Central

Dhar, Prajnaparamita; Cao, Yanyan; Fischer, Thomas M.; Zasadzinski, J. A.

2012-01-01

The magnetically driven rotation of 300 nm diameter rods shows the surface viscosity of albumin at an air-water interface increases from 10−9 to 10−5 Ns/m over two hours while the surface pressure saturates in minutes. The increase in surface viscosity is not accompanied by a corresponding increase in elasticity, suggesting that the protein film anneals with time, resulting in a more densely packed film leading to increased resistance to shear. The nanometer dimensions of the rods provide the same sensitivity as passive microrheology with an improved ability to measure more viscous films. PMID:20366371

Study on the neotype zirconia's implant coated nanometer hydroxyapatite ceramics

NASA Astrophysics Data System (ADS)

Zhu, J. W.; Yang, D. W.

2007-07-01

In recent years, biologic ceramics is a popular material of implants and bioactive surface modification of dental implant became a research emphasis, which aims to improve bioactivity of implants materials and acquire firmer implants-bone interface. The zirconia ceramic has excellent mechanical properties and nanometer HA ceramics is a bioceramic well known for its bioactivity, therefore, nanometer HA ceramics coating on zirconia, allows combining the excellent mechanical properties of zirconia substrates with its bioactivity. This paper shows a new method for implant shape design and bioactive modification of dental implants surface. Zirconia's implant substrate was prepared by sintered method, central and lateral tunnels were drilled in the zirconia hollow porous cylindrical implants by laser processing. The HA powders and needle-like HA crystals were made by a wet precipitation and calcining method. Its surface was coated with nanometer HA ceramics which was used brush HA slurry and vacuum sintering. Mechanical testing results revealed that the attachment strength of nanometer HA ceramics coated zirconia samples is high. SEM and interface observation after inserted experiment indicated that calcium and phosphor content increased and symmetrically around coated implant-bone tissue interface. A significantly higher affinity index was demonstrated in vivo by histomorphometric evaluation in coated versus uncoated implants. SEM analysis demonstrated better bone adhesion to the material in coated implant at any situation. In addition, the hollow porous cylindrical implant coated with nanometer HA ceramics increase the interaction of bone and implant, the new bone induced into the surface of hollow porous cylindrical implant and through the most tunnels filled into central hole. The branch-like structure makes the implant and bone a body, which increased the contact area and decreased elastic ratio. Therefore, the macroscopical and microcosmic nested structure of

Platinum-ruthenium nanotubes and platinum-ruthenium coated copper nanowires as efficient catalysts for electro-oxidation of methanol

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jie; Cullen, David A.; Forest, Robert V.

2015-01-15

The sluggish kinetics of methanol oxidation reaction (MOR) is a major barrier to the commercialization of direct methanol fuel cells (DMFCs). In this study, we report a facile synthesis of platinum–ruthenium nanotubes (PtRuNTs) and platinum–ruthenium-coated copper nanowires (PtRu/CuNWs) by galvanic displacement reaction using copper nanowires as a template. The PtRu compositional effect on MOR is investigated; the optimum Pt/Ru bulk atomic ratio is about 4 and surface atomic ratio about 1 for both PtRuNTs and PtRu/CuNWs. Enhanced specific MOR activities are observed on both PtRuNTs and PtRu/CuNWs compared with the benchmark commercial carbon-supported PtRu catalyst (PtRu/C, Hispec 12100). Finally, x-raymore » photoelectron spectroscopy (XPS) reveals a larger extent of electron transfer from Ru to Pt on PtRu/CuNWs, which may lead to a modification of the d-band center of Pt and consequently a weaker bonding of CO (the poisoning intermediate) on Pt and a higher MOR activity on PtRu/CuNWs.« less

Effect of sputtering power on the growth of Ru films deposited by magnetron sputtering

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jhanwar, Prachi, E-mail: prachijhanwar87@gmail.com; Department of Electronics, Banasthali University-304022, Rajasthan; Kumar, Arvind

2016-04-13

Ruthenium is deposited by DC magnetron sputtering at different powers and is characterized. The effect of sputtering power on the electrical and structural properties of the film is investigated experimentally. High resolution X-ray diffraction is used to characterize the microstructure of Ru films deposited on SiO{sub 2} surface. The peak (002) is more sharp and intense with full width at half maximum (FWHM) of 0.37° at 250W. The grain size increases with increase in sputtering power improving the crystallinity of the film. The film deposited at high sputtering power also showed lower resistivity (12.40 µΩ-cm) and higher mobility (4.82 cm{sup 2}/V.s) asmore » compared to the film deposited at low power. The surface morphology of the film is studied by atomic force microscopy (AFM).« less

Dithia[3.3]paracyclophane-based monometal ruthenium acetylide complexes: synthesis, characterization and substituent effects.

PubMed

Zhu, Xingxun; Ou, Yaping; Zhang, Jing; Xia, Jian-Long; Yin, Jun; Yu, Guang-Ao; Liu, Sheng Hua

2013-05-21

A series of dithia[3.3]metaparacyclophane-based monometal ruthenium acetylide complexes have been synthesized. All of the complexes have been fully characterised by NMR spectrometry, X-ray crystallography and elemental analyses. At the same time, their basic optical properties, such as UV/Vis absorption spectra, and electrochemical properties have been determined. (1)H NMR and X-ray crystal structure studies reveal that there are intramolecular C-H···π interactions in these ruthenium complexes, in both solution and solid states. Electrochemical studies reveal that the substituted groups on the dithia[3.3]paracyclophane ring can clearly affect the oxidation activities of the ruthenium center by way of the intramolecular C-H···π interaction. In addition, electron-donating groups facilitate the oxidation of the ruthenium center compared with electron-deficient groups. UV/Vis absorption and IR spectra of some complexes in neutral and oxidized states also have been studied. IR spectra studies indicated that the substituents in the cyclophane have some effects on the ν(C≡C) bands of these complexes in the neutral state and little effect on ν(C≡C) of these complexes in the oxidized state.

Oxidation-induced structural changes in sub-nanometer platinum supported on alumina

DOE PAGES

DeBusk, Melanie Moses; Allard, Jr, Lawrence Frederick; Blom, Douglas Allen; ...

2015-06-26

Platinum supported on alumina is an essential component of emission treatment catalysts used in transportation. Theoretical, experimental, and mechanistic aspects of platinum particles supported on a variety of supports have been extensively studied; however, available experimental information on the behavior of single vs. sub-nanometer platinum is extremely limited. To bridge the knowledge gap between single supported platinum and well-formed supported platinum nanoparticles, we have carried out synthesis, characterization, and CO and NO oxidation studies of sub-nanometer platinum supported on α, θ, and γ-Al 2O 3 and monitored changes in structure upon exposure to CO and NO oxidation conditions. Furthermore, wemore » find that sub-nanometer Pt is highly effective for CO oxidation due to high platinum dispersion but is not very efficient as NO oxidation catalyst. Lastly, sub-nanometer platinum agglomerates rapidly under CO or NO oxidation conditions to form nanoparticles.« less

Decarboxylation of cinnamic acids using a ruthenium sawhorse

USDA-ARS?s Scientific Manuscript database

The ruthenium sawhorse has proven effective in the conversion of trans-cinnamic acid, and substituted trans-cinnamic acids, giving an effective source of biobased styrene and styrene analogues. The reaction is especially versatile, as it achieves product without utilising co-reagents. However, the o...

Layer-by-layer modification of thin-film metal-semiconductor multilayers with ultrashort laser pulses

NASA Astrophysics Data System (ADS)

Romashevskiy, S. A.; Tsygankov, P. A.; Ashitkov, S. I.; Agranat, M. B.

2018-05-01

The surface modifications in a multilayer thin-film structure (50-nm alternating layers of Si and Al) induced by a single Gaussian-shaped femtosecond laser pulse (350 fs, 1028 nm) in the air are investigated by means of atomic-force microscopy (AFM), scanning electron microscopy (SEM), and optical microscopy (OM). Depending on the laser fluence, various modifications of nanometer-scale metal and semiconductor layers, including localized formation of silicon/aluminum nanofoams and layer-by-layer removal, are found. While the nanofoams with cell sizes in the range of tens to hundreds of nanometers are produced only in the two top layers, layer-by-layer removal is observed for the four top layers under single pulse irradiation. The 50-nm films of the multilayer structure are found to be separated at their interfaces, resulting in a selective removal of several top layers (up to 4) in the form of step-like (concentric) craters. The observed phenomenon is associated with a thermo-mechanical ablation mechanism that results in splitting off at film-film interface, where the adhesion force is less than the bulk strength of the used materials, revealing linear dependence of threshold fluences on the film thickness.

Silicifying Biofilm Exopolymers on a Hot-Spring Microstromatolite: Templating Nanometer-Thick Laminae

NASA Astrophysics Data System (ADS)

Handley, Kim M.; Turner, Sue J.; Campbell, Kathleen A.; Mountain, Bruce W.

2008-08-01

Exopolymeric substances (EPS) are an integral component of microbial biofilms; however, few studies have addressed their silicification and preservation in hot-spring deposits. Through comparative analyses with the use of a range of microscopy techniques, we identified abundant EPS significant to the textural development of spicular, microstromatolitic, siliceous sinter at Champagne Pool, Waiotapu, New Zealand. Examination of biofilms coating sinter surfaces by confocal laser scanning microscopy (CLSM), environmental scanning electron microscopy (ESEM), cryo-scanning electron microscopy (cryo-SEM), and transmission electron microscopy (TEM) revealed contraction of the gelatinous EPS matrix into films (approximately 10 nm thick) or fibrillar structures, which is common in conventional SEM analyses and analogous to products of naturally occurring desiccation. Silicification of fibrillar EPS contributed to the formation of filamentous sinter. Matrix surfaces or dehydrated films templated sinter laminae (nanometers to microns thick) that, in places, preserved fenestral voids beneath. Laminae of similar thickness are, in general, common to spicular geyserites. This is the first report to demonstrate EPS templation of siliceous stromatolite laminae. Considering the ubiquity of biofilms on surfaces in hot-spring environments, EPS silicification studies are likely to be important to a better understanding of the origins of laminae in other modern and ancient stromatolitic sinters, and EPS potentially may serve as biosignatures in extraterrestrial rocks.

Improvement of ruthenium based decarboxylation of carboxylic acids

USDA-ARS?s Scientific Manuscript database

The removal of oxygen atoms from biobased carboxylic acids is an attractive route to provide the drop in replacement feedstocks that industry needs to continue to provide high performance products. Through the use of ruthenium catalysis, an efficient method where this process can be accomplished on ...

Thermodynamic assessment of the rhodium-ruthenium-oxygen (Rh-Ru-O) system

NASA Astrophysics Data System (ADS)

Gossé, S.; Bordier, S.; Guéneau, C.; Brackx, E.; Domenger, R.; Rogez, J.

2018-03-01

Ruthenium (Ru) and rhodium (Rh) are abundant platinum-group metals formed during burn-up of nuclear fuels. Under normal operating conditions, Rh and Ru accumulate and predominantly form metallic precipitates with other fission products like Mo, Pd and Tc. In the framework of vitrification of high-level nuclear waste, these fission products are poorly soluble in molten glasses. They precipitate as metallic particles and oxide phases. Moreover, these Ru and Rh rich phases strongly depend on temperature and the oxygen fugacity of the glass melt. In case of severe accidental conditions with air ingress, oxidation of the Ru and Rh is possible. At low temperatures (T < 1422 K for rhodium sesquioxide and T < 1815 K for ruthenium dioxide), the formed oxides are relatively stable. On the other hand, at high temperatures (T > 1422 K for rhodium sesquioxide and T > 1815 K for ruthenium dioxide), they may decompose into (Rh)-FCC or (Ru)-HCP metallic phases and radiotoxic volatile gaseous species. A thermodynamic assessment of the Rh-Ru-O system will enable the prediction of: (1) the metallic and oxide phases that form during the vitrification of high-level nuclear wastes and (2) the release of volatile gaseous species during a severe accident. The Calphad method developed herein employs a thermodynamic approach in the investigation of the thermochemistry of rhodium and ruthenium at high temperatures. Current literature on the thermodynamic properties and phase diagram data enables preliminary thermodynamic assessments of the Rh-O and Ru-O systems. Additionally, select compositions in the ternary Rh-Ru-O system underwent experimental tests to complement data found in literature and to establish the phase equilibria in the ternary system.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

NASA Astrophysics Data System (ADS)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.; Ketchum, Douglas R.; Ghodssi, Reza

2015-10-01

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 with solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.

Selective deposition of nanostructured ruthenium oxide using Tobacco mosaic virus for micro-supercapacitors in solid Nafion electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gnerlich, Markus; Ben-Yoav, Hadar; Culver, James N.

A three-dimensional micro-supercapacitor has been developed using a novel bottom-up assembly method combining genetically modified Tobacco mosaic virus (TMV-1Cys), photolithographically defined micropillars and selective deposition of ruthenium oxide on multi-metallic microelectrodes. The three-dimensional microelectrodes consist of a titanium nitride current collector with two functionalized areas: (1) gold coating on the active electrode area promotes TMV-1Cys adhesion, and (2) sacrificial nickel pads dissolve in ruthenium tetroxide plating solution to produce ruthenium oxide on all electrically connected areas. The microfabricated electrodes are arranged in an interdigitated pattern, and the capacitance per electrode has been measured as high as 203 mF cm-2 withmore » solid Nafion electrolyte. The process integration of bio-templated ruthenium oxide with microfabricated electrodes and solid electrolyte is an important advance towards the energy storage needs of mass produced self-sufficient micro-devices.« less

Nanometer-scale features in dolomite from Pennsylvanian rocks, Paradox Basin, Utah

NASA Astrophysics Data System (ADS)

Gournay, Jonas P.; Kirkland, Brenda L.; Folk, Robert L.; Lynch, F. Leo

1999-07-01

Scanning electron microscopy reveals an association between early dolomite in the Pennsylvanian Desert Creek (Paradox Fm.) and small (approximately 0.1 μm) nanometer-scale textures, termed `nannobacteria'. Three diagenetically distinct dolomites are present: early dolomite, limpid dolomite, and baroque dolomite. In this study, only the early dolomite contained nanometer-scale features. These textures occur as discrete balls and rods, clumps of balls, and chains of balls. Precipitation experiments demonstrate that these textures may be the result of precipitation in an organic-rich micro-environment. The presence of these nanometer-scale textures in Pennsylvanian rocks suggests that these early dolomites precipitated in organic-rich, bacterial environments.

Mononuclear ruthenium(III) complexes containing chelating thiosemicarbazones: Synthesis, characterization and catalytic property

NASA Astrophysics Data System (ADS)

Raja, N.; Ramesh, R.

2010-02-01

Mononuclear ruthenium(III) complexes of the type [RuX(EPh 3) 2(L)] (E = P or As; X = Cl or Br; L = dibasic terdentate dehydroacetic acid thiosemicarbazones) have been synthesized from the reaction of thiosemicarbazone ligands with ruthenium(III) precursors, [RuX 3(EPh 3) 3] (where E = P, X = Cl; E = As, X = Cl or Br) and [RuBr 3(PPh 3) 2(CH 3OH)] in benzene. The compositions of the complexes have been established by elemental analysis, magnetic susceptibility measurement, FT-IR, UV-vis and EPR spectral data. These complexes are paramagnetic and show intense d-d and charge transfer transitions in dichloromethane. The complexes show rhombic EPR spectra at LNT which are typical of low-spin distorted octahedral ruthenium(III) species. All the complexes are redox active and display an irreversible metal centered redox processes. Complex [RuCl(PPh 3) 2(DHA-PTSC)] ( 5) was used as catalyst for transfer hydrogenation of ketones in the presence of isopropanol/KOH and was found to be the active species.

New ruthenium carboxylate complexes having a 1-5-. eta. sup 5 -cyclooctadienyl ligand

DOE Office of Scientific and Technical Information (OSTI.GOV)

Osakada, Kohtaro; Grohmann, A.; Yamamoto, Akio

1990-07-01

Reaction of 3-butenoic acid with Ru(cod)(cot) (cod) = 1-2-{eta}{sup 2}:5-6-{eta}{sup 2}-cyclooctadiene; cot = 1-6-{eta}{sup 6}-cyclooctatriene in the presence of PMe{sub 3} gives a new ruthenium(II) complex formulated as Ru(1-5-{eta}{sup 5}-C{sub 8}H{sub 11}){eta}{sup 1}(O),{eta}{sup 2}(C,C{prime}-OCOCH{sub 2}CH{double bond}CH{sub 2})(PMe{sub 3}) (1). X-ray crystallography revealed its structure as having a piano-stool coordination around the ruthenium center. Crystals of 1 are tetragonal, space group P4{sub 3}2{sub 1}2, with a = 12.559 (3) {angstrom}, c = 20.455 (4) {angstrom}, and Z = 8. {sup 1}H and {sup 13}C({sup 1}H) NMR spectra of 1 agree well for the structure with the allyl entity of the carboxylatemore » {pi}-bonded through the C{double bond}C double bond to ruthenium.« less

Molecular Models of Ruthenium(II) Organometallic Complexes

ERIC Educational Resources Information Center

Coleman, William F.

2007-01-01

This article presents the featured molecules for the month of March, which appear in the paper by Ozerov, Fafard, and Hoffman, and which are related to the study of the reactions of a number of "piano stool" complexes of ruthenium(II). The synthesis of compound 2a offers students an alternative to the preparation of ferrocene if they are only…

Reaction of a (Salen)ruthenium(VI) nitrido complex with thiols. C-H bond activation by (Salen)ruthenium(IV) sulfilamido species.

PubMed

Man, Wai-Lun; Lam, William W Y; Kwong, Hoi-Ki; Peng, Shie-Ming; Wong, Wing-Tak; Lau, Tai-Chu

2010-01-04

The reaction of [Ru(VI)(N)(L)(MeOH)](PF(6)) [1; L = N,N'-bis(salicylidene)-o-cyclohexyldiamine dianion] with a stoichiometric amount of RSH in CH(3)CN gives the corresponding (salen)ruthenium(IV) sulfilamido species [Ru(IV){N(H)SR}(L)(NCCH(3))](PF(6)) (2a, R = (t)Bu; 2b, R = Ph). Metathesis of 2a with NaN(3) in methanol affords [Ru(IV){N(H)S(t)Bu}(L)(N(3))] (2c). 2a undergoes further reaction with 1 equiv of RSH to afford a (salen)ruthenium(III) sulfilamine species, [Ru(III){N(H)(2)S(t)Bu}(L)(NCCH(3))](PF(6)) (3). On the other hand, 2b reacts with 2 equiv of PhSH to give a (salen)ruthenium(III) ammine species [Ru(III)(NH(3))(L)(NCCH(3))](PF(6)) (4); this species can also be prepared by treatment of 1 with 3 equiv of PhSH. The X-ray structures of 2c and 4 have been determined. Kinetic studies of the reaction of 1 with excess RSH indicate the following schemes: 1 --> 2a --> 3 (R = (t)Bu), 1 --> 2b --> 4 (R = Ph). The conversion of 1 to 2 probably involves nucleophilic attack of RSH at the nitrido ligand, followed by a proton shift. The conversions of 2a to 3 and 2b to 4 are proposed to involve rate-limiting H-atom abstraction from RSH by 2a or 2b. 2a and 2b are also able to abstract H atoms from hydrocarbons with weak C-H bonds. These reactions occur with large deuterium isotope effects; the kinetic isotope effect values for the oxidation of 9,10-dihydroanthracene, 1,4-cyclohexadiene, and fluorene by 2a are 51, 56, and 11, respectively.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise.

PubMed

Rapp, Teresa L; Phillips, Susan R; Dmochowski, Ivan J

2016-12-13

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently "caging" biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model "caged" acetonitrile complex, Ru(2,2'-bipyridine) 2 (acetonitrile) 2 , or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV-vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course.

Kinetics and Photochemistry of Ruthenium Bisbipyridine Diacetonitrile Complexes: An Interdisciplinary Inorganic and Physical Chemistry Laboratory Exercise

PubMed Central

2016-01-01

The study of ruthenium polypyridyl complexes can be widely applied across disciplines in the undergraduate curriculum. Ruthenium photochemistry has advanced many fields including dye-sensitized solar cells, photoredox catalysis, light-driven water oxidation, and biological electron transfer. Equally promising are ruthenium polypyridyl complexes that provide a sterically bulky, photolabile moiety for transiently “caging” biologically active molecules. Photouncaging involves the use of visible (1-photon) or near-IR (2-photon) light to break one or more bonds between ruthenium and coordinated ligand(s), which can occur on short time scales and in high quantum yields. In this work we demonstrate the use of a model “caged” acetonitrile complex, Ru(2,2′-bipyridine)2(acetonitrile)2, or RuMeCN in an advanced synthesis and physical chemistry laboratory. Students made RuMeCN in an advanced synthesis laboratory course and performed UV–vis spectroscopy and electrochemistry. The following semester students investigated RuMeCN photolysis kinetics in a physical chemistry laboratory. These two exercises may also be combined to create a 2-week module in an advanced undergraduate laboratory course. PMID:28649139

Instability of confined water films between elastic surfaces.

PubMed

de Beer, Sissi; 't Mannetje, Dieter; Zantema, Sietske; Mugele, Frieder

2010-03-02

We investigated the dynamics of nanometer thin water films at controlled ambient humidity adsorbed onto two atomically smooth mica sheets upon rapidly bringing the surfaces into contact. Using a surface forces apparatus (SFA) in imaging mode, we found that the water films break up into a distribution of drops with a typical thickness of a few nanometers and a characteristic lateral size and spacing of several micrometers. Whereas the characteristic length is found to be independent of the ambient humidity, the characteristic time of the breakup decreases from approximately 1 to 0.01 s with increasing humidity. The existence of characteristic length and time scales shows that this breakup is controlled by an instability rather than a conventional nucleation and growth mechanism for SFA experiments. These findings cannot be explained by a dispersion-driven instability mechanism. In contrast, a model involving the elastic energies for the deformation of both the mica sheets and the underlying glue layer correctly reproduces the scaling of the characteristic length and time with humidity.

Hydrogenation of Carbon Dioxide to Methane by Ruthenium Nanoparticles in Ionic Liquid.

PubMed

Melo, Catarina I; Szczepańska, Anna; Bogel-Łukasik, Ewa; Nunes da Ponte, Manuel; Branco, Luís C

2016-05-23

The efficient transformation of carbon dioxide into fuels can be an excellent alternative to sequestration. In this work, we describe CO2 hydrogenation to methane in imidazolium-based ionic liquid media, using ruthenium nanoparticles prepared in situ as catalyst. The best yield of methane (69 %) was achieved using 0.24 mol % ruthenium catalyst (in [omim][NTf2 ], 1-octyl-3-methylimidazolium bistrifluoromethanesulfonylimide, at 40 bar of hydrogen pressure plus 40 bar of CO2 pressure, and at 150 °C. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Membranes for nanometer-scale mass fast transport

DOEpatents

Bakajin, Olgica [San Leandro, CA; Holt, Jason [Berkeley, CA; Noy, Aleksandr [Belmont, CA; Park, Hyung Gyu [Oakland, CA

2011-10-18

Nanoporous membranes comprising single walled, double walled, and multiwalled carbon nanotubes embedded in a matrix material were fabricated for fluid mechanics and mass transfer studies on the nanometer scale and commercial applications. Average pore size can be 2 nm to 20 nm, or seven nm or less, or two nanometers or less. The membrane can be free of large voids spanning the membrane such that transport of material such as gas or liquid occurs exclusively through the tubes. Fast fluid, vapor, and liquid transport are observed. Versatile micromachining methods can be used for membrane fabrication. A single chip can comprise multiple membranes. These membranes are a robust platform for the study of confined molecular transport, with applications in liquid and gas separations and chemical sensing including desalination, dialysis, and fabric formation.

Syntheses and Characterization of Ruthenium(II) Tetrakis(pyridine)complexes: An Advanced Coordination Chemistry Experiment or Mini-Project

ERIC Educational Resources Information Center

Coe, Benjamin J.

2004-01-01

An experiment for third-year undergraduate a student is designed which provides synthetic experience and qualitative interpretation of the spectroscopic properties of the ruthenium complexes. It involves the syntheses and characterization of several coordination complexes of ruthenium, the element found directly beneath iron in the middle of the…

Ruthenium(III) catalyzed oxidation of sugar alcohols by dichloroisocyanuric acid—A kinetic study

NASA Astrophysics Data System (ADS)

Lakshman Kumar, Y.; Venkata Nadh, R.; Radhakrishnamurti, P. S.

2016-02-01

Kinetics of ruthenium(III) catalyzed oxidation of biologically important sugar alcohols (myo-inositol, D-sorbitol, and D-mannitol) by dichloroisocyanuric acid was carried out in aqueous acetic acid—perchloric medium. The reactions were found to be first order in case of oxidant and ruthenium(III). Zero order was observed with the concentrations of sorbitol and mannitol whereas, a positive fractional order was found in the case of inositol concentration. An inverse fractional order was observed with perchloric acid in oxidation of three substrates. Arrhenius parameters were calculated and a plausible mechanism was proposed.

Parameters governing ruthenium sawhorse-based decarboxylation of oleic acid

USDA-ARS?s Scientific Manuscript database

Ruthenium-catalyzed decarboxylation of 9-cisoctadecenoic is a path to produce biobased olefins. Here, a mechanistic study of this reaction was undertaken utilizing a closed reaction system and a pressure reactor. The proposed mechanism of an isomerization followed by a decarboxylation reaction was c...

Mononuclear ruthenium polypyridine complexes that catalyze water oxidation

DOE PAGES

Tong, Lianpeng; Thummel, Randolph P.

2016-08-05

Over the past decade, significant advances have been made in the development of molecular water oxidation catalysts (WOCs) in the context of developing a system that would accomplish artificial photosynthesis. Mononuclear ruthenium complexes with polypyridine ligands have drawn considerable attention in this regard, due to their high catalytic activity and relatively simple structure. In this perspective review, we will discuss mononuclear Ru polypyridine WOCs by organizing them into four groups according to their ligand environments. Each group will be discussed with regard to three fundamental questions: first, how does the catalyst initiate O–O bond formation? Second, which step in themore » catalytic cycle is rate-determining? Third, how efficient is the catalyst according to the specific descriptors such as turnover frequency? All discussion is based on the high-valent ruthenium intermediates that are proposed in the catalytic cycle according to experimental observation and theoretical simulation. Two fundamental mechanisms are set forth. An acid–base mechanism that involves the attack of a water molecule on the oxo of a high valent Ru=O species to form the O–O bond. Subsequent steps lead to dissociation of O 2 and rehydration of the metal center. A second mechanism involves the formation of a Ru–O˙ radical species, two of which then couple to form a Ru–O–O–Ru species that can release O 2 afterwards. The acid–base mechanism appears to be more common and mechanistic differences could result from variation directly related to polypyridine ligand structures. Thus, understanding how electronic, steric, and conformational properties can effect catalyst performance will lead to the rational design of more effective WOCs with not only ruthenium but also other transition metals.« less

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: Aqueous hydration of nitriles to amides

EPA Science Inventory

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involve the in situ generation of magnetic silica (Fe3O4@ SiO2) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this...

Half-sandwich ruthenium(II) biotin conjugates as biological vectors to cancer cells.

PubMed

Babak, Maria V; Plażuk, Damian; Meier, Samuel M; Arabshahi, Homayon John; Reynisson, Jóhannes; Rychlik, Błażej; Błauż, Andrzej; Szulc, Katarzyna; Hanif, Muhammad; Strobl, Sebastian; Roller, Alexander; Keppler, Bernhard K; Hartinger, Christian G

2015-03-23

Ruthenium(II)-arene complexes with biotin-containing ligands were prepared so that a novel drug delivery system based on tumor-specific vitamin-receptor mediated endocytosis could be developed. The complexes were characterized by spectroscopic methods and their in vitro anticancer activity in cancer cell lines with various levels of major biotin receptor (COLO205, HCT116 and SW620 cells) was tested in comparison with the ligands. In all cases, coordination of ruthenium resulted in significantly enhanced cytotoxicity. The affinity of Ru(II) -biotin complexes to avidin was investigated and was lower than that of unmodified biotin. Hill coefficients in the range 2.012-2.851 suggest strong positive cooperation between the complexes and avidin. To estimate the likelihood of binding to the biotin receptor/transporter, docking studies with avidin and streptavidin were conducted. These explain, to some extent, the in vitro anticancer activity results and support the conclusion that these novel half-sandwich ruthenium(II)-biotin conjugates may act as biological vectors to cancer cells, although no clear relationship between the cellular Ru content, the cytotoxicity, and the presence of the biotin moiety was observed. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermal Stress Behavior of Micro- and Nano-Size Aluminum Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hanabusa, T.; Kusaka, K.; Nishida, M.

2008-03-17

In-situ observation of thermal stresses in thin films deposited on silicon substrate was made by X-ray and synchrotron radiation. Specimens prepared in this experiment were micro- and nano-size thin aluminum films with and without passivation film. The thickness of the film was 1 micrometer for micro-size films and 10, 20 and 50 nanometer for nano-size films. The stress measurement in micro-size films was made by X-ray radiation whereas the measurement of nano-size films was made by synchrotron radiation. Residual stress measurement revealed tensile stresses in all as-deposited films. Thermal stresses were measured in a series of heating- and cooling-stage. Thermalmore » stress behavior of micro-size films revealed hysteresis loop during a heating and cooling process. The width of a hysteresis loop was larger in passivated film that unpassivated film. No hysteresis loops were observed in nano-size films with SiO{sub 2} passivation. Strengthning mechanism in thin films was discussed on a passivation film and a film thickness.« less

Optically Transparent Ferromagnetic Nanogranular Films with Tunable Transmittance

PubMed Central

Kobayashi, Nobukiyo; Masumoto, Hiroshi; Takahashi, Saburo; Maekawa, Sadamichi

2016-01-01

Developing optically transparent magnets at room temperature is an important challenge. They would bring many innovations to various industries, not only for electronic and magnetic devices but also for optical applications. Here we introduce FeCo-(Al-fluoride) nanogranular films exhibiting ferromagnetic properties with high optical transparency in the visible light region. These films have a nanocomposite structure, in which nanometer-sized FeCo ferromagnetic granules are dispersed in an Al-fluoride crystallized matrix. The optical transmittance of these films is controlled by changing the magnetization. This is a new type of magneto-optical effect and is explained by spin-dependent charge oscillation between ferromagnetic granules due to quantum-mechanical tunneling. PMID:27677710

Complex of transferrin with ruthenium for medical applications. [Ru 97, Ru 103

DOEpatents

Richards, P.; Srivastava, S.C.; Meinken, G.E.

1980-11-03

A novel Ruthenium-transferrin complex, prepared by reacting iron-free human transferrin dissolved in a sodium acetate solution at pH 7 with ruthenium by heating at about 40/sup 0/C for about 2 hours, and purifying said complex by means of gel chromatography with pH 7 sodium acetate as eluent. The mono- or di-metal complex produced can be used in nuclear medicine in the diagnosis and/or treatment of tumors and abscesses. Comparitive results with Ga-67-citrate, which is the most widely used tumor-localizing agent in nuclear medicine, indicate increased sensitivity of detection and greater tumor uptake with the Ru-transferrin complex.

Electrooxidative Ruthenium-Catalyzed C-H/O-H Annulation by Weak O-Coordination.

PubMed

Qiu, Youai; Tian, Cong; Massignan, Leonardo; Rogge, Torben; Ackermann, Lutz

2018-05-14

Electrocatalysis has been identified as a powerful strategy for organometallic catalysis, and yet electrocatalytic C-H activation is restricted to strongly N-coordinating directing groups. The first example of electrocatalytic C-H activation by weak O-coordination is presented, in which a versatile ruthenium(II) carboxylate catalyst enables electrooxidative C-H/O-H functionalization for alkyne annulations in the absence of metal oxidants; thereby exploiting sustainable electricity as the sole oxidant. Mechanistic insights provide strong support for a facile organometallic C-H ruthenation and an effective electrochemical reoxidation of the key ruthenium(0) intermediate. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Properties of antibacterial polypropylene/nanometal composite fibers

USDA-ARS?s Scientific Manuscript database

Melt spinning of polypropylene fibers containing silver and zinc nanoparticles was investigated. The nanometals were generally uniformly dispersed in polypropylene, but aggregation of these materials was observed on fiber surface and in fiber cross-sections. The mechanical properties of the resulted...

Platinum-ruthenium-palladium alloys for use as a fuel cell catalyst

DOEpatents

Gorer, Alexander

2002-01-01

A noble metal alloy composition for a fuel cell catalyst, a ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Precise ruthenium fission product isotopic analysis using dynamic reaction cell inductively coupled plasma mass spectrometry (DRC-ICP-MS)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Brown, Christopher F.; Dresel, P. Evan; Geiszler, Keith N.

2006-05-09

99Tc is a subsurface contaminant of interest at numerous federal, industrial, and international facilities. However, as a mono-isotopic fission product, 99Tc lacks the ability to be used as a signature to differentiate between the different waste disposal pathways that could have contributed to subsurface contamination at these facilities. Ruthenium fission-product isotopes are attractive analogues for the characterization of 99Tc sources because of their direct similarity to technetium with regard to subsurface mobility, and their large fission yields and low natural background concentrations. We developed an inductively coupled plasma mass spectrometry (ICP-MS) method capable of measuring ruthenium isotopes in groundwater samplesmore » and extracts of vadose zone sediments. Samples were analyzed directly on a Perkin Elmer ELAN DRC II ICP-MS after a single pass through a 1-ml bed volume of Dowex AG 50W-X8 100-200 mesh cation exchange resin. Precise ruthenium isotopic ratio measurements were achieved using a low-flow Meinhard-type nebulizer and long sample acquisition times (150,000 ms). Relative standard deviations of triplicate replicates were maintained at less than 0.5% when the total ruthenium solution concentration was 0.1 ng/ml or higher. Further work was performed to minimize the impact caused by mass interferences using the dynamic reaction cell (DRC) with O2 as the reaction gas. The aqueous concentrations of 96Mo and 96Zr were reduced by more than 99.7% in the reaction cell prior to injection of the sample into the mass analyzer quadrupole. The DRC was used in combination with stable-mass correction to quantitatively analyze samples containing up to 2-orders of magnitude more zirconium and molybdenum than ruthenium. The analytical approach documented herein provides an efficient and cost-effective way to precisely measure ruthenium isotopes and quantitate total ruthenium (natural vs. fission-product) in aqueous matrixes.« less

Study on volatilization mechanism of ruthenium tetroxide from nitrosyl ruthenium nitrate by using mass spectrometer

NASA Astrophysics Data System (ADS)

Kato, Tetsuya; Usami, Tsuyoshi; Tsukada, Takeshi; Shibata, Yuki; Kodama, Takashi

2016-10-01

In a cooling malfunction accident of a high-level liquid waste (HLLW) tank, behavior of ruthenium (Ru) attracts much attention, since Ru could be oxidized to a volatile chemical form in the boiling and drying of HLLW, and part of radioactive Ru can potentially be released to the environment. In this study, nitrosyl Ru nitrate (Ru(NO)(NO3)3) dissolved in nitric acid (HNO3), which is commonly contained in a simulated HLLW, was dried and heated up to 723 K, and the evolved gas was introduced into a mass spectrometer. The well-known volatile species, ruthenium tetroxide (RuO4) was detected in a temperature range between 390 K and 500 K with the peak top around 440 K. Various gases such as HNO3, nitrogen dioxide (NO2), nitrogen monoxide (NO) also evolved due to evaporation of the nitric acid and decomposition of the nitrate ions. The ion current of RuO4 seems to increase with the increasing decomposition of nitrate, while the evaporation of HNO3 decreases. More volatilization of RuO4 was observed from the HNO3 solution containing not only Ru(NO)(NO3)3 but also cerium nitrate (Ce(NO3)3·6H2O) which was added for extra supply of nitrate ion, compared with that from the HNO3 solution containing only Ru(NO)(NO3)3. These experimental results suggest that Ru could be oxidized to form RuO4 by the nitrate ion as well as HNO3.

COMPLEX RUTHENIUM ACIDO-NITROS COMPOUNDS (in Russian)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zvyagintsev, O.E.; Starostin, S.M.

1961-06-01

The chemical nature of the water in the complex ruthenium acidonitroso compounds is studied by measuring certain acid properties, reactions, and behaviors of the compounds in aqueous solution. The dependence of molecular electrical conductivity on time and dilution, variations of specific electroconductivity, the optical density, and the light absorption of the compounds at 200 to 800 m mu wave range were investigated and the dissociation constants were calculated. (R.V.J.)

Endoresection with adjuvant ruthenium brachytherapy for selected uveal melanoma patients - the Tuebingen experience.

PubMed

Süsskind, Daniela; Dürr, Carina; Paulsen, Frank; Kaulich, Theodor; Bartz-Schmidt, Karl U

2017-12-01

To evaluate the treatment of selected patients with uveal melanoma with endoresection and adjuvant ruthenium brachytherapy. Thirty-five patients with uveal melanoma not suitable for ruthenium plaque monotherapy were treated with endoresection and adjuvant ruthenium brachytherapy between January 2001 and October 2013. Recurrence-free survival, globe retention, course of visual acuity (VA), occurrence of therapy-related complications and metastasis-free and overall survival were analysed retrospectively. Eight patients (22.9%) had a tumour recurrence after a median follow-up of 49.5 months (range: 21-134 months). Enucleation was necessary in eight patients. Thirty-two patients (91%) had a loss of VA with a median loss of nine lines (range: 0 to -39 lines); VA was stable in three patients and no patients had a gain in VA. Four patients (11.4%) developed radiation retinopathy. Metastases were detected in seven patients (20.0%) during follow-up. The occurrence of metastasis was significantly associated with monosomy 3 (p < 0.0001). Twenty-four patients (68.6%) were alive at the end of follow-up. Five patients (14.3%) died because of uveal melanoma (UM) metastasis. Endoresection with adjuvant ruthenium brachytherapy is an option for selected patients with UM who cannot be treated with brachytherapy as monotherapy. About two-thirds of eyes can be retained long term without recurrences. Visual acuity cannot be maintained in most cases, and may even decrease considerably. Radiation complications are comparatively rare and not a significant problem. © 2016 Acta Ophthalmologica Scandinavica Foundation. Published by John Wiley & Sons Ltd.

Electrochemical Analysis of Conducting Polymer Thin Films

PubMed Central

Vyas, Ritesh N.; Wang, Bin

2010-01-01

Polyelectrolyte multilayers built via the layer-by-layer (LbL) method has been one of the most promising systems in the field of materials science. Layered structures can be constructed by the adsorption of various polyelectrolyte species onto the surface of a solid or liquid material by means of electrostatic interaction. The thickness of the adsorbed layers can be tuned precisely in the nanometer range. Stable, semiconducting thin films are interesting research subjects. We use a conducting polymer, poly(p-phenylene vinylene) (PPV), in the preparation of a stable thin film via the LbL method. Cyclic voltammetry and electrochemical impedance spectroscopy have been used to characterize the ionic conductivity of the PPV multilayer films. The ionic conductivity of the films has been found to be dependent on the polymerization temperature. The film conductivity can be fitted to a modified Randle’s circuit. The circuit equivalent calculations are performed to provide the diffusion coefficient values. PMID:20480052

Large-scale freestanding nanometer-thick graphite pellicles for mass production of nanodevices beyond 10 nm.

PubMed

Kim, Seul-Gi; Shin, Dong-Wook; Kim, Taesung; Kim, Sooyoung; Lee, Jung Hun; Lee, Chang Gu; Yang, Cheol-Woong; Lee, Sungjoo; Cho, Sang Jin; Jeon, Hwan Chul; Kim, Mun Ja; Kim, Byung-Gook; Yoo, Ji-Beom

2015-09-21

Extreme ultraviolet lithography (EUVL) has received much attention in the semiconductor industry as a promising candidate to extend dimensional scaling beyond 10 nm. We present a new pellicle material, nanometer-thick graphite film (NGF), which shows an extreme ultraviolet (EUV) transmission of 92% at a thickness of 18 nm. The maximum temperature induced by laser irradiation (λ = 800 nm) of 9.9 W cm(-2) was 267 °C, due to the high thermal conductivity of the NGF. The freestanding NGF was found to be chemically stable during annealing at 500 °C in a hydrogen environment. A 50 × 50 mm large area freestanding NGF was fabricated using the wet and dry transfer (WaDT) method. The NGF can be used as an EUVL pellicle for the mass production of nanodevices beyond 10 nm.

Narrow-band tunable terahertz emission from ferrimagnetic Mn{sub 3-x}Ga thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Awari, N.; University of Groningen, 9747 AG Groningen; Kovalev, S., E-mail: s.kovalev@hzdr.de, E-mail: c.fowley@hzdr.de, E-mail: rodek@tcd.ie

2016-07-18

Narrow-band terahertz emission from coherently excited spin precession in metallic ferrimagnetic Mn{sub 3-x}Ga Heusler alloy nanofilms has been observed. The efficiency of the emission, per nanometer film thickness, is comparable or higher than that of classical laser-driven terahertz sources based on optical rectification. The center frequency of the emission from the films can be tuned precisely via the film composition in the range of 0.20–0.35 THz, making this type of metallic film a candidate for efficient on-chip terahertz emitters. Terahertz emission spectroscopy is furthermore shown to be a sensitive probe of magnetic properties of ultra-thin films.

Structure-reactivity relationships in the hydrogenation of carbon dioxide with ruthenium complexes bearing pyridinylazolato ligands.

PubMed

Muller, Keven; Sun, Yu; Heimermann, Andreas; Menges, Fabian; Niedner-Schatteburg, Gereon; van Wüllen, Christoph; Thiel, Werner R

2013-06-10

Pyridinylazolato (N-N') ruthenium(II) complexes of the type [(N-N')RuCl(PMe3)3] have been obtained in high yields by treating the corresponding functionalised azolylpyridines with [RuCl2 (PMe3)4] in the presence of a base. (15)N NMR spectroscopy was used to elucidate the electronic influence of the substituents attached to the azolyl ring. The findings are in agreement with slight differences in the bond lengths of the ruthenium complexes. Furthermore, the electronic nature of the azolate moiety modulates the catalytic activity of the ruthenium complexes in the hydrogenation of carbon dioxide under supercritical conditions and in the transfer hydrogenation of acetophenone. DFT calculations were performed to shed light on the mechanism of the hydrogenation of carbon dioxide and to clarify the impact of the electronic nature of the pyridinylazolate ligands. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochromic Behavior of Ionically Self-Assembled Thin Films

NASA Astrophysics Data System (ADS)

Janik, J. A.; Heflin, J. R.; Marciu, D.; Miller, M. B.; Davis, R. M.

2001-03-01

Ionically self-assembled monolayers (ISAMs), fabricated by alternate adsorption of cationic and anionic components, yield exceptionally homogeneous thin films with sub-nanometer control of the thickness and relative special location of the component materials. Using organic electrochromic materials such as polyaniline, we report studies of electrochromic responses in ISAM films. Reversible changes in the absorption spectrum are observed with the application of voltages on the order of 1.0 V. Measurements are made using both liquid electrolytes and in all-solid state devices incorporating solid polyelectrolytes such as poly(2-acylamido 2-methyl propane sulfonic acid) (PAMPS).

C-H functionalization of phenols using combined ruthenium and photoredox catalysis: in situ generation of the oxidant.

PubMed

Fabry, David C; Ronge, Meria A; Zoller, Jochen; Rueping, Magnus

2015-02-23

A combination of ruthenium and photoredox catalysis allowed the ortho olefination of phenols. Using visible light, the direct C-H functionalization of o-(2-pyridyl)phenols occurred, and diverse phenol ethers were obtained in good yields. The regeneration of the ruthenium catalyst was accomplished by a photoredox-catalyzed oxidative process. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Flexible barrier film, method of forming same, and organic electronic device including same

DOEpatents

Blizzard, John; Tonge, James Steven; Weidner, William Kenneth

2013-03-26

A flexible barrier film has a thickness of from greater than zero to less than 5,000 nanometers and a water vapor transmission rate of no more than 1.times.10.sup.-2 g/m.sup.2/day at 22.degree. C. and 47% relative humidity. The flexible barrier film is formed from a composition, which comprises a multi-functional acrylate. The composition further comprises the reaction product of an alkoxy-functional organometallic compound and an alkoxy-functional organosilicon compound. A method of forming the flexible barrier film includes the steps of disposing the composition on a substrate and curing the composition to form the flexible barrier film. The flexible barrier film may be utilized in organic electronic devices.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cell Stacks

NASA Technical Reports Server (NTRS)

Valdez, Thomas I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

Dissolution of ruthenium was observed in the 80-cell stack. Duration testing was performed in single cell MEAs to determine the pathway of cell degradation. EDAX analysis on each of the single cell MEAs has shown that the Johnson Matthey commercial catalyst is stable in DMFC operation for 250 hours, no ruthenium dissolution was observed. Changes in the hydrophobicity of the cathode backing papers was minimum. Electrode polarization analysis revealed that the MEA performance loss is attributed to changes in the cathode catalyst layer. Ruthenium migration does not seem to occur during cell operation but can occur when methanol is absent from the anode compartment, the cathode compartment has access to air, and the cells in the stack are electrically connected to a load (Shunt Currents). The open-to-air cathode stack design allowed for: a) The MEAs to have continual access to oxygen; and b) The stack to sustain shunt currents. Ruthenium dissolution in a DMFC stack can be prevented by: a) Developing an internally manifolded stacks that seal reactant compartments when not in operation; b) Bringing the cell voltages to zero quickly when not in operation; and c) Limiting the total number of cells to 25 in an effort to limit shunt currents.

Probing the structural evolution of ruthenium doped germanium clusters: Photoelectron spectroscopy and density functional theory calculations

PubMed Central

Jin, Yuanyuan; Lu, Shengjie; Hermann, Andreas; Kuang, Xiaoyu; Zhang, Chuanzhao; Lu, Cheng; Xu, Hongguang; Zheng, Weijun

2016-01-01

We present a combined experimental and theoretical study of ruthenium doped germanium clusters, RuGen− (n = 3–12), and their corresponding neutral species. Photoelectron spectra of RuGen− clusters are measured at 266 nm. The vertical detachment energies (VDEs) and adiabatic detachment energies (ADEs) are obtained. Unbiased CALYPSO structure searches confirm the low-lying structures of anionic and neutral ruthenium doped germanium clusters in the size range of 3 ≤ n ≤ 12. Subsequent geometry optimizations using density functional theory (DFT) at PW91/LANL2DZ level are carried out to determine the relative stability and electronic properties of ruthenium doped germanium clusters. It is found that most of the anionic and neutral clusters have very similar global features. Although the global minimum structures of the anionic and neutral clusters are different, their respective geometries are observed as the low-lying isomers in either case. In addition, for n > 8, the Ru atom in RuGen−/0 clusters is absorbed endohedrally in the Ge cage. The theoretically predicted vertical and adiabatic detachment energies are in good agreement with the experimental measurements. The excellent agreement between DFT calculations and experiment enables a comprehensive evaluation of the geometrical and electronic structures of ruthenium doped germanium clusters. PMID:27439955

A facile one-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica: aqueous hydration of nitriles to amides.

PubMed

Baig, R B Nasir; Varma, Rajender S

2012-06-25

One-pot synthesis of ruthenium hydroxide nanoparticles on magnetic silica is described which involves the in situ generation of magnetic silica (Fe(3)O(4)@SiO(2)) and ruthenium hydroxide immobilization; the hydration of nitriles occurs in high yield and excellent selectivity using this catalyst which proceeds exclusively in aqueous medium under neutral conditions.

Carboxylate-assisted ruthenium-catalyzed alkyne annulations by C-H/Het-H bond functionalizations.

PubMed

Ackermann, Lutz

2014-02-18

To improve the atom- and step-economy of organic syntheses, researchers would like to capitalize upon the chemistry of otherwise inert carbon-hydrogen (C-H) bonds. During the past decade, remarkable progress in organometallic chemistry has set the stage for the development of increasingly viable metal catalysts for C-H bond activation reactions. Among these methods, oxidative C-H bond functionalizations are particularly attractive because they avoid the use of prefunctionalized starting materials. For example, oxidative annulations that involve sequential C-H and heteroatom-H bond cleavages allow for the modular assembly of regioselectively decorated heterocycles. These structures serve as key scaffolds for natural products, functional materials, crop protecting agents, and drugs. While other researchers have devised rhodium or palladium complexes for oxidative alkyne annulations, my laboratory has focused on the application of significantly less expensive, yet highly selective ruthenium complexes. This Account summarizes the evolution of versatile ruthenium(II) complexes for annulations of alkynes via C-H/N-H, C-H/O-H, or C-H/N-O bond cleavages. To achieve selective C-H bond functionalizations, we needed to understand the detailed mechanism of the crucial C-H bond metalation with ruthenium(II) complexes and particularly the importance of carboxylate assistance in this process. As a consequence, our recent efforts have resulted in widely applicable methods for the versatile preparation of differently decorated arenes and heteroarenes, providing access to among others isoquinolones, 2-pyridones, isoquinolines, indoles, pyrroles, or α-pyrones. Most of these reactions used Cu(OAc)2·H2O, which not only acted as the oxidant but also served as the essential source of acetate for the carboxylate-assisted ruthenation manifold. Notably, the ruthenium(II)-catalyzed oxidative annulations also occurred under an ambient atmosphere of air with cocatalytic amounts of Cu(OAc)2�

Programmable nanometer-scale electrolytic metal deposition and depletion

DOEpatents

Lee, James Weifu [Oak Ridge, TN; Greenbaum, Elias [Oak Ridge, TN

2002-09-10

A method of nanometer-scale deposition of a metal onto a nanostructure includes the steps of: providing a substrate having thereon at least two electrically conductive nanostructures spaced no more than about 50 .mu.m apart; and depositing metal on at least one of the nanostructures by electric field-directed, programmable, pulsed electrolytic metal deposition. Moreover, a method of nanometer-scale depletion of a metal from a nanostructure includes the steps of providing a substrate having thereon at least two electrically conductive nanostructures spaced no more than about 50 .mu.m apart, at least one of the nanostructures having a metal disposed thereon; and depleting at least a portion of the metal from the nanostructure by electric field-directed, programmable, pulsed electrolytic metal depletion. A bypass circuit enables ultra-finely controlled deposition.

Enhanced heat transfer is dependent on thickness of graphene films: the heat dissipation during boiling

PubMed Central

Ahn, Ho Seon; Kim, Jin Man; Kim, TaeJoo; Park, Su Cheong; Kim, Ji Min; Park, Youngjae; Yu, Dong In; Hwang, Kyoung Won; Jo, HangJin; Park, Hyun Sun; Kim, Hyungdae; Kim, Moo Hwan

2014-01-01

Boiling heat transfer (BHT) is a particularly efficient heat transport method because of the latent heat associated with the process. However, the efficiency of BHT decreases significantly with increasing wall temperature when the critical heat flux (CHF) is reached. Graphene has received much recent research attention for applications in thermal engineering due to its large thermal conductivity. In this study, graphene films of various thicknesses were deposited on a heated surface, and enhancements of BHT and CHF were investigated via pool-boiling experiments. In contrast to the well-known surface effects, including improved wettability and liquid spreading due to micron- and nanometer-scale structures, nanometer-scale folded edges of graphene films provided a clue of BHT improvement and only the thermal conductivity of the graphene layer could explain the dependence of the CHF on the thickness. The large thermal conductivity of the graphene films inhibited the formation of hot spots, thereby increasing the CHF. Finally, the provided empirical model could be suitable for prediction of CHF. PMID:25182076

Room temperature ferroelectricity in continuous croconic acid thin films

NASA Astrophysics Data System (ADS)

Jiang, Xuanyuan; Lu, Haidong; Yin, Yuewei; Zhang, Xiaozhe; Wang, Xiao; Yu, Le; Ahmadi, Zahra; Costa, Paulo S.; DiChiara, Anthony D.; Cheng, Xuemei; Gruverman, Alexei; Enders, Axel; Xu, Xiaoshan

2016-09-01

Ferroelectricity at room temperature has been demonstrated in nanometer-thin quasi 2D croconic acid thin films, by the polarization hysteresis loop measurements in macroscopic capacitor geometry, along with observation and manipulation of the nanoscale domain structure by piezoresponse force microscopy. The fabrication of continuous thin films of the hydrogen-bonded croconic acid was achieved by the suppression of the thermal decomposition using low evaporation temperatures in high vacuum, combined with growth conditions far from thermal equilibrium. For nominal coverages ≥20 nm, quasi 2D and polycrystalline films, with an average grain size of 50-100 nm and 3.5 nm roughness, can be obtained. Spontaneous ferroelectric domain structures of the thin films have been observed and appear to correlate with the grain patterns. The application of this solvent-free growth protocol may be a key to the development of flexible organic ferroelectric thin films for electronic applications.

Paradoxical Long-Timespan Opening of the Hole in Self-Supported Water Films of Nanometer Thickness.

PubMed

Barkay, Z; Bormashenko, E

2017-05-16

The opening of holes in self-supported thin (nanoscaled) water films has been investigated in situ with the environmental scanning electron microscope. The opening of a hole occurs within a two-stage process. In the first stage, the rim surrounding a hole is formed, resembling the process that is observed under the puncturing of soap bubbles. In the second stage, the exponential growth of the hole is observed, with a characteristic time of a dozen seconds. We explain the exponential kinetics of hole growth by the balance between inertia (gravity) and viscous dissipation. The kinetics of opening a microscaled hole is governed by the processes taking place in the nanothick bulk of the self-supported liquid film. Nanoparticles provide markers for the visualization of the processes occurring in self-supported thin nanoscale liquid films.

Arsenate Adsorption On Ruthenium Oxides: A Spectroscopic And Kinetic Investigation

EPA Science Inventory

Arsenate adsorption on amorphous (RuO₂•1.1H₂O) and crystalline (RuO₂) ruthenium oxides was evaluated using spectroscopic and kinetic methods to elucidate the adsorption mechanism. Extended X-ray absorption fine structure spectroscopy (EXAFS) was ...

In Vitro Effects of Novel Ruthenium Complexes in Neospora caninum and Toxoplasma gondii Tachyzoites

PubMed Central

Barna, Fabienne; Debache, Karim; Küster, Tatiana

2013-01-01

Upon the screening of 16 antiproliferative compounds against Toxoplasma gondii and Neospora caninum, two hydrolytically stable ruthenium complexes (compounds 16 and 18) exhibited 50% inhibitory concentrations of 18.7 and 41.1 nM (T. gondii) and 6.7 and 11.3 nM (N. caninum). To achieve parasiticidal activity with compound 16, long-term treatment (22 to 27 days at 80 to 160 nM) was required. Transmission electron microscopy demonstrated the rapid impact on and ultrastructural alterations in both parasites. These preliminary findings suggest that the potential of ruthenium-based compounds should thus be further exploited. PMID:23979747

Synthesis and Catalytic Activity of Ruthenium-Indenylidene Complexes for Olefin Metathesis: Microscale Experiments for the Undergraduate Inorganic or Organometallic Laboratories

ERIC Educational Resources Information Center

Pappenfus, Ted M.; Hermanson, David L.; Ekerholm, Daniel P.; Lilliquist, Stacie L.; Mekoli, Megan L.

2007-01-01

A series of experiments for undergraduate laboratory courses (e.g., inorganic, organometallic or advanced organic) have been developed. These experiments focus on understanding the design and catalytic activity of ruthenium-indenylidene complexes for olefin metathesis. Included in the experiments are the syntheses of two ruthenium-indenylidene…

Accounting for nanometer-thick adventitious carbon contamination in X-ray absorption spectra of carbon-based materials.

PubMed

Mangolini, Filippo; McClimon, J Brandon; Rose, Franck; Carpick, Robert W

2014-12-16

Near-edge X-ray absorption fine structure (NEXAFS) spectroscopy is a powerful technique for characterizing the composition and bonding state of nanoscale materials and the top few nanometers of bulk and thin film specimens. When coupled with imaging methods like photoemission electron microscopy, it enables chemical imaging of materials with nanometer-scale lateral spatial resolution. However, analysis of NEXAFS spectra is often performed under the assumption of structural and compositional homogeneity within the nanometer-scale depth probed by this technique. This assumption can introduce large errors when analyzing the vast majority of solid surfaces due to the presence of complex surface and near-surface structures such as oxides and contamination layers. An analytical methodology is presented for removing the contribution of these nanoscale overlayers from NEXAFS spectra of two-layered systems to provide a corrected photoabsorption spectrum of the substrate. This method relies on the subtraction of the NEXAFS spectrum of the overlayer adsorbed on a reference surface from the spectrum of the two-layer system under investigation, where the thickness of the overlayer is independently determined by X-ray photoelectron spectroscopy (XPS). This approach is applied to NEXAFS data acquired for one of the most challenging cases: air-exposed hard carbon-based materials with adventitious carbon contamination from ambient exposure. The contribution of the adventitious carbon was removed from the as-acquired spectra of ultrananocrystalline diamond (UNCD) and hydrogenated amorphous carbon (a-C:H) to determine the intrinsic photoabsorption NEXAFS spectra of these materials. The method alters the calculated fraction of sp(2)-hybridized carbon from 5 to 20% and reveals that the adventitious contamination can be described as a layer containing carbon and oxygen ([O]/[C] = 0.11 ± 0.02) with a thickness of 0.6 ± 0.2 nm and a fraction of sp(2)-bonded carbon of 0.19 ± 0.03. This

Synthesis science of SrRuO3 and CaRuO3 epitaxial films with high residual resistivity ratios

NASA Astrophysics Data System (ADS)

Nair, Hari P.; Liu, Yang; Ruf, Jacob P.; Schreiber, Nathaniel J.; Shang, Shun-Li; Baek, David J.; Goodge, Berit H.; Kourkoutis, Lena F.; Liu, Zi-Kui; Shen, Kyle M.; Schlom, Darrell G.

2018-04-01

Epitaxial SrRuO3 and CaRuO3 films were grown under an excess flux of elemental ruthenium in an adsorption-controlled regime by molecular-beam epitaxy (MBE), where the excess volatile RuOx (x = 2 or 3) desorbs from the growth front leaving behind a single-phase film. By growing in this regime, we were able to achieve SrRuO3 and CaRuO3 films with residual resistivity ratios (ρ300 K/ρ4 K) of 76 and 75, respectively. A combined phase stability diagram based on the thermodynamics of MBE (TOMBE) growth, termed a TOMBE diagram, is employed to provide improved guidance for the growth of complex materials by MBE.

In vitro and in vivo antiproliferative and trypanocidal activities of ruthenium NO donors

PubMed Central

Silva, J J N; Osakabe, A L; Pavanelli, W R; Silva, J S; Franco, D W

2007-01-01

Background and purpose: Many compounds liberating NO (NO donors) have been used as therapeutic agents. Here we test two ruthenium nitrosyls, which release NO when activated by biological reducing agents, for their effects in vitro and in vivo against Trypanasoma cruzi, the agent responsible for the American trypanosomiasis (Chagas' disease). Experimental approach: Ruthenium NO donors were incubated with a partially drug-resistant strain of T. cruzi and the anti-proliferative and trypanocidal activities evaluated. In a mouse model of acute Chagas' disease, trypanocidal activity was evaluated by measuring parasitemia, survival rate of infected mice and elimination of amastigotes in myocardial tissue. Key results: In vitro, the observed anti-proliferative and trypanocidal activities of trans-[Ru(NO)(NH3)4isn](BF4)3 and trans-[Ru(NO)(NH3)4imN](BF4)3 were due to NO liberated upon reduction of these nitrosyls. Ru(NO)isn had a lower IC50epi (67 μM) than the NO donor, sodium nitroprusside (IC50epi=244 μM) and Ru(NO)imN (IC50try=52 μM) was more potent than gentian violet (IC50try=536 μM), currently used in the treatment of blood. Both ruthenium nitrosyls eliminated, in vivo, extracellular as well as intracellular forms of T. cruzi in the bloodstream and myocardial tissue and allowed survival of up to 80% of infected mice at a dose (100 nmol kg−1 day−1) much lower than the optimal dose for benznidazole (385 μmol kg−1 day−1). Conclusions and implications: Our data strongly suggest that NO liberated is responsible for the anti-proliferative and trypanocidal activities of the ruthenium NO donors and that these compounds are promising leads for novel and effective anti-parasitic drugs. PMID:17603548

Spin waves in micro-structured yttrium iron garnet nanometer-thick films

DOE PAGES

Jungfleisch, Matthias B.; Zhang, Wei; Jiang, Wanjun; ...

2015-03-24

Here, we investigated the spin-wave propagation in a micro-structured yttrium iron garnet waveguide of 40 nm thickness. Utilizing spatially-resolved Brillouin light scattering microscopy, an exponential decay of the spinwave amplitude of 10 μm was observed. This leads to an estimated Gilbert damping constant of α = (8.79 ± 0.73) x 10 $-$4, which is larger than damping values obtained through ferromagnetic resonance measurements in unstructured films. Furthermore, we compared the theoretically calculated spatial interference of waveguide modes to the spin-wave pattern observed experimentally by means of Brillouin light scattering spectroscopy.

Analysis on ultrashort-pulse laser ablation for nanoscale film of ceramics

NASA Astrophysics Data System (ADS)

Ho, C. Y.; Tsai, Y. H.; Chiou, Y. J.

2017-06-01

This paper uses the dual-phase-lag model to study the ablation characteristics of femtosecond laser processing for nanometer-sized ceramic films. In ultrafast process and ultrasmall size where the two lags occur, a dual-phase-lag can be applied to analyse the ablation characteristics of femtosecond laser processing for materials. In this work, the ablation rates of nanometer-sized lead zirconate titanate (PZT) ceramics are investigated using a dual-phase-lag and the model is solved by Laplace transform method. The results obtained from this work are validated by the available experimental data. The effects of material thermal properties on the ablation characteristics of femtosecond laser processing for ceramics are also discussed.

Development of a direct patterning method for functional oxide thin films using ultraviolet irradiation and hybrid-cluster gels and its application to thin-film transistor fabrication

NASA Astrophysics Data System (ADS)

Yoshimoto, Yuuki; Li, Jinwang; Shimoda, Tatsuya

2018-04-01

A gel state exists in the solution-solid conversion process. We found that solidification can be promoted by irradiating the gel with ultraviolet (UV) light. In this study, a patterning method without using a vacuum system or employing photoresist materials has been proposed wherein solidification was applied to a gel by UV irradiation. Indium oxide gel, indium gallium oxide gel, lanthanum zirconium oxide gel, and lanthanum ruthenium oxide gels were successfully patterned by using our technique. Moreover, an oxide thin-film transistor was fabricated by our novel patterning method and was successfully operated.

Ruthenium-catalyzed regioselective allylic amination of 2,3,3-trifluoroallylic carbonates.

PubMed

Isobe, Shin-Ichi; Terasaki, Shou; Hanakawa, Taisyun; Mizuno, Shota; Kawatsura, Motoi

2017-04-05

We demonstrated the ruthenium-catalyzed allylic amination of 2,3,3-trifluoroallylic carbonates with several types of amines. The reactions proceeded with several types of amines, and succeeded in obtaining polyfluorinated terminal alkenes possessing branched allylic amines as a single regioisomer.

Design and fabrication of self-assembled thin films

NASA Astrophysics Data System (ADS)

Topasna, Daniela M.; Topasna, Gregory A.

2015-10-01

Students experience the entire process of designing, fabricating and testing thin films during their capstone course. The films are fabricated by the ionic-self assembled monolayer (ISAM) technique, which is suited to a short class and is relatively rapid, inexpensive and environmentally friendly. The materials used are polymers, nanoparticles, and small organic molecules that, in various combinations, can create films with nanometer thickness and with specific properties. These films have various potential applications such as pH optical sensors or antibacterial coatings. This type of project offers students an opportunity to go beyond the standard lecture and labs and to experience firsthand the design and fabrication processes. They learn new techniques and procedures, as well as familiarize themselves with new instruments and optical equipment. For example, students learn how to characterize the films by using UV-Vis-NIR spectrophotometry and in the process learn how the instruments operate. This work compliments a previous exercise that we introduced where students use MATHCAD to numerically model the transmission and reflection of light from thin films.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Preparation of olefins from synthesis gas using ruthenium supported on ceric oxide

DOEpatents

Pierantozzi, R.

1985-04-09

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ceria-supported ruthenium nanoparticles as highly active and long-lived catalysts in hydrogen generation from the hydrolysis of ammonia borane.

PubMed

Akbayrak, Serdar; Tonbul, Yalçın; Özkar, Saim

2016-07-05

Ruthenium(0) nanoparticles supported on ceria (Ru(0)/CeO2) were in situ generated from the reduction of ruthenium(iii) ions impregnated on ceria during the hydrolysis of ammonia borane. Ru(0)/CeO2 was isolated from the reaction solution by centrifugation and characterized by ICP-OES, BET, XRD, TEM, SEM-EDS and XPS techniques. All the results reveal that ruthenium(0) nanoparticles were successfully supported on ceria and the resulting Ru(0)/CeO2 is a highly active, reusable and long-lived catalyst for hydrogen generation from the hydrolysis of ammonia borane with a turnover frequency value of 361 min(-1). The reusability tests reveal that Ru(0)/CeO2 is still active in the subsequent runs of hydrolysis of ammonia borane preserving 60% of the initial catalytic activity even after the fifth run. Ru(0)/CeO2 provides a superior catalytic lifetime (TTO = 135 100) in hydrogen generation from the hydrolysis of ammonia borane at 25.0 ± 0.1 °C before deactivation. The work reported here includes the formation kinetics of ruthenium(0) nanoparticles. The rate constants for the slow nucleation and autocatalytic surface growth of ruthenium(0) nanoparticles were obtained using hydrogen evolution as a reporter reaction. An evaluation of rate constants at various temperatures enabled the estimation of activation energies for both the reactions, Ea = 60 ± 7 kJ mol(-1) for the nucleation and Ea = 47 ± 2 kJ mol(-1) for the autocatalytic surface growth of ruthenium(0) nanoparticles, as well as the activation energy of Ea = 51 ± 2 kJ mol(-1) for the catalytic hydrolysis of ammonia borane.

The study of voids in the AuAl thin-film system using the nuclear microprobe

NASA Astrophysics Data System (ADS)

de Waal, H. S.; Pretorius, R.; Prozesky, V. M.; Churms, C. L.

1997-07-01

A Nuclear Microprobe (NMP) was used to study void formation in thin film gold-aluminium systems. Microprobe Rutherford Backscattering Spectrometry (μRBS) was utilised to effectively obtain a three-dimensional picture of the void structure on the scale of a few nanometers in the depth dimension and a few microns in the in-plane dimension. This study illustrates the usefulness of the NMP in the study of materials and specifically thin-film structures.

Role of Mediator and Effects of Temperature on ortho-C-N Bond Fusion Reactions of Aniline Using Ruthenium Templates: Isolation and Characterization of New Ruthenium Complexes of the in-Situ-Generated Ligands.

PubMed

Roy, Suman K; Sengupta, Debabrata; Rath, Santi Prasad; Saha, Tanushri; Samanta, Subhas; Goswami, Sreebrata

2017-05-01

In this work, ortho-C-N bond fusion reactions of aniline are followed by the use of two different ruthenium mediators. Reaction of aniline with [Ru III (terpy)Cl 3 ] (terpy = 2,2':6',2″-terpyridine) resulted in a trans bis-aniline ruthenium(II) complex [1] + which upon oxidation with H 2 O 2 produced compound [2] + of a bidentate ligand, N-phenyl-1,2-benzoquinonediimine, due to an oxidative ortho-C-N bond fusion reaction. Complex [1] + and aniline (neat) at 185 °C produced a bis-chelated ruthenium complex (3). A previously reported complex [Ru II (N-phenyl-1,2-benzoquinonediimine)(aniline) 2 (Cl) 2 ] (5) undergoes similar oxidation by air at 185 °C to produce complex [3]. A separate chemical reaction between aniline and strongly oxidizing tetra-n-propylammonium perruthenate [(n-pr) 4 N] + [RuO 4 ] - in air produced a ruthenium complex [4] of a N 4 -tetraamidophenylmacrocycle ligand via multiple ortho-C-N bond fusion reaction. Notably, the yield of this product is low (5%) at 100 °C but increases to 25% in refluxing aniline. All these complexes are characterized fully by their physicochemical characterizations and X-ray structure determination. From their structural parameters and other spectroscopic studies, complex [2] + is assigned as [Ru II (terpy)(N-phenyl-1,2-benzoquinonediimine)(Cl)] + whereas complex [4] is described as a ruthenium(VI) complex comprised of a reduced deprotonated N-phenyl-1,2-diamidobenzene and N 4 -tetraamidophenylmacrocyclic ligand. Complex [2] + exhibits one reversible oxidation at 1.32 V and one reversible reduction at -0.75 V vs Ag/AgCl reference electrode. EPR of the electrogenerated complexes has revealed that the oxidized complex is a ruthenium(III) complex with an axial EPR spectrum at g av = 2.06. The reduced complex [2], on the other hand, shows a single-line EPR signal at g av = 1.998. In contrast, complex [4] shows two successive one-electron oxidation waves at 0.5 and 0.8 V and an irreversible reduction wave at -0.9 V. EPR

Tracking the Oxygen Status in the Cell Nucleus with a Hoechst-Tagged Phosphorescent Ruthenium Complex.

PubMed

Hara, Daiki; Umehara, Yui; Son, Aoi; Asahi, Wataru; Misu, Sotaro; Kurihara, Ryohsuke; Kondo, Teruyuki; Tanabe, Kazuhito

2018-05-04

Molecular oxygen in living cells is distributed and consumed inhomogeneously, depending on the activity of each organelle. Therefore, tractable methods that can be used to monitor the oxygen status in each organelle are needed to understand cellular function. Here we report the design of a new oxygen-sensing probe for use in the cell nucleus. We prepared "Ru-Hoechsts", each consisting of a phosphorescent ruthenium complex linked to a Hoechst 33258 moiety, and characterized their properties as oxygen sensors. The Hoechst unit shows strong DNA-binding properties in the nucleus, and the ruthenium complex shows oxygen-dependent phosphorescence. Thus, Ru-Hoechsts accumulated in the cell nucleus and showed oxygen-dependent signals that could be monitored. Of the Ru-Hoechsts prepared in this study, Ru-Hoechst b, in which the ruthenium complex and the Hoechst unit were linked through a hexyl chain, showed the most suitable properties for monitoring the oxygen status. Ru-Hoechsts are probes with high potential for visualizing oxygen fluctuations in the nucleus. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

PRECIPITATION OF ZIRCONIUM, NIOBIUM, AND RUTHENIUM FROM AQUEOUS SOLUTIONS

DOEpatents

Wilson, A.S.

1958-08-12

An improvement on the"head end process" for decontaminating dissolver solutions of their Zr, Ni. and Ru values. The process consists in adding a water soluble symmetrical dialkyl ketone. e.g. acetone, before the formation of the manganese dioxide precipitate. The effect is that upon digestion, the ruthenium oxide does not volatilize, but is carried on the manganese dioxide precipitate.

Electrospraying and ultraviolet light curing of nanometer-thin polydimethylsiloxane membranes for low-voltage dielectric elastomer transducers

NASA Astrophysics Data System (ADS)

Osmani, Bekim; Töpper, Tino; Siketanc, Matej; Kovacs, Gabor M.; Müller, Bert

2017-04-01

Dielectric elastomer transducers (DETs) have attracted interest as actuators, sensors, and even as self-sensing actuators for applications in medicine, soft robotics, and microfluidics. To reach strains of more than 10 %, they currently require operating voltages of several hundred volts. In medical applications for artificial muscles, however, their operation is limited to a very few tens of volts, which implies high permittivity materials and thin-film structures. Such micro- or nanostructures can be prepared using electro-spraying, a cost-effective technique that allows upscaling using multiple nozzles for the fabrication of silicone films down to nanometer thickness. Deposition rates of several micrometers per hour have already been reached. It has been recently demonstrated that such membranes can be fabricated by electro-spraying and subsequent ultraviolet light irradiation. Herein, we introduce a relatively fast deposition of a dimethyl silicone copolymer fluid that contains mercaptopropyl side chains in addition to the methyl groups. Its elastic modulus was tuned with the irradiation dose of the 200 W Hg-Xe lamp. We also investigated the formation of elastomer films, using polymer concentrations in ethyl acetate of 1, 2, 5 and 10 vol%. After curing, the surface roughness was measured by means of atomic force microscopy. This instrument also enabled us to determine the average elastic modulus out of, for example, 400 nanoindentation measurements, using a spherical tip with a radius of 500 nm. The elastomer films were cured for a period of less than one minute, a speed that makes it feasible to combine electro-spraying and in situ curing in a single process step for fabricating low-voltage, multilayer DETs.

Room temperature ferroelectricity in continuous croconic acid thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiang, Xuanyuan; Lu, Haidong; Yin, Yuewei

2016-09-05

Ferroelectricity at room temperature has been demonstrated in nanometer-thin quasi 2D croconic acid thin films, by the polarization hysteresis loop measurements in macroscopic capacitor geometry, along with observation and manipulation of the nanoscale domain structure by piezoresponse force microscopy. The fabrication of continuous thin films of the hydrogen-bonded croconic acid was achieved by the suppression of the thermal decomposition using low evaporation temperatures in high vacuum, combined with growth conditions far from thermal equilibrium. For nominal coverages ≥20 nm, quasi 2D and polycrystalline films, with an average grain size of 50–100 nm and 3.5 nm roughness, can be obtained. Spontaneous ferroelectric domain structuresmore » of the thin films have been observed and appear to correlate with the grain patterns. The application of this solvent-free growth protocol may be a key to the development of flexible organic ferroelectric thin films for electronic applications.« less

Fundamental Factors Impacting the Stability of Phosphonate-Derivatized Ruthenium Polypyridyl Sensitizers Adsorbed on Metal Oxide Surfaces.

PubMed

Raber, McKenzie; Brady, Matthew David; Troian-Gautier, Ludovic; Dickenson, John; Marquard, Seth L; Hyde, Jacob; Lopez, Santiago; Meyer, Gerald J; Meyer, Thomas J; Harrison, Daniel P

2018-06-08

A series of 18 ruthenium(II) polypyridyl complexes were synthesized and evaluated under electrochemically oxidative conditions, which generates the Ru(III) oxidation state and mimics the harsh conditions experienced during the kinetically-limited regime that can occur in dye-sensitized solar cells (DSSCs) and dye-sensitized photoelectrosynthesis cells (DSPECs), to further develop fundamental insights into the factors governing molecular sensitizer surface stability in aqueous 0.1 M HClO4 (aq). Both desorption and oxidatively induced ligand substitution were observed on planar fluorine doped tin oxide, FTO, electrodes, with a dependence on the E1/2 Ru(III/II) redox potential dictating the comparative ratios of the processes. Complexes such as RuP4OMe (E1/2 = 0.91 vs Ag/AgCl) displayed virtually only desorption, while complexes such as RuPbpz (E1/2 > 1.62 V vs Ag/AgCl) displayed only chemical decomposition. Comparing isomers of 4,4'- and 5,5-disubstituted-2,2'-bipyridine ancillary polypyridyl ligands, a dramatic increase in the rate of desorption of the Ru(III) complexes was observed for the 5,5'-ligands. Nanoscopic indium doped tin oxide thin films, nanoITO, were also sensitized and analyzed with cyclic voltammetry, UV-Vis absorption spectroscopy, and XPS, allowing for further distinction of desorption versus ligand substitution processes. Desorption loss to bulk solution associated with the planar surface of FTO is essentially non-existent on nanoITO, where both desorption and ligand substitution are shut down with RuP4OMe. These results revealed that minimizing time spent in the oxidized form, incorporating electron donating groups, maximizing hydrophobicity, and minimizing molecular bulk near the adsorbed ligand are critical to optimizing the performance of ruthenium(II) polypyridyl complexes in dye-sensitized solar cell devices.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Corbea, Javier Jesus Concepcion; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L.; Hoertz, Paul; Meyer, Thomas J.

2013-09-03

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Ruthenium or osmium complexes and their uses as catalysts for water oxidation

DOEpatents

Concepcion Corbea, Javier Jesus; Chen, Zuofeng; Jurss, Jonah Wesley; Templeton, Joseph L; Hoertz, Paul; Meyer, Thomas J

2014-10-28

The present invention provides ruthenium or osmium complexes and their uses as a catalyst for catalytic water oxidation. Another aspect of the invention provides an electrode and photo-electrochemical cells for electrolysis of water molecules.

Antiproliferative effects of ruthenium-based nucleolipidic nanoaggregates in human models of breast cancer in vitro: insights into their mode of action

PubMed Central

Irace, Carlo; Misso, Gabriella; Capuozzo, Antonella; Piccolo, Marialuisa; Riccardi, Claudia; Luchini, Alessandra; Caraglia, Michele; Paduano, Luigi; Montesarchio, Daniela; Santamaria, Rita

2017-01-01

Looking for new metal-based anticancer treatments, in recent years many ruthenium complexes have been proposed as effective and safe potential drugs. In this context we have recently developed a novel approach for the in vivo delivery of Ru(III) complexes, preparing stable ruthenium-based nucleolipidic nanoaggregates endowed with significant antiproliferative activity. Herein we describe the cellular response to our ruthenium-containing formulations in selected models of human breast cancer. By in vitro bioscreens in the context of preclinical studies, we have focused on their ability to inhibit breast cancer cell proliferation by the activation of the intrinsic apoptotic pathway, possibly via mitochondrial perturbations involving Bcl-2 family members and predisposing to programmed cell death. In addition, the most efficient ruthenium-containing cationic nanoaggregates we have hitherto developed are able to elicit both extrinsic and intrinsic apoptosis, as well as autophagy. To limit chemoresistance and counteract uncontrolled proliferation, multiple cell death pathways activation by metal-based chemotherapeutics is a challenging, yet very promising strategy for targeted therapy development in aggressive cancer diseases, such as triple-negative breast cancer with limited treatment options. These outcomes provide valuable, original knowledge on ruthenium-based candidate drugs and new insights for future optimized cancer treatment protocols. PMID:28349991

Formation of polycyclic lactones through a ruthenium-catalyzed ring-closing metathesis/hetero-Pauson-Khand reaction sequence.

PubMed

Finnegan, David F; Snapper, Marc L

2011-05-20

Processes that form multiple carbon-carbon bonds in one operation can generate molecular complexity quickly and therefore be used to shorten syntheses of desirable molecules. We selected the hetero-Pauson-Khand (HPK) cycloaddition and ring-closing metathesis (RCM) as two unique carbon-carbon bond-forming reactions that could be united in a tandem ruthenium-catalyzed process. In doing so, complex polycyclic products can be obtained in one reaction vessel from acyclic precursors using a single ruthenium additive that can catalyze sequentially two mechanistically distinct transformations.

Infrared characteristics of VO2 thin films for smart window and laser protection applications

NASA Astrophysics Data System (ADS)

Huang, Zhangli; Chen, Sihai; Lv, Chaohong; Huang, Ying; Lai, Jianjun

2012-11-01

Vanadium dioxide (VO2) films with a low semiconductor-to-metal transition temperature of 45 °C were fabricated through direct current magnetron sputtering followed by a post-annealing. Atomic force microscopy measurements show that the VO2 grain size is about one hundred of nanometers. Infrared (IR) characteristic is well investigated by applying a He-Ne laser power intensity measurement, and the result reveals that the VO2 film exhibits excellent IR switching property. Furthermore, solar smart window and laser protection experiments demonstrate that the obtained VO2 thin film is a promising material for the application in related fields.

Engineering polyelectrolyte multilayer structure at the nanometer length scale by tuning polymer solution conformation.

NASA Astrophysics Data System (ADS)

Boddohi, Soheil; Killingsworth, Christopher; Kipper, Matt

2008-03-01

Chitosan (a weak polycation) and heparin (a strong polyanion) are used to make polyelectrolyte multilayers (PEM). PEM thickness and composition are determined as a function of solution pH (4.6 to 5.8) and ionic strength (0.1 to 0.5 M). Over this range, increasing pH increases the PEM thickness; however, the sensitivity to changes in pH is a strong function of ionic strength. The PEM thickness data are correlated to the polymer conformation in solution. Polyelectrolyte conformation in solution is characterized by gel permeation chromatography (GPC). The highest sensitivity of PEM structure to pH is obtained at intermediate ionic strength. Different interactions govern the conformation and adsorption phenomena at low and high ionic strength, leading to reduced sensitivity to solution pH at extreme ionic strengths. The correspondence between PEM thickness and polymer solution conformation offers opportunities to tune polymer thin film structure at the nanometer length scale by controlling simple, reproducible processing conditions.

Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

NASA Astrophysics Data System (ADS)

Su, Jianwei; Yang, Yang; Xia, Guoliang; Chen, Jitang; Jiang, Peng; Chen, Qianwang

2017-04-01

The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm-2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon-hydrogen bond, thereby lowing ΔGH* of HER.

Selective catalytic reduction system and process for treating NOx emissions using a palladium and rhodium or ruthenium catalyst

DOEpatents

Sobolevskiy, Anatoly [Orlando, FL; Rossin, Joseph A [Columbus, OH; Knapke, Michael J [Columbus, OH

2011-07-12

A process for the catalytic reduction of nitrogen oxides (NOx) in a gas stream (29) in the presence of H.sub.2 is provided. The process comprises contacting the gas stream with a catalyst system (38) comprising zirconia-silica washcoat particles (41), a pre-sulfated zirconia binder (44), and a catalyst combination (40) comprising palladium and at least one of rhodium, ruthenium, or a mixture of ruthenium and rhodium.

Electronic-Reconstruction-Enhanced Tunneling Conductance at Terrace Edges of Ultrathin Oxide Films.

PubMed

Wang, Lingfei; Kim, Rokyeon; Kim, Yoonkoo; Kim, Choong H; Hwang, Sangwoon; Cho, Myung Rae; Shin, Yeong Jae; Das, Saikat; Kim, Jeong Rae; Kalinin, Sergei V; Kim, Miyoung; Yang, Sang Mo; Noh, Tae Won

2017-11-01

Quantum mechanical tunneling of electrons across ultrathin insulating oxide barriers has been studied extensively for decades due to its great potential in electronic-device applications. In the few-nanometers-thick epitaxial oxide films, atomic-scale structural imperfections, such as the ubiquitously existed one-unit-cell-high terrace edges, can dramatically affect the tunneling probability and device performance. However, the underlying physics has not been investigated adequately. Here, taking ultrathin BaTiO 3 films as a model system, an intrinsic tunneling-conductance enhancement is reported near the terrace edges. Scanning-probe-microscopy results demonstrate the existence of highly conductive regions (tens of nanometers wide) near the terrace edges. First-principles calculations suggest that the terrace-edge geometry can trigger an electronic reconstruction, which reduces the effective tunneling barrier width locally. Furthermore, such tunneling-conductance enhancement can be discovered in other transition metal oxides and controlled by surface-termination engineering. The controllable electronic reconstruction can facilitate the implementation of oxide electronic devices and discovery of exotic low-dimensional quantum phases. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Epitaxial Growth of GaN Films by Pulse-Mode Hot-Mesh Chemical Vapor Deposition

NASA Astrophysics Data System (ADS)

Komae, Yasuaki; Yasui, Kanji; Suemitsu, Maki; Endoh, Tetsuo; Ito, Takashi; Nakazawa, Hideki; Narita, Yuzuru; Takata, Masasuke; Akahane, Tadashi

2009-07-01

Intermittent gas supplies for hot-mesh chemical vapor deposition (CVD) for the epitaxial growth of gallium nitride (GaN) films were investigated to improve film crystallinity and optical properties. The GaN films were deposited on SiC/Si(111) substrates using an alternating-source gas supply or an intermittent supply of source gases such as ammonia (NH3) and trimethylgallium (TMG) in hot-mesh CVD after deposition of an aluminum nitride (AlN) buffer layer. The AlN layer was deposited using NH3 and trimethylaluminum (TMA) on a SiC layer grown by carbonization of a Si substrate using propane (C3H8). GaN films were grown on the AlN layer by a reaction between NHx radicals generated on a ruthenium (Ru)-coated tungsten (W) mesh and TMG molecules. After testing various gas supply modes, GaN films with good crystallinity and surface morphology were obtained using an intermittent supply of TMG and a continuous supply of NH3 gas. An optimal interval for the TMG gas supply was also obtained for the apparatus employed.

Subtractive fabrication of ferroelectric thin films with precisely controlled thickness

NASA Astrophysics Data System (ADS)

Ievlev, Anton V.; Chyasnavichyus, Marius; Leonard, Donovan N.; Agar, Joshua C.; Velarde, Gabriel A.; Martin, Lane W.; Kalinin, Sergei V.; Maksymovych, Petro; Ovchinnikova, Olga S.

2018-04-01

The ability to control thin-film growth has led to advances in our understanding of fundamental physics as well as to the emergence of novel technologies. However, common thin-film growth techniques introduce a number of limitations related to the concentration of defects on film interfaces and surfaces that limit the scope of systems that can be produced and studied experimentally. Here, we developed an ion-beam based subtractive fabrication process that enables creation and modification of thin films with pre-defined thicknesses. To accomplish this we transformed a multimodal imaging platform that combines time-of-flight secondary ion mass spectrometry with atomic force microscopy to a unique fabrication tool that allows for precise sputtering of the nanometer-thin layers of material. To demonstrate fabrication of thin-films with in situ feedback and control on film thickness and functionality we systematically studied thickness dependence of ferroelectric switching of lead-zirconate-titanate, within a single epitaxial film. Our results demonstrate that through a subtractive film fabrication process we can control the piezoelectric response as a function of film thickness as well as improve on the overall piezoelectric response versus an untreated film.

Subtractive fabrication of ferroelectric thin films with precisely controlled thickness

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ievlev, Anton; Chyasnavichyus, Marius; Leonard, Donovan N.

The ability to control thin-film growth has led to advances in our understanding of fundamental physics as well as to the emergence of novel technologies. However, common thin-film growth techniques introduce a number of limitations related to the concentration of defects on film interfaces and surfaces that limit the scope of systems that can be produced and studied experimentally. Here, we developed an ion-beam based subtractive fabrication process that enables creation and modification of thin films with pre-defined thicknesses. To accomplish this we transformed a multimodal imaging platform that combines time-of-flight secondary ion mass spectrometry with atomic force microscopy tomore » a unique fabrication tool that allows for precise sputtering of the nanometer-thin layers of material. To demonstrate fabrication of thin-films with in situ feedback and control on film thickness and functionality we systematically studied thickness dependence of ferroelectric switching of lead-zirconate-titanate, within a single epitaxial film. Lastly, our results demonstrate that through a subtractive film fabrication process we can control the piezoelectric response as a function of film thickness as well as improve on the overall piezoelectric response versus an untreated film.« less

Subtractive fabrication of ferroelectric thin films with precisely controlled thickness

DOE PAGES

Ievlev, Anton; Chyasnavichyus, Marius; Leonard, Donovan N.; ...

2018-02-22

The ability to control thin-film growth has led to advances in our understanding of fundamental physics as well as to the emergence of novel technologies. However, common thin-film growth techniques introduce a number of limitations related to the concentration of defects on film interfaces and surfaces that limit the scope of systems that can be produced and studied experimentally. Here, we developed an ion-beam based subtractive fabrication process that enables creation and modification of thin films with pre-defined thicknesses. To accomplish this we transformed a multimodal imaging platform that combines time-of-flight secondary ion mass spectrometry with atomic force microscopy tomore » a unique fabrication tool that allows for precise sputtering of the nanometer-thin layers of material. To demonstrate fabrication of thin-films with in situ feedback and control on film thickness and functionality we systematically studied thickness dependence of ferroelectric switching of lead-zirconate-titanate, within a single epitaxial film. Lastly, our results demonstrate that through a subtractive film fabrication process we can control the piezoelectric response as a function of film thickness as well as improve on the overall piezoelectric response versus an untreated film.« less

Subtractive fabrication of ferroelectric thin films with precisely controlled thickness.

PubMed

Ievlev, Anton V; Chyasnavichyus, Marius; Leonard, Donovan N; Agar, Joshua C; Velarde, Gabriel A; Martin, Lane W; Kalinin, Sergei V; Maksymovych, Petro; Ovchinnikova, Olga S

2018-04-02

The ability to control thin-film growth has led to advances in our understanding of fundamental physics as well as to the emergence of novel technologies. However, common thin-film growth techniques introduce a number of limitations related to the concentration of defects on film interfaces and surfaces that limit the scope of systems that can be produced and studied experimentally. Here, we developed an ion-beam based subtractive fabrication process that enables creation and modification of thin films with pre-defined thicknesses. To accomplish this we transformed a multimodal imaging platform that combines time-of-flight secondary ion mass spectrometry with atomic force microscopy to a unique fabrication tool that allows for precise sputtering of the nanometer-thin layers of material. To demonstrate fabrication of thin-films with in situ feedback and control on film thickness and functionality we systematically studied thickness dependence of ferroelectric switching of lead-zirconate-titanate, within a single epitaxial film. Our results demonstrate that through a subtractive film fabrication process we can control the piezoelectric response as a function of film thickness as well as improve on the overall piezoelectric response versus an untreated film.

Complex biomembrane mimetics on the sub-nanometer scale

DOE PAGES

Heberle, Frederick A.; Pabst, Georg

2017-07-17

Biomimetic lipid vesicles are indispensable tools for gaining insight into the biophysics of cell physiology on the molecular level. The level of complexity of these model systems has steadily increased, and now spans from domain forming lipid mixtures to asymmetric lipid bilayers. We review recent progress in the development and application of elastic neutron and X-ray scattering techniques for studying these systems in situ and under physiologically relevant conditions on the nanometer to sub-nanometer length scales. Particularly we focus on: (i) structural details of coexisting liquid-ordered and liquid-disordered domains, including their thickness and lipid packing mismatch as a function ofmore » a size transition from nanoscopic to macroscopic domains; (ii) membrane-mediated protein partitioning into lipid domains; (iii) the role of the aqueous medium in tuning interactions between membranes and domains; and (iv) leaflet specific structure in asymmetric bilayers and passive lipid flip-flop.« less

Complex biomembrane mimetics on the sub-nanometer scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Heberle, Frederick A.; Pabst, Georg

Biomimetic lipid vesicles are indispensable tools for gaining insight into the biophysics of cell physiology on the molecular level. The level of complexity of these model systems has steadily increased, and now spans from domain forming lipid mixtures to asymmetric lipid bilayers. We review recent progress in the development and application of elastic neutron and X-ray scattering techniques for studying these systems in situ and under physiologically relevant conditions on the nanometer to sub-nanometer length scales. Particularly we focus on: (i) structural details of coexisting liquid-ordered and liquid-disordered domains, including their thickness and lipid packing mismatch as a function ofmore » a size transition from nanoscopic to macroscopic domains; (ii) membrane-mediated protein partitioning into lipid domains; (iii) the role of the aqueous medium in tuning interactions between membranes and domains; and (iv) leaflet specific structure in asymmetric bilayers and passive lipid flip-flop.« less

Substrate comprising a nanometer-scale projection array

DOEpatents

Cui, Yi; Zhu, Jia; Hsu, Ching-Mei; Connor, Stephen T; Yu, Zongfu; Fan, Shanhui; Burkhard, George

2012-11-27

A method for forming a substrate comprising nanometer-scale pillars or cones that project from the surface of the substrate is disclosed. The method enables control over physical characteristics of the projections including diameter, sidewall angle, and tip shape. The method further enables control over the arrangement of the projections including characteristics such as center-to-center spacing and separation distance.

Characterization of ultraviolet light cured polydimethylsiloxane films for low-voltage, dielectric elastomer actuators

NASA Astrophysics Data System (ADS)

Töpper, Tino; Wohlfender, Fabian; Weiss, Florian; Osmani, Bekim; Müller, Bert

2016-04-01

The reduction the operation voltage has been the key challenge to realize of dielectric elastomer actuators (DEA) for many years - especially for the application fields of robotics, lens systems, haptics and future medical implants. Contrary to the approach of manipulating the dielectric properties of the electrically activated polymer (EAP), we intend to realize low-voltage operation by reducing the polymer thickness to the range of a few hundred nanometers. A study recently published presents molecular beam deposition to reliably grow nanometer-thick polydimethylsiloxane (PDMS) films. The curing of PDMS is realized using ultraviolet (UV) radiation with wavelengths from 180 to 400 nm radicalizing the functional side and end groups. The understanding of the mechanical properties of sub-micrometer-thin PDMS films is crucial to optimize DEAs actuation efficiency. The elastic modulus of UV-cured spin-coated films is measured by nano-indentation using an atomic force microscope (AFM) according to the Hertzian contact mechanics model. These investigations show a reduced elastic modulus with increased indentation depth. A model with a skin-like SiO2 surface with corresponding elastic modulus of (2.29 +/- 0.31) MPa and a bulk modulus of cross-linked PDMS with corresponding elastic modulus of (87 +/- 7) kPa is proposed. The surface morphology is observed with AFM and 3D laser microscopy. Wrinkled surface microstructures on UV-cured PDMS films occur for film thicknesses above (510 +/- 30) nm with an UV-irradiation density of 7.2 10-4 J cm-2 nm-1 at a wavelength of 190 nm.

Characteristics of a promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Ohta, Toshitaka; Vining, Cronin B.; Allevato, Camillo E.

1991-01-01

A preliminary study on arc-melted samples has indicated that ruthenium silicide has the potential to obtain figure-of-merit values four times higher than that of conventional silicon-germanium material. In order to realize the high figure-of-merit values, high-quality crystal from the melt is needed. A Bridgman-like method has been employed and has realized much better crystals than arc-melted ones.

Elastic modulus and surface tension of a polyurethane rubber in nanometer thick films

NASA Astrophysics Data System (ADS)

Zhai, Meiyu; McKenna, Gregory

2014-03-01

Estane is a kind of polyurethane with thermodynamically incompatible hard and soft segments. In this study the macro and micro properties of Estane have been characterized and compared. The viscoelastic properties of this material in bulk scale have been determined using dynamic rheometry. Time-temperature superposition was found to be applicable for this material, and a master curve was successfully constructed from the dynamic shear responses of G'(ω) and G''(ω) . Also a novel nano bubble inflation method was used to obtain the creep compliance of the Estane ultrathin films and the results show stiffening in the rubbery region for the Estane over thicknesses ranging from 110nm to 22nm. The dependence of the rubbery stiffening on film thickness is studied and the relative influences of nano confinement and surface tension effect are analyzed using both a direct stress strain analysis and an energy balance method for the membrane. The contributions of surface tension and nano confinement are considered separately. Office of Naval Research under project No.N00014-11-1-0424.

Ruthenium(II) polypyridyl complexes as dual inhibitors of telomerase and topoisomerase.

PubMed

Liao, Guoliang; Chen, Xiang; Wu, Jingheng; Qian, Chen; Wang, Yi; Ji, Liangnian; Chao, Hui

2015-09-14

One novel ruthenium polypyridyl complex, [Ru(bpy)2(icip)](2+) (1), and two previously reported ruthenium polypyridyl complexes, [Ru(bpy)2(pdppz)](2+) ()2 and [Ru(bpy)2(tactp)](2+) (3) (bpy = 2,2'-bipyridine, icip = 2-(indeno[2,1-b]chromen-6-yl)-1H-imidazo[4,5-f][1,10]phenanthroline, pdppz = phenanthro[4,5-abc]dipyrido[3,2-h:2',3'-j]phenazine, tactp = 4,5,9,18-tetraazachryseno[9,10-b]-triphenylene), have been synthesised. As expected, these complexes show inhibition towards telomerase by inducing and stabilising the G-quadruplex structure, and behave as topoisomerase I/II poisons at the same time. Additionally, the acute and chronic cytotoxicities of the complexes are considered. Furthermore, cell apoptosis experiments are used to briefly study the mechanism. Because studies involving multi-target inhibition towards topoisomerase and telomerase of Ru(II) complexes have not been reported previously, the present research may help to develop innovative chemical strategies and therapies.

Long-laser-pulse method of producing thin films

DOEpatents

Balooch, Mehdi; Olander, Donald K.; Russo, Richard E.

1991-01-01

A method of depositing thin films by means of laser vaporization employs a long-pulse laser (Nd-glass of about one millisecond duration) with a peak power density typically in the range 10.sup.5 -10.sup.6 W/cm.sup.2. The method may be used to produce high T.sub.c superconducting films of perovskite material. In one embodiment, a few hundred nanometers thick film of YBa.sub.2 Cu.sub.3 O.sub.7-x is produced on a SrTiO.sub.3 crystal substrate in one or two pulses. In situ-recrystallization and post-annealing, both at elevated temperature and in the presence of an oxidizing agen The invention described herein arose in the course of, or under, Contract No. DE-C03-76SF0098 between the United States Department of Energy and the University of California.

Performance of a Nanometer Resolution BPM System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Walston, S.; Chung, C.; Fitsos, P.

2007-04-24

International Linear Collider (ILC) interaction region beam sizes and component position stability requirements will be as small as a few nanometers. It is important to the ILC design effort to demonstrate that these tolerances can be achieved ideally using beam-based stability measurements. It has been estimated that RF cavity beam position monitors (BPMs) could provide position measurement resolutions of less than one nanometer and could form the basis of the desired beam-based stability measurement. We have developed a high resolution RF cavity BPM system. A triplet of these BPMs has been installed in the extraction line of the KEK Acceleratormore » Test Facility (ATF) for testing with its ultra-low emittance beam. The three BPMs are rigidly mounted inside an alignment frame on variable-length struts which allow movement in position and angle. We have developed novel methods for extracting the position and tilt information from the BPM signals including a calibration algorithm which is immune to beam jitter. To date, we have been able to demonstrate a resolution of approximately 20 nm over a dynamic range of +/- 20 microns. We report on the progress of these ongoing tests.« less

Stretchable, adhesive and ultra-conformable elastomer thin films.

PubMed

Sato, Nobutaka; Murata, Atsushi; Fujie, Toshinori; Takeoka, Shinji

2016-11-16

Thermoplastic elastomers are attractive materials because of the drastic changes in their physical properties above and below the glass transition temperature (T g ). In this paper, we report that free-standing polystyrene (PS, T g : 100 °C) and polystyrene-polybutadiene-polystyrene triblock copolymer (SBS, T g : -70 °C) thin films with a thickness of hundreds of nanometers were prepared by a gravure coating method. Among the mechanical properties of these thin films determined by bulge testing and tensile testing, the SBS thin films exhibited a much lower elastic modulus (ca. 0.045 GPa, 212 nm thickness) in comparison with the PS thin films (ca. 1.19 GPa, 217 nm thickness). The lower elastic modulus and lower thickness of the SBS thin films resulted in higher conformability and thus higher strength of adhesion to an uneven surface such as an artificial skin model with roughness (R a = 10.6 μm), even though they both have similar surface energies. By analyzing the mechanical properties of the SBS thin films, the elastic modulus and thickness of the thin films were strongly correlated with their conformability to a rough surface, which thus led to a high adhesive strength. Therefore, the SBS thin films will be useful as coating layers for a variety of materials.

Fabrication of Nanometer- and Micrometer-Scale Protein Structures by Site-Specific Immobilization of Histidine-Tagged Proteins to Aminosiloxane Films with Photoremovable Protein-Resistant Protecting Groups

PubMed Central

2016-01-01

The site-specific immobilization of histidine-tagged proteins to patterns formed by far-field and near-field exposure of films of aminosilanes with protein-resistant photolabile protecting groups is demonstrated. After deprotection of the aminosilane, either through a mask or using a scanning near-field optical microscope, the amine terminal groups are derivatized first with glutaraldehyde and then with N-(5-amino-1-carboxypentyl)iminodiacetic acid to yield a nitrilo-triacetic-acid-terminated surface. After complexation with Ni2+, this surface binds histidine-tagged GFP and CpcA-PEB in a site-specific fashion. The chemistry is simple and reliable and leads to extensive surface functionalization. Bright fluorescence is observed in fluorescence microscopy images of micrometer- and nanometer-scale patterns. X-ray photoelectron spectroscopy is used to study quantitatively the efficiency of photodeprotection and the reactivity of the modified surfaces. The efficiency of the protein binding process is investigated quantitatively by ellipsometry and by fluorescence microscopy. We find that regions of the surface not exposed to UV light bind negligible amounts of His-tagged proteins, indicating that the oligo(ethylene glycol) adduct on the nitrophenyl protecting group confers excellent protein resistance; in contrast, exposed regions bind His-GFP very effectively, yielding strong fluorescence that is almost completely removed on treatment of the surface with imidazole, confirming a degree of site-specific binding in excess of 90%. This simple strategy offers a versatile generic route to the spatially selective site-specific immobilization of proteins at surfaces. PMID:26820378

Visualizing cell extracellular matrix (ECM) deposited by cells cultured on aligned bacteriophage M13 thin films.

PubMed

Wu, Laying; Lee, L Andrew; Niu, Zhongwei; Ghoshroy, Soumitra; Wang, Qian

2011-08-02

Topographical features ranging from micro- to nanometers can affect cell orientation and migratory pathways, which are important factors in tissue engineering and tumor migration. In our previous study, a convective assembly of bacteriophage M13 resulted in thin films which could be used to control the alignment of cells. However, several questions regarding its underlying reasons to dictate cell alignment remained unanswered. Here, we further study the nanometer topographical features generated by the bacteriophage M13 crystalline film, which results in the alignment of the cells and extracellular matrix (ECM) proteins. Sequential imaging analyses at micro- and nanoscale levels of aligned cells and fibrillar matrix proteins were documented using scanning electron microscopy and immunofluorescence microscopy. As a result, we observed baby hamster kidney cells with higher degree of alignment on the ordered M13 substrates than NIH-3T3 fibroblasts, a difference which could be attributed to the intrinsic nature of the cells' production of ECM proteins. The results from this study provide a crucial insight into the topographical features of a biological thin film, which can be utilized to control the orientation of cells and surrounding ECM proteins.

Room Temperature Ferroelectricity in Ultrathin SnTe Films

NASA Astrophysics Data System (ADS)

Chang, Kai; Liu, Junwei; Lin, Haicheng; Zhao, Kun; Zhong, Yong; Ji, Shuai-Hua; He, Ke; Wang, Lili; Ma, Xucun; Fu, Liang; Chen, Xi; Xue, Qi-Kun

2015-03-01

The ultrathin SnTe films with several unit cell thickness grown on graphitized SiC(0001) surface have been studied by the scanning tunneling microscopy and spectroscopy (STM/S). The domain structures, local lattice distortion and the electronic band bending at film edges induced by the in-plane spontaneous polarization along < 110 > have been revealed at atomic scale. The experiments at variant temperature show that the Curie temperature Tc of the one unit cell thick (two atomic layers) SnTe film is as high as 280K, much higher than that of the bulk counterpart (~100K) and the 2-4 unit cell thick films even indicate robust ferroelectricity at room temperature. This Tc enhancement is attributed to the stress-free interface, larger electronic band gap and greatly reduced Sn vacancy concentration in the ultrathin films. The lateral domain size varies from several tens to several hundreds of nanometers, and the spontaneous polarization direction could be modified by STM tip. Those properties of ultrathin SnTe films show the potential application on ferroelectric devices. The work was financially supported by Ministry of Science and Technology of China, National Science Foundation and Ministry of Education of China.

Nucleophilic addition of amines to ruthenium carbenes: ortho-(alkynyloxy)benzylamine cyclizations towards 1,3-benzoxazines.

PubMed

González-Rodríguez, Carlos; Suárez, José Ramón; Varela, Jesús A; Saá, Carlos

2015-02-23

A new ruthenium-catalyzed cyclization of ortho-(alkynyloxy)benzylamines to dihydro-1,3-benzoxazines is reported. The cyclization is thought to take place via the vinyl ruthenium carbene intermediates which are easily formed from [Cp*RuCl(cod)] and N2 CHSiMe3 . The mild reaction conditions and the efficiency of the procedure allow the easy preparation of a broad range of new 2-vinyl-2-substituted 1,3-benzoxazine derivatives. Rearrangement of an internal C(sp) in the starting material into a tetrasubstituted C(sp(3) ) atom in the final 1,3-benzoxazine is highly remarkable. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Characterization of thin films on the nanometer scale by Auger electron spectroscopy and X-ray photoelectron spectroscopy

NASA Astrophysics Data System (ADS)

Powell, C. J.; Jablonski, A.; Werner, W. S. M.; Smekal, W.

2005-01-01

We describe two NIST databases that can be used to characterize thin films from Auger electron spectroscopy (AES) and X-ray photoelectron spectroscopy (XPS) measurements. First, the NIST Electron Effective-Attenuation-Length Database provides values of effective attenuation lengths (EALs) for user-specified materials and measurement conditions. The EALs differ from the corresponding inelastic mean free paths on account of elastic-scattering of the signal electrons. The database supplies "practical" EALs that can be used to determine overlayer-film thicknesses. Practical EALs are plotted as a function of film thickness, and an average value is shown for a user-selected thickness. The average practical EAL can be utilized as the "lambda parameter" to obtain film thicknesses from simple equations in which the effects of elastic-scattering are neglected. A single average practical EAL can generally be employed for a useful range of film thicknesses and for electron emission angles of up to about 60°. For larger emission angles, the practical EAL should be found for the particular conditions. Second, we describe a new NIST database for the Simulation of Electron Spectra for Surface Analysis (SESSA) to be released in 2004. This database provides data for many parameters needed in quantitative AES and XPS (e.g., excitation cross-sections, electron-scattering cross-sections, lineshapes, fluorescence yields, and backscattering factors). Relevant data for a user-specified experiment are automatically retrieved by a small expert system. In addition, Auger electron and photoelectron spectra can be simulated for layered samples. The simulated spectra, for layer compositions and thicknesses specified by the user, can be compared with measured spectra. The layer compositions and thicknesses can then be adjusted to find maximum consistency between simulated and measured spectra, and thus, provide more detailed characterizations of multilayer thin-film materials. SESSA can also

Photosensitizing effects of nanometer TiO2 on chlorothalonil photodegradation in aqueous solution and on the surface of pepper.

PubMed

Tan, Yong Qiang; Xiong, Hai Xia; Shi, Tao Zhong; Hua, Ri Mao; Wu, Xiang Wei; Cao, Hai Qun; Li, Xue De; Tang, Jun

2013-05-29

The present study examined the effects of anatase nanometer TiO2 on photochemical degradation of chlorothalonil in aqueous solution and on the plant surface. Results showed that nanometer TiO2 exhibited a strong photosensitizing effect on the degradation of chlorothalonil both in aqueous solution and on the surface of green pepper. The photosensitization rate was the highest in the sunlight compared to illumination under high-pressure mercury and UV lamps. Use of distinct hydroxyl radical scavengers indicated that nanometer TiO2 acted by producing hydroxyl radicals with strong oxidizing capacity. Notably, nanometer TiO2 facilitated complete photodegradation of chlorothalonil with no detectable accumulation of the intermediate chlorothalonil-4-hydroxy. Nanometer TiO2 was also active on the surface of green pepper under natural sunlight both inside and outside of plastic greenhouse. These results together suggest that nanometer TiO2 can be used as a photosensitizer to accelerate degradation of the pesticides under greenhouse conditions.

Structural and morphological modifications of polymer thin film in the presence of nonsolvent

DOE Office of Scientific and Technical Information (OSTI.GOV)

Talukdar, Hrishikesh, E-mail: hiasst@yahoo.in; Kundu, Sarathi

Thin films of sodium poly(acrylic acid) salt (Na-PAA) have been investigated to obtain the modification of the out-of-plane structure and surface morphology in the presence of toluene which is considered as nonsolvent for Na-PAA. X-ray reflectivity analysis show that the out-of-plane thickness of the Na-PAA film increases if the film is kept for longer time inside the toluene. For the thicker film the effect of toluene is more pronounced than the thinner one. Surface morphology obtained from the atomic force microscopy shows that the top surface becomes relatively rough after the dipping of the Na-PAA film inside toluene. Although toluenemore » is nonsolvent for Na-PAA molecules, however, the effect of restructuring of the nanometer-thick polymer film cannot be ignored. The reason for such structural modification has been proposed.« less

Superstable Ultrathin Water Film Confined in a Hydrophilized Carbon Nanotube.

PubMed

Tomo, Yoko; Askounis, Alexandros; Ikuta, Tatsuya; Takata, Yasuyuki; Sefiane, Khellil; Takahashi, Koji

2018-03-14

Fluids confined in a nanoscale space behave differently than in the bulk due to strong interactions between fluid molecules and solid atoms. Here, we observed water confined inside "open" hydrophilized carbon nanotubes (CNT), with diameter of tens of nanometers, using transmission electron microscopy (TEM). A 1-7 nm water film adhering to most of the inner wall surface was observed and remained stable in the high vacuum (order of 10 -5 Pa) of the TEM. The superstability of this film was attributed to a combination of curvature, nanoroughness, and confinement resulting in a lower vapor pressure for water and hence inhibiting its vaporization. Occasional, suspended ultrathin water film with thickness of 3-20 nm were found and remained stable inside the CNT. This film thickness is 1 order of magnitude smaller than the critical film thickness (about 40 nm) reported by the Derjaguin-Landau-Verwey-Overbeek theory and previous experimental investigations. The stability of the suspended ultrathin water film is attributed to the additional molecular interactions due to the extended water meniscus, which balances the rest of the disjoining pressures.

Probing dynamics and pinning of single vortices in superconductors at nanometer scales.

PubMed

Embon, L; Anahory, Y; Suhov, A; Halbertal, D; Cuppens, J; Yakovenko, A; Uri, A; Myasoedov, Y; Rappaport, M L; Huber, M E; Gurevich, A; Zeldov, E

2015-01-07

The dynamics of quantized magnetic vortices and their pinning by materials defects determine electromagnetic properties of superconductors, particularly their ability to carry non-dissipative currents. Despite recent advances in the understanding of the complex physics of vortex matter, the behavior of vortices driven by current through a multi-scale potential of the actual materials defects is still not well understood, mostly due to the scarcity of appropriate experimental tools capable of tracing vortex trajectories on nanometer scales. Using a novel scanning superconducting quantum interference microscope we report here an investigation of controlled dynamics of vortices in lead films with sub-Angstrom spatial resolution and unprecedented sensitivity. We measured, for the first time, the fundamental dependence of the elementary pinning force of multiple defects on the vortex displacement, revealing a far more complex behavior than has previously been recognized, including striking spring softening and broken-spring depinning, as well as spontaneous hysteretic switching between cellular vortex trajectories. Our results indicate the importance of thermal fluctuations even at 4.2 K and of the vital role of ripples in the pinning potential, giving new insights into the mechanisms of magnetic relaxation and electromagnetic response of superconductors.

Probing dynamics and pinning of single vortices in superconductors at nanometer scales

NASA Astrophysics Data System (ADS)

Embon, L.; Anahory, Y.; Suhov, A.; Halbertal, D.; Cuppens, J.; Yakovenko, A.; Uri, A.; Myasoedov, Y.; Rappaport, M. L.; Huber, M. E.; Gurevich, A.; Zeldov, E.

2015-01-01

The dynamics of quantized magnetic vortices and their pinning by materials defects determine electromagnetic properties of superconductors, particularly their ability to carry non-dissipative currents. Despite recent advances in the understanding of the complex physics of vortex matter, the behavior of vortices driven by current through a multi-scale potential of the actual materials defects is still not well understood, mostly due to the scarcity of appropriate experimental tools capable of tracing vortex trajectories on nanometer scales. Using a novel scanning superconducting quantum interference microscope we report here an investigation of controlled dynamics of vortices in lead films with sub-Angstrom spatial resolution and unprecedented sensitivity. We measured, for the first time, the fundamental dependence of the elementary pinning force of multiple defects on the vortex displacement, revealing a far more complex behavior than has previously been recognized, including striking spring softening and broken-spring depinning, as well as spontaneous hysteretic switching between cellular vortex trajectories. Our results indicate the importance of thermal fluctuations even at 4.2 K and of the vital role of ripples in the pinning potential, giving new insights into the mechanisms of magnetic relaxation and electromagnetic response of superconductors.

Synthesis of thin films and materials utilizing a gaseous catalyst

DOEpatents

Morse, Daniel E; Schwenzer, Birgit; Gomm, John R; Roth, Kristian M; Heiken, Brandon; Brutchey, Richard

2013-10-29

A method for the fabrication of nanostructured semiconducting, photoconductive, photovoltaic, optoelectronic and electrical battery thin films and materials at low temperature, with no molecular template and no organic contaminants. High-quality metal oxide semiconductor, photovoltaic and optoelectronic materials can be fabricated with nanometer-scale dimensions and high dopant densities through the use of low-temperature biologically inspired synthesis routes, without the use of any biological or biochemical templates.

Critical current densities of powder-in-tube MgB2 tapes fabricated with nanometer-size Mg powder

NASA Astrophysics Data System (ADS)

Yamada, H.; Hirakawa, M.; Kumakura, H.; Matsumoto, A.; Kitaguchi, H.

2004-03-01

We fabricated powder-in-tube MgB2/Fe tapes using a powder mixture of nanometer-size Mg and commercial amorphous B and investigated the transport properties. High-purity nanometer-size Mg powder was fabricated by applying the thermal plasma method. 5-10 mol % SiC powder doping was tried to enhance the Jc properties. We found that the use of nanometer-size Mg powder was effective to increase the Jc values. The transport Jc values of the nondoped and 10 mol % SiC-doped tapes prepared with nanometer-size Mg powder reached 90 and 250 A/mm2 at 4.2 K and 10 T, respectively. These values were about five times higher than those of the tapes prepared with commercial Mg powder.

Seebeck coefficient of synthesized Titanium Dioxide thin film on FTO glass substrate

NASA Astrophysics Data System (ADS)

Usop, R.; Hamed, N. K. A.; Megat Hasnan, M. M. I.; Ikeda, H.; Sabri, M. F. M.; Ahmad, M. K.; Said, S. M.; Salleh, F.

2018-04-01

In order to fabricate a thermoelectric device on glass substrate for harvesting waste heat energy through house appliances, the Seebeck coefficient of translucent TiO2 thin film was investigated. The TiO2 thin film was synthesized by using hydrothermal method with F-SnO2 coated glass as substrate. From scanning electron microscopy analysis, the synthesized TiO2 thin film was found to be in nanometer-scale rod structure with a thickness of 4 µm. The Seebeck coefficient was measured in the temperature range of 300 – 400 K. The Seebeck coefficient is found to be in negative value which shows that synthesized film is an n-type semiconductor material, and is lower than the value of bulk-size material. This reduction in Seebeck coefficient of TiO2 thin film is likely due to the low dimensional effect and the difference of carrier concentration.

High-density regular arrays of nanometer-scale rods formed on silicon surfaces via femtosecond laser irradiation in water.

PubMed

Shen, Mengyan; Carey, James E; Crouch, Catherine H; Kandyla, Maria; Stone, Howard A; Mazur, Eric

2008-07-01

We report on the formation of high-density regular arrays of nanometer-scale rods using femtosecond laser irradiation of a silicon surface immersed in water. The resulting surface exhibits both micrometer-scale and nanometer-scale structures. The micrometer-scale structure consists of spikes of 5-10 mum width, which are entirely covered by nanometer-scale rods that are roughly 50 nm wide and normal to the surface of the micrometer-scale spikes. The formation of the nanometer-scale rods involves several processes: refraction of laser light in highly excited silicon, interference of scattered and refracted light, rapid cooling in water, roughness-enhanced optical absorptance, and capillary instabilities.

Cytotoxic hydrogen bridged ruthenium quinaldamide complexes showing induced cancer cell death by apoptosis.

PubMed

Lord, Rianne M; Allison, Simon J; Rafferty, Karen; Ghandhi, Laura; Pask, Christopher M; McGowan, Patrick C

2016-08-16

This report presents the first known p-cymene ruthenium quinaldamide complexes which are stabilised by a hydrogen-bridging atom, [{(p-cym)Ru(II)X(N,N)}{H(+)}{(N,N)XRu(II)(p-cym)}][PF6] (N,N = functionalised quinaldamide and X = Cl or Br). These complexes are formed by a reaction of [p-cymRu(μ-X)2]2 with a functionalised quinaldamide ligand. When filtered over NH4PF6, and under aerobic conditions the equilibrium of NH4PF6 ⇔ NH3 + HPF6 enables incorporation of HPF6 and the stabilisation of two monomeric ruthenium complexes by a bridging H(+), which are counter-balanced by a PF6 counterion. X-ray crystallographic analysis is presented for six new structures with OO distances of 2.420(4)-2.448(15) Å, which is significant for strong hydrogen bonds. Chemosensitivity studies against HCT116, A2780 and cisplatin-resistant A2780cis human cancer cells showed the ruthenium complexes with a bromide ancillary ligand to be more potent than those with a chloride ligand. The 4'-fluoro compounds show a reduction in potency for both chloride and bromide complexes against all cell lines, but an increase in selectivity towards cancer cells compared to non-cancer ARPE-19 cells, with a selectivity index >1. Mechanistic studies showed a clear correlation between IC50 values and induction of cell death by apoptosis.

Chemiluminescence reactions with cationic, neutral, and anionic ruthenium(II) complexes containing 2,2'-bipyridine and bathophenanthroline disulfonate ligands.

PubMed

Francis, Paul S; Papettas, Dimitra; Zammit, Elizabeth M; Barnett, Neil W

2010-07-15

Ruthenium complexes containing 4,7-diphenyl-1,10-phenanthroline disulfonate (bathophenanthroline disulfonate; BPS) ligands, Ru(BPS)(3)(4-), Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), were compared to tris(2,2'-bipyridine)ruthenium(II) (Ru(bipy)(3)(2+)), including examination of the wavelengths of maximum absorption and corrected emission intensity, photoluminescence quantum yield, stability of their oxidised ruthenium(III) form, and relative chemiluminescence intensities and signal-to-blank ratios with cerium(IV) sulfate and six analytes (codeine, morphine cocaine, potassium oxalate, furosemide and hydrochlorothiazide) in acidic aqueous solution. The presence of BPS ligands in the complex increased the photoluminescence quantum yield, but decreased the stability of the oxidised form of the reagent. In contrast to previous evidence showing much greater electrochemiluminescence intensities using Ru(BPS)(2)(bipy)(2-) and Ru(BPS)(bipy)(2), these complexes did not provide superior chemiluminescence signals than their homoleptic analogues. Copyright 2010 Elsevier B.V. All rights reserved.

Formation of vinyl halides via a ruthenium-catalyzed three-component coupling.

PubMed

Trost, Barry M; Pinkerton, Anthony B

2002-06-26

The ruthenium-catalyzed three-component coupling of an alkyne, an enone, and halide ion to form E- or Z-vinyl halides has been investigated. Through systematic optimization experiments, the conditions effecting the olefin selectivity were examined. In general, more polar solvents such as DMF favored the formation of the E-isomer, and less polar solvents such as acetone favored formation of the Z-isomer. The optimized conditions for the formation of E-vinyl chlorides were found to be the use of cyclopentadienyl ruthenium (II) cyclooctadiene chloride, stannic chloride pentahydrate as a cocatalyst, and for a chloride source, either ammonium chloride in DMF/water mixtures or tetramethylammonium chloride in DMF. A range of several other ruthenium (II) catalysts was also shown to be effective. A wide variety of vinyl chlorides could be formed under these conditions. Substrates with tethered alcohols or ketones either five or six carbons from the alkyne portion gave instead diketone or cyclohexenone products. For formation of vinyl bromides, a catalyst system involving the use of cyclopentadienylruthenium (II) tris(acetonitrile) hexafluorophosphate with stannic bromide as a cocatalyst was found to be most effective. The use of ammonium bromide in DMF/acetone mixtures was optimal for the synthesis of E-vinyl bromides, and the use of lithium bromide in acetone was optimal for formation of the corresponding Z-isomer. Under either set of conditions, a wide range of vinyl bromides could be formed. When alkynes with propargylic substituents are used, enhanced selectivity for formation of the Z-isomer is observed. When aryl acetylenes are used as the coupling partners, complete selectivity for the Z-isomer is obtained. A mechanism involving a cis or trans halometalation is invoked to explain formation of the observed products. The vinyl halides have been shown to be precursors to alpha-hydroxy ketones and cyclopentenones, and as coupling partners in Suzuki-type reactions.

Ultrathin Polymer Films, Patterned Arrays, and Microwells

NASA Astrophysics Data System (ADS)

Yan, Mingdi

2002-05-01

The ability to control and tailor the surface and interface properties of materials is important in microelectronics, cell growth control, and lab-on-a-chip devices. Modification of material surfaces with ultrathin polymer films is attractive due to the availability of a variety of polymers either commercially or by synthesis. We have developed two approaches to the attachment of ultrathin polymer films on solid substrates. In the first method, a silane-functionalized perfluorophenyl azide (PFPA-silane) was synthesized and used to covalently immobilize polymer thin films on silicon wafers. Silanization of the wafer surface with the PFPA-silane introduced a monolayer of azido groups which in turn covalently attached the polymer film by way of photochemically initiated insertion reactions. The thickness of the film could be adjusted by the type and the molecular weight of the polymer. The method is versatile due to the general C-H and/or N-H insertion reactions of crosslinker; and therefore, no specific reactive functional groups on the polymers are required. Using this method, a new type of microwell array was fabricated from covalently immobilized polymer thin films on flat substrates. The arrays were characterized with AFM, XPS, and TOF-SIMS. The second method describes the attachment of polymer thin films on solid substrates via UV irradiation. The procedure consisted of spin-coating a polymer film and irradiating the film with UV light. Following solvent extraction, a thin film remained. The thickness of the film, from a few to over a hundred nanometers, was controlled by varying solution concentration and the molecular weight of the polymer.

SORPTION OF LEAD ON A RUTHENIUM COMPOUND: A MACROSCOPIC AND MICROSCOPIC STUDY

EPA Science Inventory

The objective of this study was to elucidate the sorption mechanism of Pb on the high-affinity ruthenium compound with time at pH 6 employing batch methods and X-ray absorption fine structure (XAFS) and X-ray diffraction (XRD) spectroscopies. For the spectroscopic studies, Pb so...

SEPARATION OF URANYL AND RUTHENIUM VALUES BY THE TRIBUTYL PHOSPHATE EXTRACTION PROCESS

DOEpatents

Wilson, A.S.

1961-05-01

A process is given for separating uranyl values from ruthenium values contained in an aqueous 3 to 4 M nitric acid solution. After the addition of hydrogen peroxide to obtain a concentration of 0.3 M, the uranium is selectively extracted with kerosene-diluted tributyl phosphate.

Studies on the synthesis, spectra, catalytic and antibacterial activities of binuclear ruthenium(II) complexes.

PubMed

Krishnamoorthy, P; Sathyadevi, P; Deepa, K; Dharmaraj, N

2010-09-15

A new series of stable binuclear ruthenium(II) carbonyl complexes of the general formula [{RuX(CO)(EPh(3))(2)}(2)L] (where X=H or Cl; E=P or As and L=dibasic tetradentate diacetyl resorcinol (H(2)-DAR)) have been synthesised by reacting ruthenium(II) starting complexes [RuHX(CO)(EPh(3))(3)] (where X=H or Cl; E=P or As) and 4,6-diacetylresorcinol (H(2)-DAR) ligand in benzene medium. The structure of the new binuclear ruthenium(II) carbonyl complexes was established using elemental analysis, spectra (FT-IR, UV-vis and (1)H NMR), electrochemical and thermal studies. In these reactions, the 4,6-diacetylresorcinol (H(2)-DAR) ligand behaves as a binegative tetradentate chelating ligand coordinating through O,O atoms of both the carbonyl and phenolic C-O groups by replacing a molecule of PPh(3)/AsPh(3) and a hydride ion from the starting complexes. Further, all these complexes were also employed as new catalysts for the oxidation of primary and secondary alcohols in the presence of N-methylmorpholine-N-oxide (NMO) as a more viable co-oxidant. The free ligand and their metal complexes have also been screened for their antibacterial activity against the growth of gram +ve and gram -ve bacterial cultures. Copyright 2010 Elsevier B.V. All rights reserved.

Three-dimensional ruthenium-doped TiO 2 sea urchins for enhanced visible-light-responsive H 2 production

DOE PAGES

Nguyen-Phan, Thuy -Duong; Luo, Si; Vovchok, Dimitriy; ...

2016-05-23

Here, three-dimensional (3D) monodispersed sea urchin-like Ru-doped rutile TiO 2 hierarchical architectures composed of radially aligned, densely-packed TiO 2 nanorods have been successfully synthesized via an acid-hydrothermal method at low temperature without the assistance of any structure-directing agent and post annealing treatment. The addition of a minuscule concentration of ruthenium dopants remarkably catalyzes the formation of the 3D urchin structure and drives the enhanced photocatalytic H 2 production under visible light irradiation, not possible on undoped and bulk rutile TiO 2. Increasing ruthenium doping dosage not only increases the surface area up to 166 m 2 g –1 but alsomore » induces enhanced photoresponse in the regime of visible and near infrared light. The doping introduces defect impurity levels, i.e. oxygen vacancy and under-coordinated Ti 3+, significantly below the conduction band of TiO 2, and ruthenium species act as electron donors/acceptors that accelerate the photogenerated hole and electron transfer and efficiently suppress the rapid charge recombination, therefore improving the visible-light-driven activity.« less

Determination of ruthenium in pharmaceutical compounds by graphite furnace atomic absorption spectroscopy.

PubMed

Jia, Xiujuan; Wang, Tiebang; Bu, Xiaodong; Tu, Qiang; Spencer, Sandra

2006-04-11

A graphite furnace atomic absorption (GFAA) spectrometric method for the determination of ruthenium (Rh) in solid and liquid pharmaceutical compounds has been developed. Samples are dissolved or diluted in dimethyl sulfoxide (DMSO) without any other treatment before they were analyzed by GFAA with a carefully designed heating program to avoid pre-atomization signal loss and to achieve suitable sensitivity. Various inorganic and organic solvents were tested and compared and DMSO was found to be the most suitable. In addition, ruthenium was found to be stable in DMSO for at least 5 days. Spike recoveries ranged from 81 to 100% and the limit of quantitation (LOQ) was determined to be 0.5 microg g(-1) for solid samples or 0.005 microg ml(-1) for liquid samples based a 100-fold dilution. The same set of samples was also analyzed by ICP-MS with a different sample preparation method, and excellent agreement was achieved.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, R.

1985-04-02

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

Ruthenium carbonyl catalyst supported on ceric oxide for preparation of olefins from synthesis gas

DOEpatents

Pierantozzi, Ronald

1985-01-01

A catalyst comprising a ruthenium carbonyl compound deposited on a cerium oxide-containing support material provides for the selective synthesis of low molecular weight olefinic hydrocarbons from mixtures of hydrogen and carbon monoxide.

3D nanometer images of biological fibers by directed motion of gold nanoparticles.

PubMed

Estrada, Laura C; Gratton, Enrico

2011-11-09

Using near-infrared femtosecond pulses, we move single gold nanoparticles (AuNPs) along biological fibers, such as collagen and actin filaments. While the AuNP is sliding on the fiber, its trajectory is measured in three dimensions (3D) with nanometer resolution providing a high-resolution image of the fiber. Here, we systematically moved a single AuNP along nanometer-size collagen fibers and actin filament inside chinese hamster ovary K1 living cells, mapping their 3D topography with high fidelity.

Development of a ruthenium/phosphite catalyst system for domino hydroformylation-reduction of olefins with carbon dioxide.

PubMed

Liu, Qiang; Wu, Lipeng; Fleischer, Ivana; Selent, Detlef; Franke, Robert; Jackstell, Ralf; Beller, Matthias

2014-06-02

An efficient domino ruthenium-catalyzed reverse water-gas-shift (RWGS)-hydroformylation-reduction reaction of olefins to alcohols is reported. Key to success is the use of specific bulky phosphite ligands and triruthenium dodecacarbonyl as the catalyst. Compared to the known ruthenium/chloride system, the new catalyst allows for a more efficient hydrohydroxymethylation of terminal and internal olefins with carbon dioxide at lower temperature. Unwanted hydrogenation of the substrate is prevented. Preliminary mechanism investigations uncovered the homogeneous nature of the active catalyst and the influence of the ligand and additive in individual steps of the reaction sequence. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydrogen generation from water/methanol under visible light using aerogel prepared strontium titanate (SrTiO3) nanomaterials doped with ruthenium and rhodium metals

NASA Astrophysics Data System (ADS)

Kuo, Yenting; Klabunde, Kenneth J.

2012-07-01

Nanostructured strontium titanate visible-light-driven photocatalysts containing rhodium and ruthenium were synthesized by a modified aerogel synthesis using ruthenium chloride and rhodium nitrate as dopant precursors, and titanium isopropoxide and strontium metal as the metal sources. The well-defined crystalline SrTiO3 structure was confirmed by means of x-ray diffraction. After calcination at 500 °C, diffuse reflectance spectroscopy shows an increase in light absorption at 370 nm due to the presence of Rh3 + ; however an increase of the calcination temperature to 600 °C led to a decrease in intensity, probably due to a loss of surface area. An increase in the rhodium doping level also led to an increase in absorption at 370 nm however, the higher amounts of dopant lowered the photocatalytic activity. The modified aerogel synthesis allows greatly enhanced H2 production performance from an aqueous methanol solution under visible light irradiation compared with lower surface area conventional materials. We believe that this enhanced activity is due to the higher surface areas while high quality nanocrystalline materials are still obtained. Furthermore, the surface properties of these nanocrystalline aerogel materials are different, as exhibited by the higher activities in alkaline solutions, while conventional materials (obtained via high temperature solid-state synthesis methods) only exhibit reasonable hydrogen production in acidic solutions. Moreover, an aerogel synthesis approach gives the possibility of thin-film formation and ease of incorporation into practical solar devices.

Skating on a Film of Air: Drops Impacting on a Surface

NASA Astrophysics Data System (ADS)

Kolinski, John M.; Rubinstein, Shmuel M.; Mandre, Shreyas; Brenner, Michael P.; Weitz, David A.; Mahadevan, L.

2012-02-01

The commonly accepted description of drops impacting on a surface typically ignores the essential role of the air that is trapped between the impacting drop and the surface. Here we describe a new imaging modality that is sensitive to the behavior right at the surface. We show that a very thin film of air, only a few tens of nanometers thick, remains trapped between the falling drop and the surface as the drop spreads. The thin film of air serves to lubricate the drop enabling the fluid to skate on the air film laterally outward at surprisingly high velocities, consistent with theoretical predictions. Eventually this thin film of air breaks down as the fluid wets the surface via a spinodal-like mechanism. Our results show that the dynamics of impacting drops are much more complex than previously thought, with a rich array of unexpected phenomena that require rethinking classic paradigms.

In Situ FTIR and NMR Spectroscopic Investigations on Ruthenium-Based Catalysts for Alkene Hydroformylation.

PubMed

Kubis, Christoph; Profir, Irina; Fleischer, Ivana; Baumann, Wolfgang; Selent, Detlef; Fischer, Christine; Spannenberg, Anke; Ludwig, Ralf; Hess, Dieter; Franke, Robert; Börner, Armin

2016-02-18

Homogeneous ruthenium complexes modified by imidazole-substituted monophosphines as catalysts for various highly efficient hydroformylation reactions were characterized by in situ IR spectroscopy under reaction conditions and NMR spectroscopy. A proper protocol for the preformation reaction from [Ru3 (CO)12] is decisive to prevent the formation of inactive ligand-modified polynuclear complexes. During catalysis, ligand-modified mononuclear ruthenium(0) carbonyls were detected as resting states. Changes in the ligand structure have a crucial impact on the coordination behavior of the ligand and consequently on the catalytic performance. The substitution of CO by a nitrogen atom of the imidazolyl moiety in the ligand is not a general feature, but it takes place when structural prerequisites of the ligand are fulfilled. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bioimaging of isosteric osmium and ruthenium anticancer agents by LA-ICP-MS.

PubMed

Klose, Matthias H M; Theiner, Sarah; Kornauth, Christoph; Meier-Menches, Samuel M; Heffeter, Petra; Berger, Walter; Koellensperger, Gunda; Keppler, Bernhard K

2018-03-01

Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used to study the spatial distribution of two metallodrugs with anticancer activities in vivo, namely the organoruthenium plecstatin-1 (1) and its isosteric osmium analogue (2), in liver, kidneys, muscles and tumours of treated mice bearing a CT-26 tumour after single-dose i.p. administration. To the best of our knowledge, this is the first time that the spatial distribution of an osmium drug candidate has been investigated using LA-ICP-MS in tissues. Independent measurements of the average ruthenium and osmium concentration via microwave digestion and ICP-MS in organs and tumours were in good agreement with the LA-ICP-MS results. Matrix-matched standards (MMS) ranging from 1 to 30 μg g -1 were prepared to quantify the spatial distributions of the metals and the average metal content of the MMS samples was additionally quantified by ICP-MS after microwave digestion. The recoveries for osmium and ruthenium in the MMS were 105% and 101% on average, respectively, validating the sample preparation procedure of the MMS. Preparation of MMS was carried out under an argon atmosphere to prevent oxidation of osmium-species to the volatile OsO 4 . The highest metal concentrations were found in the liver, followed by kidney, lung and tumour tissues, while muscles displayed only very low quantities of the respective metal. Both metallodrugs accumulated in the cortex of the kidneys more strongly compared to the medulla. Interestingly, osmium from 2 was largely located at the periphery and tissue edges, whereas ruthenium from 1 was observed to penetrate deeper into the organs and tumours.

Fabrication of nanometer- and micrometer-scale protein structures by site-specific immobilization of histidine-tagged proteins to aminosiloxane films with photoremovable protein-resistant protecting groups

DOE PAGES

Xia, Sijing; Cartron, Michael; Morby, James; ...

2016-01-28

The site-specific immobilization of histidine-tagged proteins to patterns formed by far-field and near-field exposure of films of aminosilanes with protein-resistant photolabile protecting groups is demonstrated. After deprotection of the aminosilane, either through a mask or using a scanning near-field optical microscope, the amine terminal groups are derivatized first with glutaraldehyde and then with N-(5-amino-1-carboxypentyl)iminodiacetic acid to yield a nitrilo-triacetic-acid-terminated surface. After complexation with Ni 2+, this surface binds histidine-tagged GFP and CpcA-PEB in a site-specific fashion. The chemistry is simple and reliable and leads to extensive surface functionalization. Bright fluorescence is observed in fluorescence microscopy images of micrometer- and nanometer-scalemore » patterns. X-ray photoelectron spectroscopy is used to study quantitatively the efficiency of photodeprotection and the reactivity of the modified surfaces. The efficiency of the protein binding process is investigated quantitatively by ellipsometry and by fluorescence microscopy. We find that regions of the surface not exposed to UV light bind negligible amounts of His-tagged proteins, indicating that the oligo(ethylene glycol) adduct on the nitrophenyl protecting group confers excellent protein resistance; in contrast, exposed regions bind His-GFP very effectively, yielding strong fluorescence that is almost completely removed on treatment of the surface with imidazole, confirming a degree of site-specific binding in excess of 90%. As a result, this simple strategy offers a versatile generic route to the spatially selective site-specific immobilization of proteins at surfaces.« less

Construction and enzymatic degradation of multilayered poly-l-lysine/DNA films.

PubMed

Ren, Kefeng; Ji, Jian; Shen, Jiacong

2006-03-01

The layer-by-layer (LbL) self-assembly of poly-l-lysine (PLL) and deoxyribonucleic acid (DNA) was used to construct the enzymatic biodegradable multilayered films. The LbL build up of DNA multilayers was monitored by UV-vis spectrometry, and atomic force microscopy (AFM). AFM, UV-vis spectrometry and fluorescence spectrometry measurements indicated that 90% of DNA within the films was released almost linearly under 5 U mL(-1)alpha-chymotrypsin in PBS at 37 degrees C in 35 h. TEM and zeta potential experiments revealed that the released DNA molecules were condensed into the slight positive complexes with size from 20 to several hundred nanometers. The well-structured, easy processed enzymatic biodegradable multilayered film may have great potential for gene applications in tissue engineering, medical implants, etc.

Elasticity, biodegradability and cell adhesive properties of chitosan/hyaluronan multilayer films

NASA Astrophysics Data System (ADS)

Schneider, Aurore; Richert, Ludovic; Francius, Gregory; Voegel, Jean-Claude; Picart, Catherine

2007-03-01

In the bioengineering field, a recent and promising approach to modifying biomaterial surfaces is the layer-by-layer (LbL) technique used to build thin polyelectrolyte multilayer films. In this work, we focused on polyelectrolyte multilayer films made of two polysaccharides, chitosan (CHI) and hyaluronan (HA), and on the control of their physico-chemical and cell adhesive properties by chemical cross-linking. CHI/HA films were cross-linked using a water soluble carbodiimide and observed by confocal laser scanning microscopy (CLSM) with a fluorescently labeled CHI. Film thicknesses were similar for native and cross-linked films. The film nanometer roughness was measured by atomic force microscopy and was found to be higher for cross-linked films. Cross-linking the films also leads to a drastic change in film stiffness. The elastic modulus of the films (Young's modulus) as measured by AFM nano-indentation was about tenfold increased for cross-linked films as compared to native ones. From a biological point of view, cross-liked films are more resistant to enzymatic degradation by hyaluronidase. Furthermore, the increase in film stiffness has a favorable effect on the adhesion and spreading of chondrosarcoma cells. Thus, the CHI/HA cross-linked films could be used for various applications due to their adhesive properties and to their mechanical properties (including stability in enzymatic media).

Rapid Water Permeation Through Carbon Nanomembranes with Sub-Nanometer Channels.

PubMed

Yang, Yang; Dementyev, Petr; Biere, Niklas; Emmrich, Daniel; Stohmann, Patrick; Korzetz, Riko; Zhang, Xianghui; Beyer, André; Koch, Sascha; Anselmetti, Dario; Gölzhäuser, Armin

2018-05-22

The provision of clean water is a global challenge, and membrane filtration is a key technology to address it. Conventional filtration membranes are constrained by a trade-off between permeance and selectivity. Recently, some nanostructured membranes demonstrated the ability to overcome this limitation by utilizing well-defined carbon nanoconduits that allow a coordinated passage of water molecules. The fabrication of these materials is still very challenging, but their performance inspires research toward nanofabricated membranes. This study reports on molecularly thin membranes with sub-nanometer channels that combine high water selectivity with an exceptionally high permeance. Carbon nanomembranes (CNMs) of ∼1.2 nm thickness are fabricated from terphenylthiol (TPT) monolayers. Scanning probe microscopy and transport measurements reveal that TPT CNMs consist of a dense network of sub-nanometer channels that efficiently block the passage of most gases and liquids. However, water passes through with an extremely high permeance of ∼1.1 × 10 -4 mol·m -2 ·s -1 ·Pa -1 , as does helium, but with a ∼ 2500 times lower flux. Assuming all channels in a TPT CNM are active in mass transport, we find a single-channel permeation of ∼66 water molecules·s -1 ·Pa -1 . This suggests that water molecules translocate fast and cooperatively through the sub-nanometer channels, similar to carbon nanotubes and membrane proteins (aquaporins). CNMs are thus scalable two-dimensional sieves that can be utilized toward energy-efficient water purification.

Graphene/Ionic Liquid Composite Films and Ion Exchange

PubMed Central

Mo, Yufei; Wan, Yunfang; Chau, Alicia; Huang, Fuchuan

2014-01-01

Wettability of graphene is adjusted by the formation of various ionic surfaces combining ionic liquid (IL) self-assembly with ion exchange. The functionalized ILs were designed and synthesized with the goal of obtaining adjustable wettability. The wettability of the graphene surface bearing various anions was measured systematically. The effect of solvent systems on ion exchange ratios on the graphene surface has also been investigated. Meanwhile, the mechanical properties of the graphene/IL composite films were investigated on a nanometer scale. The elasticity and adhesion behavior of the thin film was determined with respected to the indentation deformation by colloid probe nanoindentation method. The results indicate that anions played an important role in determining graphene/IL composite film properties. In addition, surface wetting and mechanics can be quantitatively determined according to the counter-anions on the surface. This study might suggest an alternate way for quantity detection of surface ions by surface force. PMID:24970602

Observing Optical Plasmons on a Single Nanometer Scale

PubMed Central

Cohen, Moshik; Shavit, Reuven; Zalevsky, Zeev

2014-01-01

The exceptional capability of plasmonic structures to confine light into deep subwavelength volumes has fashioned rapid expansion of interest from both fundamental and applicative perspectives. Surface plasmon nanophotonics enables to investigate light - matter interaction in deep nanoscale and harness electromagnetic and quantum properties of materials, thus opening pathways for tremendous potential applications. However, imaging optical plasmonic waves on a single nanometer scale is yet a substantial challenge mainly due to size and energy considerations. Here, for the first time, we use Kelvin Probe Force Microscopy (KPFM) under optical illumination to image and characterize plasmonic modes. We experimentally demonstrate unprecedented spatial resolution and measurement sensitivity both on the order of a single nanometer. By comparing experimentally obtained images with theoretical calculation results, we show that KPFM maps may provide valuable information on the phase of the optical near field. Additionally, we propose a theoretical model for the relation between surface plasmons and the material workfunction measured by KPFM. Our findings provide the path for using KPFM for high resolution measurements of optical plasmons, prompting the scientific frontier towards quantum plasmonic imaging on submolecular scales. PMID:24556874

Understanding batteries on the micro- and nanometer scale

ScienceCinema

None

2018-01-16

In order to understand performance limitations and failure mechanisms of batteries, one has to investigate processes on the micro- and nanometer scale. A typical failure mechanism in lithium metal batteries is dendritic growth. During discharge, lithium is stripped of the anode surface and migrates to the cathode. During charge, lithium is deposited back on the anode. Repeated cycling can result in stripping and re-deposition that roughens the surface. The roughening of the surface changes the electric field and draws more metal to spikes that are beginning to grow. These can grow with tremendous mechanical force, puncture the separator, and directly connect the anode with the cathode which can create an internal short circuit. This can lead to an uncontrolled discharge reaction, which heats the cell and causes additional exothermic reactions leading to what is called thermal runaway. ORNL has developed a new technology called liquid electron microscopy. In a specially designed sample holder micro-chamber with electron-transparent windows, researchers can hold a liquid and take images of structures and particles at nanometer size. It's the first microscope holder of its kind used to investigate the inside of a battery while cycled.

Nanometals for Solar-to-Chemical Energy Conversion: From Semiconductor-Based Photocatalysis to Plasmon-Mediated Photocatalysis and Photo-Thermocatalysis.

PubMed

Meng, Xianguang; Liu, Lequan; Ouyang, Shuxin; Xu, Hua; Wang, Defa; Zhao, Naiqin; Ye, Jinhua

2016-08-01

Nanometal materials play very important roles in solar-to-chemical energy conversion due to their unique catalytic and optical characteristics. They have found wide applications from semiconductor photocatalysis to rapidly growing surface plasmon-mediated heterogeneous catalysis. The recent research achievements of nanometals are reviewed here, with regard to applications in semiconductor photocatalysis, plasmonic photocatalysis, and plasmonic photo-thermocatalysis. As the first important topic discussed here, the latest progress in the design of nanometal cocatalysts and their applications in semiconductor photocatalysis are introduced. Then, plasmonic photocatalysis and plasmonic photo-thermocatalysis are discussed. A better understanding of electron-driven and temperature-driven catalytic behaviors over plasmonic nanometals is helpful to bridge the present gap between the communities of photocatalysis and conventional catalysis controlled by temperature. The objective here is to provide instructive information on how to take the advantages of the unique functions of nanometals in different types of catalytic processes to improve the efficiency of solar-energy utilization for more practical artificial photosynthesis. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The uniformity study of non-oxide thin film at device level using electron energy loss spectroscopy

NASA Astrophysics Data System (ADS)

Li, Zhi-Peng; Zheng, Yuankai; Li, Shaoping; Wang, Haifeng

2018-05-01

Electron energy loss spectroscopy (EELS) has been widely used as a chemical analysis technique to characterize materials chemical properties, such as element valence states, atoms/ions bonding environment. This study provides a new method to characterize physical properties (i.e., film uniformity, grain orientations) of non-oxide thin films in the magnetic device by using EELS microanalysis on scanning transmission electron microscope. This method is based on analyzing white line ratio of spectra and related extended energy loss fine structures so as to correlate it with thin film uniformity. This new approach can provide an effective and sensitive method to monitor/characterize thin film quality (i.e., uniformity) at atomic level for thin film development, which is especially useful for examining ultra-thin films (i.e., several nanometers) or embedded films in devices for industry applications. More importantly, this technique enables development of quantitative characterization of thin film uniformity and it would be a remarkably useful technique for examining various types of devices for industrial applications.

Performance of a Nanometer Resolution BPM System

DOE Office of Scientific and Technical Information (OSTI.GOV)

Vogel, V; Hayano, H; Honda, Y

2005-10-14

International Linear Collider (ILC) interaction region beam sizes and component position stability requirements will be as small as a few nanometers. it is important to the ongoing ILC design effort to demonstrate that these tolerances can be achieved--ideally using beam-based stability measurements. It has been estimated that an RF cavity BPM with modern waveform processing could provide a position measurement resolution of less than one nanometer. Such a system could form the basis of the desired beam-based stability measurement, as well as be used for other specialized purposes. They have developed a high resolution RF cavity BPM and associated electronics.more » A triplet comprised of these BPMs has been installed in the extraction line of the KEK Accelerator Test Facility (ATF) for testing with its ultra-low emittance beam. The three BPMs are rigidly mounted inside an alignment frame on six variable-length struts which can be used to move the BPMs in position and angle. they have developed novel methods for extracting the position and tilt information from the BPM signals including a robust calibration algorithm which is immune to beam jitter. To date, they have been able to demonstrate a resolution of approximately 20 nm over a dynamic range of {+-} 20 {micro}m. They report on the progress of these ongoing tests.« less

An electrochemiluminescence sensor based on a Ru(bpy)3(2+)-silica-chitosan/nanogold composite film.

PubMed

Cai, Zhi-min; Wu, Yan-fang; Huang, Yun-he; Li, Qiu-ping; Chen, Xiao-mei; Chen, Xi

2012-05-30

Chitosan, a cationic polysaccharide containing amino and hydroxyl groups, was used to fabricate an electrochemiluminescence (ECL) sensor. In the sensor construction, a glassy carbon electrode (GCE) was first coated by a chitosan film which embedded gold nanoparticles, and then the film was modified by introducing carboxyl groups on the surface, which were used to immobilize tris(2,2'-bipyridyl)ruthenium(II) doped amino-functional silica nanoparticles (NH(2)-RuSiNPs) through amido links. The successful modification was confirmed by scanning electronic microscopy and cyclic voltammetry. A binding model between the chitosan/nanogold composite film and NH(2)-RuSiNPs was also proposed, in which the amido link was the dominant bonding, accompanied with hydrogen bond interaction. ECL studies revealed that the sensor had very good response to different concentrations of 2-(dibutylamino) ethanol. This sensor was also applied in methamphetamine determination. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical and surface analysis of the Fe-Cr-Ru system in non-oxidizing acid solutions

NASA Astrophysics Data System (ADS)

Tjong, S. C.

1990-03-01

The effect of ruthenium addition on the spontaneous passivation behaviour of Fe-40Cr alloy in 0.5M H 2SO 4 and 0.5M HCl acid solutions has been studied. Auger and XPS techniques were also used to investigate the surface chemistries of the spontaneously passivated film. Electrochemical measurements indicate that the Fe-40Cr-0.1Ru and Fe-40Cr-0.2Ru alloys exhibit spontaneous passivation upon exposing them in both hydrochloric and sulphuric acid solutions from 25 to 85 ° C. However, the transition time for spontaneous passivation reduces dramatically with an increase in the ruthenium content and solution temperature. Furthermore, this transition time also decreases for the investigated alloys exposed in a less aggressive sulphuric acid solution. AES results show that ruthenium and chromium are enriched in the spontaneous passive films formed on the Fe-40Cr-0.1Ru alloy in both hydrochloric and sulphuric acid solutions at 25 °C, and also in the spontaneous passive film formed on the Fe-40Cr-0.2Ru alloy in hydrochloric acid solution at 25 ° C. AES does not detect the presence of ruthenium in the spontaneous passive film formed on the Fe-40Cr-0.2Ru alloy in sulphuric acid solution. However, XPS analysis shows that ruthenium and chromium are incorporated into the spontaneous passive films formed on the Fe-40Cr-0.1Ru and Fe-40Cr-0.2Ru alloys in both hydrochloric and sulphuric acid solutions as Ru 4+ and Cr 3+ species.

Note: Setup for chemical atmospheric control during in situ grazing incidence X-ray scattering of printed thin films

DOE PAGES

Pröller, Stephan; Moseguí González, Daniel; Zhu, Chenhuii; ...

2017-06-01

In order to tailor the assembling of polymers and organic molecules, a deeper understanding of the kinetics involved in thin film production is necessary. While post-production characterization only provides insight on the final film structure, more sophisticated experimental setups are needed to probe the structure formation processes in situ during deposition. The drying kinetics of a deposited organic thin film strongly influences the assembling process on the nanometer scale. Lastly, this work presents an experimental setup that enables fine control of the atmosphere composition surrounding the sample during slot die coating, while simultaneously probing the film formation kinetics using inmore » situ grazing incidence X-ray scattering and spectroscopy.« less

Fractography of glass at the nanometer scale

DOE Office of Scientific and Technical Information (OSTI.GOV)

Guilloteau, E.; Arribart, H.; Creuzet, F.

1996-12-01

The authors present a nanometer scale description of the fracture surface of soda-lime glass. This is achieved by the use of Atomic Force Microscopy. The mirror zone is shown to be built with elementary entities, the density of which increases continuously while the mist and hackle zones are approached. Moreover, the overall picture leads to some kind of self-similarity, in the sense that small regions of the hackle zone exhibit the full set of mirror, mist and hackle areas.

Low-Cost Sensors Deliver Nanometer-Accurate Measurements

NASA Technical Reports Server (NTRS)

2015-01-01

As part of a unique partnership program, Kennedy Space Center collaborated with a nearby business school to allow MBA students to examine and analyze the market potential for a selection of NASA-patented technologies. Following the semester, a group of students decided to form Winter Park, Florida-based Juntura Group Inc. to license and sell a technology they had worked with: a sensor capable of detecting position changes as small as 10 nanometers-approximately the thickness of a cell wall.

Growth of multi-component alloy films with controlled graded chemical composition on sub-nanometer scale

DOEpatents

Bajt, Sasa; Vernon, Stephen P.

2005-03-15

The chemical composition of thin films is modulated during their growth. A computer code has been developed to design specific processes for producing a desired chemical composition for various deposition geometries. Good agreement between theoretical and experimental results was achieved.

Highly crystallized nanometer-sized zeolite a with large Cs adsorption capability for the decontamination of water.

PubMed

Torad, Nagy L; Naito, Masanobu; Tatami, Junichi; Endo, Akira; Leo, Sin-Yen; Ishihara, Shinsuke; Wu, Kevin C-W; Wakihara, Toru; Yamauchi, Yusuke

2014-03-01

Nanometer-sized zeolite A with a large cesium (Cs) uptake capability is prepared through a simple post-milling recrystallization method. This method is suitable for producing nanometer-sized zeolite in large scale, as additional organic compounds are not needed to control zeolite nucleation and crystal growth. Herein, we perform a quartz crystal microbalance (QCM) study to evaluate the uptake ability of Cs ions by zeolite, to the best of our knowledge, for the first time. In comparison to micrometer-sized zeolite A, nanometer-sized zeolite A can rapidly accommodate a larger amount of Cs ions into the zeolite crystal structure, owing to its high external surface area. Nanometer-sized zeolite is a promising candidate for the removal of radioactive Cs ions from polluted water. Our QCM study on Cs adsorption uptake behavior provides the information of adsorption kinetics (e.g., adsorption amounts and rates). This technique is applicable to other zeolites, which will be highly valuable for further consideration of radioactive Cs removal in the future. Copyright © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Miscellaneous Lasing Actions in Organo-Lead Halide Perovskite Films.

PubMed

Duan, Zonghui; Wang, Shuai; Yi, Ningbo; Gu, Zhiyuan; Gao, Yisheng; Song, Qinghai; Xiao, Shumin

2017-06-21

Lasing actions in organo-lead halide perovskite films have been heavily studied in the past few years. However, due to the disordered nature of synthesized perovskite films, the lasing actions are usually understood as random lasers that are formed by multiple scattering. Herein, we demonstrate the miscellaneous lasing actions in organo-lead halide perovskite films. In addition to the random lasers, we show that a single or a few perovskite microparticles can generate laser emissions with their internal resonances instead of multiple scattering among them. We experimentally observed and numerically confirmed whispering gallery (WG)-like microlasers in polygon shaped and other deformed microparticles. Meanwhile, owing to the nature of total internal reflection and the novel shape of the nanoparticle, the size of the perovskite WG laser can be significantly decreased to a few hundred nanometers. Thus, wavelength-scale lead halide perovskite lasers were realized for the first time. All of these laser behaviors are complementary to typical random lasers in perovskite film and will help the understanding of lasing actions in complex lead halide perovskite systems.

Imaging Action Potential in Single Mammalian Neurons by Tracking the Accompanying Sub-Nanometer Mechanical Motion.

PubMed

Yang, Yunze; Liu, Xian-Wei; Wang, Hui; Yu, Hui; Guan, Yan; Wang, Shaopeng; Tao, Nongjian

2018-03-28

Action potentials in neurons have been studied traditionally by intracellular electrophysiological recordings and more recently by the fluorescence detection methods. Here we describe a label-free optical imaging method that can measure mechanical motion in single cells with a sub-nanometer detection limit. Using the method, we have observed sub-nanometer mechanical motion accompanying the action potential in single mammalian neurons by averaging the repeated action potential spikes. The shape and width of the transient displacement are similar to those of the electrically recorded action potential, but the amplitude varies from neuron to neuron, and from one region of a neuron to another, ranging from 0.2-0.4 nm. The work indicates that action potentials may be studied noninvasively in single mammalian neurons by label-free imaging of the accompanying sub-nanometer mechanical motion.

Impact of polymer film thickness and cavity size on polymer flow during embossing : towards process design rules for nanoimprint lithography.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Schunk, Peter Randall; King, William P.; Sun, Amy Cha-Tien

2006-08-01

This paper presents continuum simulations of polymer flow during nanoimprint lithography (NIL). The simulations capture the underlying physics of polymer flow from the nanometer to millimeter length scale and examine geometry and thermophysical process quantities affecting cavity filling. Variations in embossing tool geometry and polymer film thickness during viscous flow distinguish different flow driving mechanisms. Three parameters can predict polymer deformation mode: cavity width to polymer thickness ratio, polymer supply ratio, and Capillary number. The ratio of cavity width to initial polymer film thickness determines vertically or laterally dominant deformation. The ratio of indenter width to residual film thickness measuresmore » polymer supply beneath the indenter which determines Stokes or squeeze flow. The local geometry ratios can predict a fill time based on laminar flow between plates, Stokes flow, or squeeze flow. Characteristic NIL capillary number based on geometry-dependent fill time distinguishes between capillary or viscous driven flows. The three parameters predict filling modes observed in published studies of NIL deformation over nanometer to millimeter length scales. The work seeks to establish process design rules for NIL and to provide tools for the rational design of NIL master templates, resist polymers, and process parameters.« less

Structural and catalytic properties of some azo-rhodanine Ruthenium(III) complexes

NASA Astrophysics Data System (ADS)

Shoair, A. F.; El-Bindary, A. A.; Abd El-Kader, M. K.

2017-09-01

Novel azo-rhodanine ruthenium(III) complexes of the type trans-[Ru(Ln)2(AsPh3)2]Cl (Ln = monobasic bidentate anions of 5-(4‧-methoxyphenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL1), 5-(phenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL2) and 5-(4‧-chlorophenylazo)-3-phenylamino-2-thioxothiazolidin-4-one (HL3); AsPh3 = triphenylarsine) have been synthesized and characterized by elemental analysis, spectroscopic (IR, 1H NMR and UV-VIS), magnetic, X-ray diffraction, mass spectra and thermal analysis techniques. These techniques confirm the formation of octahedral ruthenium(III) complexes. The Ru(III) complexes were tested as a catalysts for the oxidation of benzyl alcohol to benzaldehyde with N-methylmorpholine-N-oxide as a co-oxidant. The effect of time, temperature, and solvent were also studied and the mechanism of this catalytic oxidation reaction is suggested. Molecular docking was used to predict the binding between azo rhodanine derivatives (HLn) with the receptor of 3qum- immune system receptor of human prostate specific antigen (PSA) in a Fab sandwich with a high affinity and a PCa selective antibody.

Surface structure of coherently strained ceria ultrathin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shi, Yezhou; Stone, Kevin H.; Guan, Zixuan

2016-11-14

Cerium oxide, or ceria, is an important material for solid oxide fuel cells and water splitting devices. Although the ceria surface is active in catalytic and electrochemical reactions, how its catalytic properties are affected by the surface structure under operating conditions is far from understood. We investigate the structure of the coherently strained CeO 2 ultrathin films on yttria-stabilized zirconia (001) single crystals by specular synchrotron x-ray diffraction (XRD) under oxidizing conditions as a first step to study the surface structure in situ. An excellent agreement between the experiment data and the model is achieved by using a “stacks andmore » islands” model that has a two-component roughness. One component is due to the tiny clusters of nanometer scale in lateral dimensions on each terrace, while the other component is due to slightly different CeO 2 thickness that span over hundreds of nanometers on neighboring terraces. We attribute the nonuniform thickness to step depairing during the thin film deposition that is supported by the surface morphology results on the microscopic level. Importantly, our model also shows that the polarity of the ceria surface is removed by a half monolayer surface coverage of oxygen. In conclusion, the successful resolution of the ceria surface structure using in situ specular synchrotron XRD paves the way to study the structural evolution of ceria as a fuel cell electrode under catalytically relevant temperatures and gas pressures.« less

Physical properties of nanometer graphene oxide films partially and fully reduced by annealing in ultra-high vacuum

NASA Astrophysics Data System (ADS)

Jernigan, Glenn G.; Nolde, Jill A.; Mahadik, Nadeem A.; Cleveland, Erin R.; Boercker, Janice E.; Katz, Michael B.; Robinson, Jeremy T.; Aifer, Edward H.

2017-08-01

The properties of reduced graphene oxide (GO) are reported from a non-chemical reduction method. Ultra-high vacuum annealing of GO films in the thickness of 1-80 nm was studied by XPS, AFM, UV-Vis-NIR, Raman, and TEM to observe the controlled removal of oxygen. We observed the loss of hydroxyl (C-OH) at low temperatures (<600 °C) followed by the complete loss of carbonyls (C = O) and epoxy (C-O-C) species by 1200 °C. As oxygen was removed, we observed a decrease in the layer spacing between the GO sheets and a concurrent decrease in the film resistance. While the Raman spectroscopy showed no change with reduction, indicating no change in the overall defect density or the general structure of the GO, the transmission spectra showed a shift in the transmission minimum from 245 nm to 260 nm, and a total decrease in transmission above 800 nm occurs as the films visibly darken. TEM indicated that there is turbostratic stacking of the graphene layers as the reduction occurs, leading us to conclude that at a certain threshold of reduction the film properties are similar to epitaxial graphene growth on the C-face of SiC, but that a reduction gone too far results in a layer spacing equivalent to graphite.

Electron mobility enhancement in ZnO thin films via surface modification by carboxylic acids

NASA Astrophysics Data System (ADS)

Spalenka, Josef W.; Gopalan, Padma; Katz, Howard E.; Evans, Paul G.

2013-01-01

Modifying the surface of polycrystalline ZnO films using a monolayer of organic molecules with carboxylic acid attachment groups increases the field-effect electron mobility and zero-bias conductivity, resulting in improved transistors and transparent conductors. The improvement is consistent with the passivation of defects via covalent bonding of the carboxylic acid and is reversible by exposure to a UV-ozone lamp. The properties of the solvent used for the attachment are crucial because solvents with high acid dissociation constants (Ka) for carboxylic acids lead to high proton activities and etching of the nanometers-thick ZnO films, masking the electronic effect.

Method for producing electricity using a platinum-ruthenium-palladium catalyst in a fuel cell

DOEpatents

Gorer, Alexander

2004-01-27

A method for producing electricity using a fuel cell that utilizes a ternary alloy composition as a fuel cell catalyst, the ternary alloy composition containing platinum, ruthenium and palladium. The alloy shows increased activity as compared to well-known catalysts.

Reverse-transformation austenite structure control with micro/nanometer size

NASA Astrophysics Data System (ADS)

Wu, Hui-bin; Niu, Gang; Wu, Feng-juan; Tang, Di

2017-05-01

To control the reverse-transformation austenite structure through manipulation of the micro/nanometer grain structure, the influences of cold deformation and annealing parameters on the microstructure evolution and mechanical properties of 316L austenitic stainless steel were investigated. The samples were first cold-rolled, and then samples deformed to different extents were annealed at different temperatures. The microstructure evolutions were analyzed by optical microscopy, scanning electron microscopy (SEM), magnetic measurements, and X-ray diffraction (XRD); the mechanical properties are also determined by tensile tests. The results showed that the fraction of stain-induced martensite was approximately 72% in the 90% cold-rolled steel. The micro/nanometric microstructure was obtained after reversion annealing at 820-870°C for 60 s. Nearly 100% reversed austenite was obtained in samples annealed at 850°C, where grains with a diameter ≤ 500 nm accounted for 30% and those with a diameter > 0.5 μm accounted for 70%. The micro/nanometer-grain steel exhibited not only a high strength level (approximately 959 MPa) but also a desirable elongation of approximately 45%.

Ruthenium(II)-catalysed remote C-H alkylations as a versatile platform to meta-decorated arenes

NASA Astrophysics Data System (ADS)

Li, Jie; Korvorapun, Korkit; de Sarkar, Suman; Rogge, Torben; Burns, David J.; Warratz, Svenja; Ackermann, Lutz

2017-06-01

The full control of positional selectivity is of prime importance in C-H activation technology. Chelation assistance served as the stimulus for the development of a plethora of ortho-selective arene functionalizations. In sharp contrast, meta-selective C-H functionalizations continue to be scarce, with all ruthenium-catalysed transformations currently requiring difficult to remove or modify nitrogen-containing heterocycles. Herein, we describe a unifying concept to access a wealth of meta-decorated arenes by a unique arene ligand effect in proximity-induced ruthenium(II) C-H activation catalysis. The transformative nature of our strategy is mirrored by providing a step-economical entry to a range of meta-substituted arenes, including ketones, acids, amines and phenols--key structural motifs in crop protection, material sciences, medicinal chemistry and pharmaceutical industries.

Biopolymer-based nanocomposites: effect of lignin acetylation in cellulose triacetate films

PubMed Central

Nevárez, Laura Alicia Manjarrez; Casarrubias, Lourdes Ballinas; Celzard, Alain; Fierro, Vanessa; Muñoz, Vinicio Torres; Davila, Alejandro Camacho; Lubian, José Román Torres; Sánchez, Guillermo González

2011-01-01

We have prepared all-biopolymer nanocomposite films using lignin as a filler and cellulose triacetate (CTA) as a polymer matrix, and characterized them by several analytical methods. Three types of lignin were tested: organosolv, hydrolytic and kraft, with or without acetylation. They were used in the form of nanoparticles incorporated at 1 wt% in CTA. Self-supported films were prepared by vapor-induced phase separation at controlled temperature (35–55 °C) and relative humidity (10–70%). The efficiency of acetylation of each type of lignin was studied and discussed, as well as its effects on film structure, homogeneity and mechanical properties. The obtained results are explained in terms of intermolecular filler-matrix interaction at the nanometer scale, for which the highest mechanical resistance was reached using hydrolytic lignin in the nanocomposite. PMID:27877425

Facile transfer of thickness controllable poly(methyl methacrylate) patterns on a nanometer scale onto SiO2 substrates via microcontact printing combined with simplified Langmuir-Schaefer technique.

PubMed

Kim, Yong-Kwan; Kim, Dae-Il; Park, Jaehyun; Shin, Gunchul; Kim, Gyu Tae; Ha, Jeong Sook

2008-12-16

We report on the facile patterning of poly(methyl methacrylate) (PMMA) layers onto SiO2 substrates via microcontact printing combined with the simplified Langmuir-Schaefer (LS) technique. Langmuir film of PMMA was formed just by dropping a dilute PMMA solution onto the air/water surface in a glass Petri dish via self-assembly, and it was used as an ink for the patterned poly(dimethylsilioxane) (PDMS) stamp. The transferred film properties were systematically investigated with variation of postannealing temperature, molecular weight of PMMA, and the inking number. The patterned PMMA film surface was smooth with no vacancy defect in a few micrometers scale AFM images over the whole film area after post-annealing process. The thickness of the PMMA patterns was controlled on the nanometer scale by the number of inkings of the LS layer of PMMA on the PDMS stamp. By using the PMMA patterns as a barrier and a sacrificial layer against the chemical etching and metal deposition, SiO2 and metal patterns were fabricated, respectively. The PMMA layers also worked as a passivation layer against the patterning of V2O5 nanowires and the selective adsorption of single-walled carbon nanotubes (SWCNTs). We also fabricated thin film transistors using patterned SWCNTs with different percolation states and investigated the electrical properties.

High Temperature Mechanical Behavior of Polycrystalline Alumina from Mixed Nanometer and Micrometer Powders

NASA Technical Reports Server (NTRS)

Goldsby, Jon C.

2001-01-01

Sintered aluminum oxide materials were formed using commercial methods from mechanically mixed powders of nano-and micrometer alumina. The powders were consolidated at 1500 and 1600 C with 3.2 and 7.2 ksi applied stress in argon. The conventional micrometer sized powders failed to consolidate. While 100 percent nanometer-sized alumina and its mixture with the micrometer powders achieved less than 99 percent density. Preliminary high temperature creep behavior indicates no super-plastic strains. However high strains (less than 0.65 percent) were generated in the nanometer powder, due to cracks and linked voids initiated by cavitation.

Anisotropic magnetism and spin-dependent transport in Co nanoparticle embedded ZnO thin films

NASA Astrophysics Data System (ADS)

Li, D. Y.; Zeng, Y. J.; Pereira, L. M. C.; Batuk, D.; Hadermann, J.; Zhang, Y. Z.; Ye, Z. Z.; Temst, K.; Vantomme, A.; Van Bael, M. J.; Van Haesendonck, C.

2013-07-01

Oriented Co nanoparticles were obtained by Co ion implantation in crystalline ZnO thin films grown by pulsed laser deposition. Transmission electron microscopy revealed the presence of elliptically shaped Co precipitates with nanometer size, which are embedded in the ZnO thin films, resulting in anisotropic magnetic behavior. The low-temperature resistance of the Co-implanted ZnO thin films follows the Efros-Shklovskii type variable-range-hopping. Large negative magnetoresistance (MR) exceeding 10% is observed in a magnetic field of 1 T at 2.5 K and the negative MR survives up to 250 K (0.3%). The negative MR reveals hysteresis as well as anisotropy that correlate well with the magnetic properties, clearly demonstrating the presence of spin-dependent transport.

Nanometer-thick gold on silicon as a proxy for single-crystal gold for the electrodeposition of epitaxial cuprous oxide thin films

DOE PAGES

Switzer, Jay A.; Hill, James C.; Mahenderkar, Naveen K.; ...

2016-05-27

Here, single-crystal Au is an excellent substrate for electrochemical epitaxial growth due to its chemical inertness, but the high cost of bulk Au single crystals prohibits their use in practical applications. Here, we show that ultrathin epitaxial films of Au electrodeposited onto Si(111), Si(100), and Si(110) wafers can serve as an inexpensive proxy for bulk single-crystal Au for the deposition of epitaxial films of cuprous oxide (Cu 2O). The Au films range in thickness from 7.7 nm for a film deposited for 5 min to 28.3 nm for a film deposited for 30 min. The film thicknesses are measured bymore » low-angle X-ray reflectivity and X-ray Laue oscillations. High-resolution TEM shows that there is not an interfacial SiO x layer between the Si and Au. The Au films deposited on the Si(111) substrates are smoother and have lower mosaic spread than those deposited onto Si(100) and Si(110). The mosaic spread of the Au(111) layer on Si(111) is only 0.15° for a 28.3 nm thick film. Au films deposited onto degenerate Si(111) exhibit ohmic behavior, whereas Au films deposited onto n-type Si(111) with a resistivity of 1.15 Ω·cm are rectifying with a barrier height of 0.85 eV. The Au and the Cu 2O follow the out-of-plane and in-plane orientations of the Si substrates, as determined by X-ray pole figures. The Au and Cu 2O films deposited on Si(100) and Si(110) are both twinned. The films grown on Si(100) have twins with a [221] orientation, and the films grown on Si(110) have twins with a [411] orientation. An interface model is proposed for all Si orientations, in which the –24.9% mismatch for the Au/Si system is reduced to only +0.13% by a coincident site lattice in which 4 unit meshes of Au coincide with 3 unit meshes of Si. Although this study only considers the deposition of epitaxial Cu 2O films on electrodeposited Au/Si, the thin Au films should serve as high-quality substrates for the deposition of a wide variety of epitaxial materials.« less

Effect of ion-plated films of germanium and silicon on friction, wear, and oxidation of 52100 bearing steel

NASA Technical Reports Server (NTRS)

Buckley, D. H.; Spalvins, T.

1977-01-01

Friction and wear experiments were conducted with ion plated films of germanium and silicon on the surface of 52100 bearing steel both dry and in the presence of mineral oil. Both silicon and germanium were found to reduce wear, with germanium being more effective than silicon. An optimum film thickness of germanium for minimum wear without surface crack formation was found to be approximately 400 nanometers (4000 A). The presence of silicon and germanium on the 52100 bearing steel surface improved resistance to oxidation.

Contact stiffness and damping of liquid films in dynamic atomic force microscope

DOE Office of Scientific and Technical Information (OSTI.GOV)

Xu, Rong-Guang; Leng, Yongsheng, E-mail: leng@gwu.edu

2016-04-21

The mechanical properties and dissipation behaviors of nanometers confined liquid films have been long-standing interests in surface force measurements. The correlation between the contact stiffness and damping of the nanoconfined film is still not well understood. We establish a novel computational framework through molecular dynamics (MD) simulation for the first time to study small-amplitude dynamic atomic force microscopy (dynamic AFM) in a simple nonpolar liquid. Through introducing a tip driven dynamics to mimic the mechanical oscillations of the dynamic AFM tip-cantilever assembly, we find that the contact stiffness and damping of the confined film exhibit distinct oscillations within 6-7 monolayermore » distances, and they are generally out-of-phase. For the solid-like film with integer monolayer thickness, further compression of the film before layering transition leads to higher stiffness and lower damping, while much lower stiffness and higher damping occur at non-integer monolayer distances. These two alternating mechanisms dominate the mechanical properties and dissipation behaviors of simple liquid films under cyclic elastic compression and inelastic squeeze-out. Our MD simulations provide a direct picture of correlations between the structural property, mechanical stiffness, and dissipation behavior of the nanoconfined film.« less

Multiple delta doping of single crystal cubic boron nitride films heteroepitaxially grown on (001)diamonds

NASA Astrophysics Data System (ADS)

Yin, H.; Ziemann, P.

2014-06-01

Phase pure cubic boron nitride (c-BN) films have been epitaxially grown on (001) diamond substrates at 900 °C. The n-type doping of c-BN epitaxial films relies on the sequential growth of nominally undoped (p-) and Si doped (n-) layers with well-controlled thickness (down to several nanometer range) in the concept of multiple delta doping. The existence of nominally undoped c-BN overgrowth separates the Si doped layers, preventing Si dopant segregation that was observed for continuously doped epitaxial c-BN films. This strategy allows doping of c-BN films can be scaled up to multiple numbers of doped layers through atomic level control of the interface in the future electronic devices. Enhanced electronic transport properties with higher hall mobility (102 cm2/V s) have been demonstrated at room temperature as compared to the normally continuously Si doped c-BN films.

Using ruthenium polypyridyl functionalized ZnO mesocrystals and gold nanoparticle dotted graphene composite for biological recognition and electrochemiluminescence biosensing

NASA Astrophysics Data System (ADS)

Liu, Suli; Zhang, Jinxing; Tu, Wenwen; Bao, Jianchun; Dai, Zhihui

2014-01-01

Using ruthenium polypyridyl functionalized ZnO mesocrystals as bionanolabels, a universal biological recognition and biosensing platform based on gold nanoparticle (AuNP) dotted reduced graphene oxide (rGO) composite was developed. AuNP-rGO accelerated electron transfer between the detection probe and the electrode, and increased the surface area of the working electrode to load greater amounts of the capture antibodies. The large surface area of ZnO mesocrystals was beneficial for loading a high content ruthenium polypyridyl complex, leading to an enhanced electrochemiluminescence signal. Using α-fetoprotein (AFP) as a model, a simple and sensitive sandwich-type electrochemiluminescence biosensor with tripropylamine (TPrA) as a coreactant for detection of AFP was constructed. The designed biosensor provided a good linear range from 0.04 to 500 ng mL-1 with a low detection limit of 0.031 ng mL-1 at a S/N of 3 for AFP determination. The proposed biological recognition and biosensing platform extended the application of ruthenium polypyridyl functionalized ZnO mesocrystals, which provided a new promising prospect.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan , Pellin, Michael J.; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-04-03

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Subnanometer and nanometer catalysts, method for preparing size-selected catalysts

DOEpatents

Vajda, Stefan [Lisle, IL; Pellin, Michael J [Naperville, IL; Elam, Jeffrey W [Elmhurst, IL; Marshall, Christopher L [Naperville, IL; Winans, Randall A [Downers Grove, IL; Meiwes-Broer, Karl-Heinz [Roggentin, GR

2012-03-27

Highly uniform cluster based nanocatalysts supported on technologically relevant supports were synthesized for reactions of top industrial relevance. The Pt-cluster based catalysts outperformed the very best reported ODHP catalyst in both activity (by up to two orders of magnitude higher turn-over frequencies) and in selectivity. The results clearly demonstrate that highly dispersed ultra-small Pt clusters precisely localized on high-surface area supports can lead to affordable new catalysts for highly efficient and economic propene production, including considerably simplified separation of the final product. The combined GISAXS-mass spectrometry provides an excellent tool to monitor the evolution of size and shape of nanocatalyst at action under realistic conditions. Also provided are sub-nanometer gold and sub-nanometer to few nm size-selected silver catalysts which possess size dependent tunable catalytic properties in the epoxidation of alkenes. Invented size-selected cluster deposition provides a unique tool to tune material properties by atom-by-atom fashion, which can be stabilized by protective overcoats.

Enhanced nonlinear current-voltage behavior in Au nanoparticle dispersed CaCu 3 Ti 4 O 12 composite films

NASA Astrophysics Data System (ADS)

Chen, Cong; Wang, Can; Ning, Tingyin; Lu, Heng; Zhou, Yueliang; Ming, Hai; Wang, Pei; Zhang, Dongxiang; Yang, Guozhen

2011-10-01

An enhanced nonlinear current-voltage behavior has been observed in Au nanoparticle dispersed CaCu 3Ti 4O 12 composite films. The double Schottky barrier model is used to explain the enhanced nonlinearity in I-V curves. According to the energy-band model and fitting result, the nonlinearity in Au: CCTO film is mainly governed by thermionic emission in the reverse-biased Schottky barrier. This result not only supports the mechanism of double Schottky barrier in CCTO, but also indicates that the nonlinearity of current-voltage behavior could be improved in nanometal composite films, which has great significance for the resistance switching devices.

Combined Atomic Force Microscope-Based Topographical Imaging and Nanometer Scale Resolved Proximal Probe Thermal Desorption/Electrospray Ionization-Mass Spectrometry

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ovchinnikova, Olga S; Nikiforov, Maxim; Bradshaw, James A

2011-01-01

Nanometer scale proximal probe thermal desorption/electrospray ionization mass spectrometry (TD/ESI-MS) was demonstrated for molecular surface sampling of caffeine from a thin film using a 30 nm diameter nano-thermal analysis (nano-TA) probe tip in an atomic force microscope (AFM) coupled via a vapor transfer line and ESI interface to a MS detection platform. Using a probe temperature of 350 C and a spot sampling time of 30 s, conical desorption craters 250 nm in diameter and 100 nm deep were created as shown through subsequent topographical imaging of the surface within the same system. Automated sampling of a 5 x 2more » array of spots, with 2 m spacing between spots, and real time selective detection of the desorbed caffeine using tandem mass spectrometry was also demonstrated. Estimated from the crater volume (~2x106 nm3), only about 10 amol (2 fg) of caffeine was liberated from each thermal desorption crater in the thin film. These results illustrate a relatively simple experimental setup and means to acquire in automated fashion sub-micrometer scale spatial sampling resolution and mass spectral detection of materials amenable to TD. The ability to achieve MS-based chemical imaging with 250 nm scale spatial resolution with this system is anticipated.« less

Morphology-dependent photo-induced polarization recovery in ferroelectric thin films

NASA Astrophysics Data System (ADS)

Wang, J. Y.; Liu, G.; Sando, D.; Nagarajan, V.; Seidel, J.

2017-08-01

We investigate photo-induced ferroelectric domain switching in a series of Pb(Zr0.2Ti0.8)O3/La0.7Sr0.3MnO3 (PZT/LSMO) bilayer thin films with varying surface morphologies by piezoresponse force microscopy under light illumination. We demonstrate that reverse poled ferroelectric regions can be almost fully recovered under laser irradiation of the PZT layer and that the recovery process is dependent on the surface morphology on the nanometer scale. The recovery process is well described by the Kolmogorov-Avrami-Ishibashi model, and the evolution speed is controlled by light intensity, sample thickness, and initial write voltage. Our findings shed light on optical control of the domain structure in ferroelectric thin films with different surface morphologies.

Effect of cholesterol on electrostatics in lipid-protein films of a pulmonary surfactant.

PubMed

Finot, Eric; Leonenko, Yuri; Moores, Brad; Eng, Lukas; Amrein, Matthias; Leonenko, Zoya

2010-02-02

We report the changes in the electrical properties of the lipid-protein film of pulmonary surfactant produced by excess cholesterol. Pulmonary surfactant (PS) is a complex lipid-protein mixture that forms a molecular film at the interface of the lung's epithelia. The defined molecular arrangement of the lipids and proteins of the surfactant film gives rise to the locally highly variable electrical surface potential of the interface, which becomes considerably altered in the presence of cholesterol. With frequency modulation Kelvin probe force microscopy (FM-KPFM) and force measurements, complemented by theoretical analysis, we showed that excess cholesterol significantly changes the electric field around a PS film because of the presence of nanometer-sized electrostatic domains and affects the electrostatic interaction of an AFM probe with a PS film. These changes in the local electrical field would greatly alter the interaction of the surfactant film with charged species and would immediately impact the manner in which inhaled (often charged) airborne nanoparticles and fibers might interact with the lung interface.

Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating.

PubMed

Schlicke, Hendrik; Schröder, Jan H; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias

2011-07-29

A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.

Freestanding films of crosslinked gold nanoparticles prepared via layer-by-layer spin-coating

NASA Astrophysics Data System (ADS)

Schlicke, Hendrik; Schröder, Jan H.; Trebbin, Martin; Petrov, Alexey; Ijeh, Michael; Weller, Horst; Vossmeyer, Tobias

2011-07-01

A new, extremely efficient method for the fabrication of films comprised of gold nanoparticles (GNPs) crosslinked by organic dithiols is presented in this paper. The method is based on layer-by-layer spin-coating of both components, GNPs and crosslinker, and enables the deposition of films several tens of nanometers in thickness within a few minutes. X-ray diffraction and conductance measurements reveal the proper adjustment concentration of the crosslinker solution of the critical is in order to prevent the destabilization and coalescence of particles. UV/vis spectroscopy, atomic force microscopy, and conductivity measurements indicate that films prepared via layer-by-layer spin-coating are of comparable quality to coatings prepared via laborious layer-by-layer self-assembly using immersion baths. Because spin-coated films are not bound chemically to the substrate, they can be lifted-off by alkaline underetching and transferred onto 3d-electrodes to produce electrically addressable, freely suspended films. Comparative measurements of the sheet resistances indicate that the transfer process does not compromise the film quality.

Friction Durability of Extremely Thin Diamond-Like Carbon Films at High Temperature

PubMed Central

Miyake, Shojiro; Suzuki, Shota; Miyake, Masatoshi

2017-01-01

To clarify the friction durability, both during and after the high-temperature heating of nanometer-thick diamond-like carbon (DLC) films, deposited using filtered cathodic vacuum arc (FCVA) and plasma chemical vapor deposition (P-CVD) methods, the dependence of the friction coefficient on the load and sliding cycles of the DLC films, were evaluated. Cluster-I consisted of a low friction area in which the DLC film was effective, while cluster-II consisted of a high friction area in which the lubricating effect of the DLC film was lost. The friction durability of the films was evaluated by statistical cluster analysis. Extremely thin FCVA-DLC films exhibited an excellent wear resistance at room temperature, but their friction durability was decreased at high temperatures. In contrast, the durability of the P-CVD-DLC films was increased at high temperatures when compared with that observed at room temperature. This inverse dependence on temperature corresponded to the nano-friction results obtained by atomic force microscopy. The decrease in the friction durability of the FCVA-DLC films at high temperatures, was caused by a complex effect of temperature and friction. The tribochemical reaction produced by the P-CVD-DLC films reduced their friction coefficient, increasing their durability at high temperatures. PMID:28772520

Friction Durability of Extremely Thin Diamond-Like Carbon Films at High Temperature.

PubMed

Miyake, Shojiro; Suzuki, Shota; Miyake, Masatoshi

2017-02-10

To clarify the friction durability, both during and after the high-temperature heating of nanometer-thick diamond-like carbon (DLC) films, deposited using filtered cathodic vacuum arc (FCVA) and plasma chemical vapor deposition (P-CVD) methods, the dependence of the friction coefficient on the load and sliding cycles of the DLC films, were evaluated. Cluster-I consisted of a low friction area in which the DLC film was effective, while cluster-II consisted of a high friction area in which the lubricating effect of the DLC film was lost. The friction durability of the films was evaluated by statistical cluster analysis. Extremely thin FCVA-DLC films exhibited an excellent wear resistance at room temperature, but their friction durability was decreased at high temperatures. In contrast, the durability of the P-CVD-DLC films was increased at high temperatures when compared with that observed at room temperature. This inverse dependence on temperature corresponded to the nano-friction results obtained by atomic force microscopy. The decrease in the friction durability of the FCVA-DLC films at high temperatures, was caused by a complex effect of temperature and friction. The tribochemical reaction produced by the P-CVD-DLC films reduced their friction coefficient, increasing their durability at high temperatures.

High-Hall-Mobility Al-Doped ZnO Films Having Textured Polycrystalline Structure with a Well-Defined (0001) Orientation

NASA Astrophysics Data System (ADS)

Nomoto, Junichi; Makino, Hisao; Yamamoto, Tetsuya

2016-06-01

Five hundred-nanometer-thick ZnO-based textured polycrystalline films consisting of 490-nm-thick Al-doped ZnO (AZO) films deposited on 10-nm-thick Ga-doped ZnO (GZO) films exhibited a high Hall mobility ( μ H) of 50.1 cm2/Vs with a carrier concentration ( N) of 2.55 × 1020 cm-3. Firstly, the GZO films were prepared on glass substrates by ion plating with dc arc discharge, and the AZO films were then deposited on the GZO films by direct current magnetron sputtering (DC-MS). The GZO interface layers with a preferential c-axis orientation play a critical role in producing AZO films with texture development of a well-defined (0001) orientation, whereas 500-nm-thick AZO films deposited by only DC-MS showed a mixture of the c-plane and the other plane orientation, to exhibit a μ H of 38.7 cm2/Vs with an N of 2.22 × 1020 cm-3.

Cyclometalated ruthenium(II) complexes with a bis-carbene CCC-pincer ligand.

PubMed

Zhang, You-Ming; Shao, Jiang-Yang; Yao, Chang-Jiang; Zhong, Yu-Wu

2012-08-21

The first series of cyclometalated ruthenium complexes with a CCC-pincer bis-carbene ligand have been obtained as bench-stable compounds. Single-crystal X-ray analysis of one of these complexes with 4'-di-p-anisylamino-2,2':6',2''-terpyridine is presented. The Ru(II/III) redox potentials and MLCT absorptions of these complexes can be varied by attaching an electron-donating or -withdrawing group on the noncyclometalating ligand.

Epitaxial patterning of nanometer-thick Y 3Fe 5O 12 films with low magnetic damping

DOE PAGES

Li, Shaozhen; Zhang, Wei; Ding, Junjia; ...

2016-11-27

Magnetic insulators such as yttrium iron garnet, Y 3Fe 5O 12, with extremely low magnetic damping have opened the door for low power spin-orbitronics due to their low energy dissipation and effcient spin current generation and transmission. We demonstrate reliable and effcient epitaxial growth and nanopatterning of Y 3Fe 5O 12 thin-film based nanostructures on insulating Gd 3Ga 5O 12 substrates. In particular, our fabrication process is compatible with conventional sputtering and liftoff, and does not require aggressive ion milling which may be detrimental to the oxide thin films. Structural and magnetic properties indicate good qualities, in particular low magneticmore » damping of both films and patterned structures. The dynamic magnetic properties of the nanostructures are systematically investigated as a function of the lateral dimension. By comparing to ferromagnetic nanowire structures, a distinct edge mode in addition to the main mode is identified by both experiments and simulations, which also exhibits cross-over with the main mode upon varying the width of the wires. In conclusion, the non-linear evolution of dynamic modes over nanostructural dimensions highlights the important role of size confinement to their material properties in magnetic devices where Y 3Fe 5O 12 nanostructures serve as the key functional component.« less

Correlation between microstructure and thermionic electron emission from Os-Ru thin films on dispenser cathodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Swartzentruber, Phillip D.; John Balk, Thomas, E-mail: john.balk@uky.edu; Effgen, Michael P.

2014-07-01

Osmium-ruthenium films with different microstructures were deposited onto dispenser cathodes and subjected to 1000 h of close-spaced diode testing. Tailored microstructures were achieved by applying substrate biasing during deposition, and these were evaluated with scanning electron microscopy, x-ray diffraction, and energy dispersive x-ray spectroscopy before and after close-spaced diode testing. Knee temperatures determined from the close-spaced diode test data were used to evaluate cathode performance. Cathodes with a large (10-11) Os-Ru film texture possessed comparatively low knee temperatures. Furthermore, a low knee temperature correlated with a low effective work function as calculated from the close-spaced diode data. It is proposedmore » that the formation of strong (10-11) texture is responsible for the superior performance of the cathode with a multilayered Os-Ru coating.« less

Spatiotemporal evolution of thin liquid films during impact of water bubbles on glass on a micrometer to nanometer scale.

PubMed

Hendrix, Maurice H W; Manica, Rogerio; Klaseboer, Evert; Chan, Derek Y C; Ohl, Claus-Dieter

2012-06-15

Collisions between millimeter-size bubbles in water against a glass plate are studied using high-speed video. Bubble trajectory and shape are tracked simultaneously with laser interferometry between the glass and bubble surfaces that monitors spatial-temporal evolution of the trapped water film. Initial bubble bounces and the final attachment of the bubble to the surface have been quantified. While the global Reynolds number is large (∼10(2)), the film Reynolds number remains small and permits analysis with lubrication theory with tangentially immobile boundary condition at the air-water interface. Accurate predictions of dimple formation and subsequent film drainage are obtained.

A simple and low temperature process for super-hydrophilic rutile TiO 2 thin films growth

NASA Astrophysics Data System (ADS)

Mane, R. S.; Joo, Oh-Shim; Min, Sun-Ki; Lokhande, C. D.; Han, Sung-Hwan

2006-11-01

We investigate an environmentally friendly aqueous solution system for rutile TiO2 violet color nanocrystalline thin films growth on ITO substrate at room temperature. Film shows considerable absorption in visible region with excitonic maxima at 434 nm. X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), selected area electron diffraction (SAED), UV-vis, water surface contact angle and energy dispersive X-ray analysis (EDX) techniques in addition to actual photo-image that shows purely rutile phase of TiO2 with violet color, super-hydrophilic and densely packed nanometer-sized spherical grains of approximate diameter 3.15 ± 0.4 nm, characterize the films. Band gap energy of 4.61 eV for direct transition was obtained for the rutile TiO2 films. Film surface shows super-hydrophilic behavior, as exhibited water contact angle was 7°. Strong visible absorption (not due to chlorine) leaves future challenge to use these films in extremely thin absorber (ETA) solar cells.

Influence of Thickness on the Electrical Transport Properties of Exfoliated Bi2Te3 Ultrathin Films

NASA Astrophysics Data System (ADS)

Mo, D. L.; Wang, W. B.; Cai, Q.

2016-08-01

In this work, the mechanical exfoliation method has been utilized to fabricate Bi2Te3 ultrathin films. The thickness of the ultrathin films is revealed to be several tens of nanometers. Weak antilocalization effects and Shubnikov de Haas oscillations have been observed in the magneto-transport measurements on individual films with different thickness, and the two-dimensional surface conduction plays a dominant role. The Fermi level is found to be 81 meV above the Dirac point, and the carrier mobility can reach ~6030 cm2/(Vs) for the 10-nm film. When the film thickness decreases from 30 to 10 nm, the Fermi level will move 8 meV far from the bulk valence band. The coefficient α in the Hikami-Larkin-Nagaoka equation is shown to be ~0.5, manifesting that only the bottom surface of the Bi2Te3 ultrathin films takes part in transport conductions. These will pave the way for understanding thoroughly the surface transport properties of topological insulators.

Advanced Electrochemistry of Individual Metal Clusters Electrodeposited Atom by Atom to Nanometer by Nanometer.

PubMed

Kim, Jiyeon; Dick, Jeffrey E; Bard, Allen J

2016-11-15

Metal clusters are very important as building blocks for nanoparticles (NPs) for electrocatalysis and electroanalysis in both fundamental and applied electrochemistry. Attention has been given to understanding of traditional nucleation and growth of metal clusters and to their catalytic activities for various electrochemical applications in energy harvesting as well as analytical sensing. Importantly, understanding the properties of these clusters, primarily the relationship between catalysis and morphology, is required to optimize catalytic function. This has been difficult due to the heterogeneities in the size, shape, and surface properties. Thus, methods that address these issues are necessary to begin understanding the reactivity of individual catalytic centers as opposed to ensemble measurements, where the effect of size and morphology on the catalysis is averaged out in the measurement. This Account introduces our advanced electrochemical approaches to focus on each isolated metal cluster, where we electrochemically fabricated clusters or NPs atom by atom to nanometer by nanometer and explored their electrochemistry for their kinetic and catalytic behavior. Such approaches expand the dimensions of analysis, to include the electrochemistry of (1) a discrete atomic cluster, (2) solely a single NP, or (3) individual NPs in the ensemble sample. Specifically, we studied the electrocatalysis of atomic metal clusters as a nascent electrocatalyst via direct electrodeposition on carbon ultramicroelectrode (C UME) in a femtomolar metal ion precursor. In addition, we developed tunneling ultramicroelectrodes (TUMEs) to study electron transfer (ET) kinetics of a redox probe at a single metal NP electrodeposited on this TUME. Owing to the small dimension of a NP as an active area of a TUME, extremely high mass transfer conditions yielded a remarkably high standard ET rate constant, k 0 , of 36 cm/s for outer-sphere ET reaction. Most recently, we advanced nanoscale

Programmable Bidirectional Folding of Metallic Thin Films for 3D Chiral Optical Antennas.

PubMed

Mao, Yifei; Zheng, Yun; Li, Can; Guo, Lin; Pan, Yini; Zhu, Rui; Xu, Jun; Zhang, Weihua; Wu, Wengang

2017-05-01

3D structures with characteristic lengths ranging from nanometer to micrometer scale often exhibit extraordinary optical properties, and have been becoming an extensively explored field for building new generation nanophotonic devices. Albeit a few methods have been developed for fabricating 3D optical structures, constructing 3D structures with nanometer accuracy, diversified materials, and perfect morphology is an extremely challenging task. This study presents a general 3D nanofabrication technique, the focused ion beam stress induced deformation process, which allows a programmable and accurate bidirectional folding (-70°-+90°) of various metal and dielectric thin films. Using this method, 3D helical optical antennas with different handedness, improved surface smoothness, and tunable geometries are fabricated, and the strong optical rotation effects of single helical antennas are demonstrated. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Long-range electron transport of ruthenium-centered multilayer films via a stepping-stone mechanism.

PubMed

Terada, Kei-ichi; Nakamura, Hisao; Kanaizuka, Katsuhiko; Haga, Masa-aki; Asai, Yoshihiro; Ishida, Takao

2012-03-27

We studied electron transport of Ru complex multilayer films, whose structure resembles redox-active complex films known in the literature to have long-range electron transport abilities. Hydrogen bond formation in terms of pH control was used to induce spontaneous growth of a Ru complex multilayer. We made a cross-check between electrochemical measurements and I-V measurements using PEDOT:PSS to eliminate the risk of pinhole contributions to the mechanism and have found small β values of 0.012-0.021 Å(-1). Our Ru complex layers exhibit long-range electron transport but with low conductance. On the basis of the results of our theoretical-experimental collaboration, we propose a modified tunneling mechanism named the "stepping-stone mechanism", where the alignment of site potentials forms a narrow band around E(F), making resonant tunneling possible. Our observations may support Tuccito et al.'s proposed mechanism. © 2012 American Chemical Society

A promising new thermoelectric material - Ruthenium silicide

NASA Technical Reports Server (NTRS)

Vining, Cronin B.; Mccormack, Joseph A.; Zoltan, Andrew; Zoltan, Leslie D.

1991-01-01

Experimental and theoretical efforts directed toward increasing thermoelectric figure of merit values by a factor of 2 or 3 have been encouraging in several respects. An accurate and detailed theoretical model developed for n-type silicon-germanium (SiGe) indicates that ZT values several times higher than currently available are expected under certain conditions. These new, high ZT materials are expected to be significantly different from SiGe, but not unreasonably so. Several promising candidate materials have been identified which may meet the conditions required by theory. One such candidate, ruthenium silicide, currently under development at JPL, has been estimated to have the potential to exhibit figure of merit values 4 times higher than conventional SiGe materials. Recent results are summarized.

Ruthenium nanoparticles decorated curl-like porous carbons for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Lou, Bih-Show; Veerakumar, Pitchaimani; Chen, Shen-Ming; Veeramani, Vediyappan; Madhu, Rajesh; Liu, Shang-Bin

2016-01-01

The synthesis of highly dispersed and stable ruthenium nanoparticles (RuNPs; ca. 2-3 nm) on porous activated carbons derived from Moringa Oleifera fruit shells (MOC) is reported and were exploited for supercapacitor applications. The Ru/MOC composites so fabricated using the biowaste carbon source and ruthenium acetylacetonate as the co-feeding metal precursors were activated at elevated temperatures (600-900 oC) in the presence of ZnCl2 as the pore generating and chemical activating agent. The as-prepared MOC carbonized at 900 oC was found to possess a high specific surface area (2522 m2 g-1) and co-existing micro- and mesoporosities. Upon incorporating RuNPs, the Ru/MOC nanocomposites loaded with modest amount of metallic Ru (1.0-1.5 wt%) exhibit remarkable electrochemical and capacitive properties, achiving a maximum capacitance of 291 F g-1 at a current density of 1 A g-1 in 1.0 M H2SO4 electrolyte. These highly stable and durable Ru/MOC electrodes, which can be facily fabricated by the eco-friendly and cost-effective route, should have great potentials for practical applications in energy storage, biosensing, and catalysis.

Improvement of corrosion resistance of NiTi sputtered thin films by anodization

NASA Astrophysics Data System (ADS)

Bayat, N.; Sanjabi, S.; Barber, Z. H.

2011-08-01

Anodization of sputtered NiTi thin films has been studied in 1 M acetic acid at 23 °C for different voltages from 2 to 10 V. The morphology and cross-sectional structures of the untreated and anodized surfaces were investigated by field emission scanning electron microscopy (FE-SEM). The results show that increasing anodization voltage leads to film surface roughening and unevenness. It can be seen that the thickness of the anodized layer formed on the NiTi surface is in the nanometer range. The corrosion resistance of anodized thin films was studied by potentiodynamic scan (PDS) and impedance spectroscopy (EIS) techniques in Hank's solution at 310 K (37 °C). It was shown that the corrosion resistance of the anodized film surface improved with increasing voltage to 6 V. Anodization of austenitic sputtered NiTi thin films has also been studied, in the same anodizing conditions, at 4 V. Comparison of anodized sputtered NiTi thin films with anodized austenitic shape memory films illustrate that the former are more corrosion resistant than the latter after 1 h immersion in Hank's solution, which is attributed to the higher grain boundary density to quickly form a stable and protective passive film.

Particle size reduction to the nanometer range: a promising approach to improve buccal absorption of poorly water-soluble drugs

PubMed Central

Rao, Shasha; Song, Yunmei; Peddie, Frank; Evans, Allan M

2011-01-01

Poorly water-soluble drugs, such as phenylephrine, offer challenging problems for buccal drug delivery. In order to overcome these problems, particle size reduction (to the nanometer range) and cyclodextrin complexation were investigated for permeability enhancement. The apparent solubility in water and the buccal permeation of the original phenylephrine coarse powder, a phenylephrine–cyclodextrin complex and phenylephrine nanosuspensions were characterized. The particle size and particle surface properties of phenylephrine nanosuspensions were used to optimize the size reduction process. The optimized phenylephrine nanosuspension was then freeze dried and incorporated into a multi-layered buccal patch, consisting of a small tablet adhered to a mucoadhesive film, yielding a phenylephrine buccal product with good dosage accuracy and improved mucosal permeability. The design of the buccal patch allows for drug incorporation without the need to change the mucoadhesive component, and is potentially suited to a range of poorly water-soluble compounds. PMID:21753876

Particle size reduction to the nanometer range: a promising approach to improve buccal absorption of poorly water-soluble drugs.

PubMed

Rao, Shasha; Song, Yunmei; Peddie, Frank; Evans, Allan M

2011-01-01

Poorly water-soluble drugs, such as phenylephrine, offer challenging problems for buccal drug delivery. In order to overcome these problems, particle size reduction (to the nanometer range) and cyclodextrin complexation were investigated for permeability enhancement. The apparent solubility in water and the buccal permeation of the original phenylephrine coarse powder, a phenylephrine-cyclodextrin complex and phenylephrine nanosuspensions were characterized. The particle size and particle surface properties of phenylephrine nanosuspensions were used to optimize the size reduction process. The optimized phenylephrine nanosuspension was then freeze dried and incorporated into a multi-layered buccal patch, consisting of a small tablet adhered to a mucoadhesive film, yielding a phenylephrine buccal product with good dosage accuracy and improved mucosal permeability. The design of the buccal patch allows for drug incorporation without the need to change the mucoadhesive component, and is potentially suited to a range of poorly water-soluble compounds.

Dual function catalysts. Dehydrogenation and asymmetric intramolecular Diels-Alder cycloaddition of N-hydroxy formate esters and hydroxamic acids: evidence for a ruthenium-acylnitroso intermediate.

PubMed

Chow, Chun P; Shea, Kenneth J

2005-03-23

The chiral ruthenium salen complex, 13b, functions as an efficient catalyst for the sequential oxidation and asymmetric Diels-Alder cycloaddition of hydroxamic acids and N-hydroxy formate esters. This result provides evidence for the formation of a ruthenium-nitroso formate (acyl nitroso) intermediate. The Diels-Alder precursors are prepared from simple building blocks, and the cycloadducts, bridged oxazinolactams, can serve as useful intermediates in organic synthesis.

Experimental correlation between nonlinear optical and magnetotransport properties observed in Au-Co thin films

DOE PAGES

Yang, Kaida; Kryutyanskiy, Victor; Kolmychek, Irina; ...

2016-01-01

Magnetic materials where at least one dimension is in the nanometer scale typically exhibit different magnetic, magnetotransport, and magnetooptical properties compared to bulk materials. Composite magnetic thin films where the matrix composition, magnetic cluster size, and overall composite film thickness can be experimentally tailored via adequate processing or growth parameters offer a viable nanoscale platform to investigate possible correlations between nonlinear magnetooptical and magnetotransport properties, since both types of properties are sensitive to the local magnetization landscape. As a result, it has been shown that the local magnetization contrast affects the nonlinear magnetooptical properties as well as the magnetotransport propertiesmore » in magnetic-metal/nonmagnetic metal multilayers; thus, nanocomposite films showcase another path to investigate possible correlations between these distinct properties which may prove useful for sensing applications.« less

Exploring the heterogeneous interfaces in organic or ruthenium dye-sensitized liquid- and solid-state solar cells.

PubMed

Kwon, Young Soo; Song, Inwoo; Lim, Jong Chul; Song, In Young; Siva, Ayyanar; Park, Taiho

2012-06-27

The interfacial properties were systematically investigated using an organic sensitizer (3-(5'-{4-[(4-tert-butyl-phenyl)-p-tolyl-amino]-phenyl}-[2,2']bithiophenyl-5-yl)-2-cyano-acrylic acid (D)) and inorganic sensitizer (bis(tetrabutylammonium) cis-bis(thiocyanato)bis(2,2'-bipyridine-4,4'-dicarboxylato) ruthenium(II) (N719)) in a liquid-state and a solid-state dye-sensitized solar cell (DSC). For liquid-DSCs, the faster charge recombination for the surface of D-sensitized TiO2 resulted in shorter diffusion length (LD) of ∼3.9 μm than that of N719 (∼7.5 μm), limiting the solar cell performance at thicker films used in liquid-DSCs. On the other hand, for solid-DSCs using thin TiO2 films (∼ 2 μm), D-sensitized device outperforms the N719-sensitized device in an identical fabrication condition, mainly due to less perfect wetting ability of solid hole conductor into the porous TiO2 network, inducing the dye monolayer act as an insulation layer, while liquid electrolyte is able to fully wet the surface of TiO2. Such insulation effect was attributed to the fact that the significant increase in recombination resistance (from 865 to 4,400 Ω/cm(2)) but shorter electron lifetime (from 10.8 to 0.8 ms) when compared to liquid-DSCs. Higher recombination resistance for solid-DSCs induced the electron transport-limited situation, showing poor performance of N719-sensitized device which has shorter electron transport time and similar LD (2.9 μm) with D-sensitized device (3.0 μm).

Room temperature aerobic oxidation of amines by a nanocrystalline ruthenium oxide pyrochlore nafion composite catalyst.

PubMed

Venkatesan, Shanmuganathan; Kumar, Annamalai Senthil; Lee, Jyh-Fu; Chan, Ting-Shan; Zen, Jyh-Myng

2012-05-14

The aerobic oxidation of primary amines to their respective nitriles has been carried out at room temperature using a highly reusable nanocrystalline ruthenium oxide pyrochlore Nafion composite catalyst (see figure). Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnetically Recoverable Supported Ruthenium Catalyst for Hydrogenation of Alkynes and Transfer Hydrogenation of Carbonyl Compounds

EPA Science Inventory

A ruthenium (Ru) catalyst supported on magnetic nanoparticles (NiFe2O4) has been successfully synthesized and used for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The cata...

Forces and thin water film drainage in deformable asymmetric nanoscale contacts.

PubMed

Schönherr, Holger

2015-01-27

Gas-liquid interfaces are omnipresent in daily life, and processes involving these interfaces are the basis for a broad range of applications that span from established industrial processes to modern microengineering, technology, and medical applications for diagnosis and treatment. Despite the rapid progress in understanding intermolecular forces at such interfaces from a theoretical point of view and, in particular, from an experimental point of view down to sub-nanometer length scales, the quantitative description of all relevant forces, particularly the hydrophobic interaction and the dynamic behavior of nanometer-scale confined water films, was until now unsatisfactory. This situation is particularly the case for the elusive description and understanding of the origins of the so-called hydrophobic interaction. For soft, deformable interfaces, such as those found in asymmetric contacts between gas bubbles and a solid, a complete picture has begun to emerge that has direct consequences for interfacial water at (bio)interfaces, functionalized gas microbubbles, surface nanobubbles, and beyond.

Fabrication and Structural Characterization of an Ultrathin Film of a Two-Dimensional-Layered Metal-Organic Framework, {Fe(py)2[Ni(CN)4]} (py = pyridine).

PubMed

Sakaida, Shun; Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

2017-07-17

We report the fabrication and characterization of the first example of a tetracyanonickelate-based two-dimensional-layered metal-organic framework, {Fe(py) 2 Ni(CN) 4 } (py = pyridine), thin film. To fabricate a nanometer-sized thin film, we utilized the layer-by-layer method, whereby a substrate was alternately soaked in solutions of the structural components. Surface X-ray studies revealed that the fabricated film was crystalline with well-controlled growth directions both parallel and perpendicular to the substrate. In addition, lattice parameter analysis indicated that the crystal system is found to be close to higher symmetry by being downsized to a thin film.

A novel interferometric method for the study of the viscoelastic properties of ultra-thin polymer films determined from nanobubble inflation

NASA Astrophysics Data System (ADS)

Chapuis, P.; Montgomery, P. C.; Anstotz, F.; Leong-Hoï, A.; Gauthier, C.; Baschnagel, J.; Reiter, G.; McKenna, G. B.; Rubin, A.

2017-09-01

Glass formation and glassy behavior remain as the important areas of investigation in soft matter physics with many aspects which are still not completely understood, especially at the nanometer size-scale. In the present work, we show an extension of the "nanobubble inflation" method developed by O'Connell and McKenna [Rev. Sci. Instrum. 78, 013901 (2007)] which uses an interferometric method to measure the topography of a large array of 5 μ m sized nanometer thick films subjected to constant inflation pressures during which the bubbles grow or creep with time. The interferometric method offers the possibility of making measurements on multiple bubbles at once as well as having the advantage over the AFM methods of O'Connell and McKenna of being a true non-contact method. Here we demonstrate the method using ultra-thin films of both poly(vinyl acetate) (PVAc) and polystyrene (PS) and discuss the capabilities of the method relative to the AFM method, its advantages and disadvantages. Furthermore we show that the results from experiments on PVAc are consistent with the prior work on PVAc, while high stress results with PS show signs of a new non-linear response regime that may be related to the plasticity of the ultra-thin film.

Cryogenic colocalization microscopy for nanometer-distance measurements.

PubMed

Weisenburger, Siegfried; Jing, Bo; Hänni, Dominik; Reymond, Luc; Schuler, Benjamin; Renn, Alois; Sandoghdar, Vahid

2014-03-17

The main limiting factor in spatial resolution of localization microscopy is the number of detected photons. Recently we showed that cryogenic measurements improve the photostability of fluorophores, giving access to Angstrom precision in localization of single molecules. Here, we extend this method to colocalize two fluorophores attached to well-defined positions of a double-stranded DNA. By measuring the separations of the fluorophore pairs prepared at different design positions, we verify the feasibility of cryogenic distance measurement with sub-nanometer accuracy. We discuss the important challenges of our method as well as its potential for further improvement and various applications.

Extraordinary optical transmission in nanopatterned ultrathin metal films without holes

DOE PAGES

Peer, Akshit; Biswas, Rana

2016-02-01

In this study, we experimentally and theoretically demonstrate that a continuous gold film on a periodically textured substrate exhibits extraordinary optical transmission, even though no holes were etched in the film. Our film synthesis started by nanoimprinting a periodic array of nanocups with a period of ~750 nm on a polystyrene film over a glass substrate. A thin non-conformal gold film was sputter-deposited on the polystyrene by angle-directed deposition. The gold film was continuous with spatial thickness variation, the film being thinnest at the bottom of the nanocup. Measurements revealed an extraordinary transmission peak at a wavelength just smaller thanmore » the period, with an enhancement of ~2.5 compared to the classically expected value. Scattering matrix simulations model well the transmission and reflectance measurements when an ultrathin gold layer (~5 nm), smaller than the skin depth is retained at the bottom of the nanocups. Electric field intensities are enhanced by >100 within the nanocup, and ~40 in the ultrathin gold layer causing transmission through it. We show a wavelength red-shift of ~30 nm in the extraordinary transmission peak when the nanocups are coated with a thin film of a few nanometers, which can be utilized for biosensing. The continuous corrugated metal films are far simpler structures to observe extraordinary transmission, circumventing the difficult process of etching the metal film. Such continuous metal films with ultrathin regions are simple platforms for non-linear optics, plasmonics, and biological and chemical sensing.« less

Progress in doping of ruthenium silicide (Ru2Si3)

NASA Technical Reports Server (NTRS)

Vining, C. B.; Allevato, C. E.

1992-01-01

Ruthenium silicide is currently under development as a promising thermoelectric material suitable for space power applications. Key to realizing the potentially high figure of merit values of this material is the development of appropriate doping techniques. In this study, manganese and iridium have been identified as useful p- and n-type dopants, respectively. Resistivity values have been reduced by more than 3 orders of magnitude. Anomalous Hall effect results, however, complicate interpretation of some of the results and further effort is required to achieve optimum doping levels.

Tracing temperature in a nanometer size region in a picosecond time period.

PubMed

Nakajima, Kaoru; Kitayama, Takumi; Hayashi, Hiroaki; Matsuda, Makoto; Sataka, Masao; Tsujimoto, Masahiko; Toulemonde, Marcel; Bouffard, Serge; Kimura, Kenji

2015-08-21

Irradiation of materials with either swift heavy ions or slow highly charged ions leads to ultrafast heating on a timescale of several picosecond in a region of several nanometer. This ultrafast local heating result in formation of nanostructures, which provide a number of potential applications in nanotechnologies. These nanostructures are believed to be formed when the local temperature rises beyond the melting or boiling point of the material. Conventional techniques, however, are not applicable to measure temperature in such a localized region in a short time period. Here, we propose a novel method for tracing temperature in a nanometer region in a picosecond time period by utilizing desorption of gold nanoparticles around the ion impact position. The feasibility is examined by comparing with the temperature evolution predicted by a theoretical model.

Reaction-diffusion-induced explosive crystallization in a metal-selenium nanometer film structure

NASA Astrophysics Data System (ADS)

Kogai, V. Ya.

2016-03-01

Experimental data for reaction-diffusion-induced explosive crystallization in a nanodimensional metal (Cu, Ag)/selenium structure are presented. It is found that after the metal layer has completely diffused into the amorphous Se film, the electrical potential rises from 0.14 to 1.21 V in the Cu(30 nm)/Se(140 nm) heterolayer and from 0.01 to 1.17 V in the Ag(30 nm)/Se(140 nm) heterolayer. The metals diffusing into the amorphous Se layer interact with Se, forming nuclei of a new phase (CuSe or Ag2Se). The intense growth of the CuSe and Ag2Se crystallization centers results in a considerable liberation of latent energy in the form of phase transformation heat and in explosive growth of CuSe and Ag2Se nanocrystalline particles. The mean size of CuSe and Ag2Se crystallites equals 25 and 50 nm, respectively.

A DFT-D study on the electronic and photophysical properties of ruthenium (II) complex with a chelating sulfoxide group

NASA Astrophysics Data System (ADS)

Li, Huifang; Zhang, Lisheng; Lin, Hui; Fan, Xiaolin

2014-06-01

Electronic and photophysical properties of [Ru(bpy)2(OSO)]+ (bpy = 2,2‧-bipyridine; OSO = methylsulfinylbenzoate) were examined theoretically to better understand the differences between S- and O-linked ruthenium sulfoxide complexes. It is found that the strength of Ru-O1 linkage is significantly larger than that of Ru-S linkage, which makes the charge transfer amount from surrounding ligands to central Ru decreased. The energy gap is closed due to the highest occupied molecular orbital energy increases to a larger extent than the lowest unoccupied molecular orbital energy. Thereby, red shifted absorption and emission maxima in such photochromic ruthenium sulfoxide complexes can be explained.

An Atom-Economic and Selective Ruthenium-Catalyzed Redox Isomerization of Propargylic Alcohols. An Efficient Strategy for the Synthesis of Leukotrienes

PubMed Central

Trost, Barry M.; Livingston, Robert C.

2008-01-01

Catalytic ruthenium complexes in conjunction with an indium cocatalyst and Bronsted acid isomerize primary and secondary propargylic alcohols in good yields to provide trans enals and enones exclusively. Readily available indenylbis(triphenylphosphine)ruthenium chloride in the presence of indium triflate and camphorsulfonic acid give the best turnover numbers and reactivity with the broadest range of substrates. Deuterium labeling experiments suggest that the process occurs through propargylic hydride migration followed by protic cleavage of the resultant vinylruthenium intermediate. Application of this method to the synthesis of leukotriene B4 demonstrates its utility and extraordinary selectivity. PMID:18702463

Electrical and optical properties of carbon films

NASA Astrophysics Data System (ADS)

Kulkarni, Pranita

Carbon and carbon-based materials, including graphite, diamond, and other thin-film structures, are being intensively researched for a wide range of electronic applications. A variety of graphitic, nano-structured carbon materials can be synthesized that have current or potential applications as thin-film transistors, photovoltaics, and supercapacitors. Diamond has been pursued for many years for electronics that can be used in extreme conditions, such as high temperature, high power, high frequency, and radiation environments. In this research study, electronic properties of diamond and graphitic films with crystallite or grain sizes in the nanometer range were investigated. The nano-structured graphitic carbon films were grown using a previously developed method based on the pyrolysis of poly(acrylonitrile) and poly(n-butyl acrylate) block copolymers (PAN-b-PBA). An important characteristic of these films is that the morphology (and therefore other properties) can be controlled by the compositions and processing of the starting block copolymers. Spherical, cylindrical, lamellar, and branched morphologies have been fabricated. The crystallite sizes, optical absorption, and morphology of PAN-b-PBA (containing 17.8% PAN) pyrolyzed between 400 and 600°C were determined and were compared to those derived by pyrolysis of PAN homopolymers at the same temperatures. Hall-effect measurements on pyrolyzed PAN-b-PBA films with spherical, cylindrical, and branched morphologies and homopolymer PAN films pyrolyzed at the same temperatures revealed that both PAN-b-PBA with different morphologies and PAN homopolymer-derived films had n-type conductivity; differences in carrier concentration and mobility values were correlated with the morphological differences of the films. Optical absorption measurements in the ultra-violet through visible wavelength range were also conducted on these films; measurements of the pseudo band-gaps and absorption coefficients were correlated with

Ruthenium brachytherapy for uveal melanoma - single institution experience.

PubMed

Rospond-Kubiak, Iwona; Wróblewska-Zierhoffer, Marta; Twardosz-Pawlik, Hanna; Kocięcki, Jarosław

2017-12-01

The aim of this study was to report on results of uveal melanoma treatment with ruthenium-106 ( 106 Ru) brachytherapy with long-term follow-up, in terms of local tumor control, eye retention rate, radiation retinopathy, and patients' survival. Medical records of patients treated with ruthenium plaque due to uveal melanoma at the Department of Ophthalmology, Poznan University of Medical Sciences, Poland, between 1994 and 2014 were retrospectively reviewed. We identified 126 patients: 53 men, 73 women, mean age 60.04 years (range, 21-89). The largest basal diameter ranged from 4.04 mm to 18.9 mm (median, 10.67 mm), tumor height was 1.9 mm to 7.42 mm (median, 4.8 mm). Median scleral radiation dose was 570 Gy (range, 235-1,500 Gy), median apical dose 100 Gy (range, 60-129 Gy). Median follow-up was 66.5 months (range, 2-261 months). We noted a total of 19 (15%) recurrences. The actuarial rate of recurrence was 9.5% at 3 years, and 13.5% at 5 years postoperatively. Nine (7%) eye globes were lost, median time to enucleation was 5 years. The eye retention rate at 5 years was 92.7% and 81% at 10 years. Forty-three (34%) patients died before the end of the study, 24 (19%) of them due to metastatic disease. Metastatic death was related to: tumor size and TNM stage at presentation ( p = 0.002 vs. p = 0.0006, respectively) but not to age, gender, and plaque dosimetry. 106 Ru brachytherapy is an effective, globe sparing treatment that provides good tumor control and a high rate of survival. However, some ocular complications tend to appear late post-treatment, and therefore long-term follow-up is advised.

Role of high microwave power on growth and microstructure of thick nanocrystalline diamond films: A comparison with large grain polycrystalline diamond films

NASA Astrophysics Data System (ADS)

Tang, C. J.; Fernandes, A. J. S.; Girão, A. V.; Pereira, S.; Shi, Fa-Nian; Soares, M. R.; Costa, F.; Neves, A. J.; Pinto, J. L.

2014-03-01

In this work, we study the growth habit of nanocrystalline diamond (NCD) films by exploring the very high power regime, up to 4 kW, in a 5 kW microwave plasma chemical vapour deposition (MPCVD) reactor, through addition of a small amount of nitrogen and oxygen (0.24%) into 4% CH4 in H2 plasma. The coupled effect of high microwave power and substrate temperature on NCD growth behaviour is systematically investigated by varying only power, while fixing the remaining operating parameters. When the power increases from 2 kW to 4 kW, resulting also in rise of the Si substrate temperature higher than 150 °C, the diamond films obtained maintain the NCD habit, while the growth rate increases significantly. The highest growth rate of 4.6 μm/h is achieved for the film grown at 4 kW, which represents a growth rate enhancement of about 15 times compared with that obtained when using 2 kW power. Possible factors responsible for such remarkable growth rate enhancement of the NCD films are discussed. The evolution of NCD growth characteristics such as morphology, microstructure and texture is studied by growing thick films and comparing it with that of large grain polycrystalline (PCD) films. One important characteristic of the NCD films obtained, in contrast to PCD films, is that irrespective of deposition time (i.e. film thickness), their grain size and surface roughness remain in the nanometer range throughout the growth. Finally, based on our present and previous experimental results, a potential parameter window is established for fast growth of NCD films under high power conditions.

Ruthenium-catalyzed aerobic oxidative decarboxylation of amino acids: a green, zero-waste route to biobased nitriles.

PubMed

Claes, Laurens; Verduyckt, Jasper; Stassen, Ivo; Lagrain, Bert; De Vos, Dirk E

2015-04-18

Oxidative decarboxylation of amino acids into nitriles was performed using molecular oxygen as terminal oxidant and a heterogeneous ruthenium hydroxide-based catalyst. A range of amino acids was oxidized in very good yield, using water as the solvent.

Preparation of high-strength nanometer scale twinned coating and foil

DOEpatents

Zhang, Xinghang [Los Alamos, NM; Misra, Amit [Los Alamos, NM; Nastasi, Michael A [Santa Fe, NM; Hoagland, Richard G [Santa Fe, NM

2006-07-18

Very high strength single phase stainless steel coating has been prepared by magnetron sputtering onto a substrate. The coating has a unique microstructure of nanometer spaced twins that are parallel to each other and to the substrate surface. For cases where the coating and substrate do not bind strongly, the coating can be peeled off to provide foil.

Atomic layer deposition of ruthenium on plasma-treated vertically aligned carbon nanotubes for high-performance ultracapacitors.

PubMed

Kim, Jun Woo; Kim, Byungwoo; Park, Suk Won; Kim, Woong; Shim, Joon Hyung

2014-10-31

It is challenging to realize a conformal metal coating by atomic layer deposition (ALD) because of the high surface energy of metals. In this study, ALD of ruthenium (Ru) on vertically aligned carbon nanotubes (CNTs) was carried out. To activate the surface of CNTs that lack surface functional groups essential for ALD, oxygen plasma was applied ex situ before ALD. X-ray photoelectron spectroscopy and Raman spectroscopy confirmed surface activation of CNTs by the plasma pretreatment. Transmission electron microscopy analysis with energy-dispersive x-ray spectroscopy composition mapping showed that ALD Ru grew conformally along CNTs walls. ALD Ru/CNTs were electrochemically oxidized to ruthenium oxide (RuOx) that can be a potentially useful candidate for use in the electrodes of ultracapacitors. Electrode performance of RuOx/CNTs was evaluated using cyclic voltammetry and galvanostatic charge-discharge measurements.

High performance sandwich structured Si thin film anodes with LiPON coating

NASA Astrophysics Data System (ADS)

Luo, Xinyi; Lang, Jialiang; Lv, Shasha; Li, Zhengcao

2018-04-01

The sandwich structured silicon thin film anodes with lithium phosphorus oxynitride (LiPON) coating are synthesized via the radio frequency magnetron sputtering method, whereas the thicknesses of both layers are in the nanometer range, i.e. between 50 and 200 nm. In this sandwich structure, the separator simultaneously functions as a flexible substrate, while the LiPON layer is regarded as a protective layer. This sandwich structure combines the advantages of flexible substrate, which can help silicon release the compressive stress, and the LiPON coating, which can provide a stable artificial solidelectrolyte interphase (SEI) film on the electrode. As a result, the silicon anodes are protected well, and the cells exhibit high reversible capacity, excellent cycling stability and good rate capability. All the results demonstrate that this sandwich structure can be a promising option for high performance Si thin film lithium ion batteries.

High performance sandwich structured Si thin film anodes with LiPON coating

NASA Astrophysics Data System (ADS)

Luo, Xinyi; Lang, Jialiang; Lv, Shasha; Li, Zhengcao

2018-06-01

The sandwich structured silicon thin film anodes with lithium phosphorus oxynitride (LiPON) coating are synthesized via the radio frequency magnetron sputtering method, whereas the thicknesses of both layers are in the nanometer range, i.e. between 50 and 200 nm. In this sandwich structure, the separator simultaneously functions as a flexible substrate, while the LiPON layer is regarded as a protective layer. This sandwich structure combines the advantages of flexible substrate, which can help silicon release the compressive stress, and the LiPON coating, which can provide a stable artificial solid-electrolyte interphase (SEI) film on the electrode. As a result, the silicon anodes are protected well, and the cells exhibit high reversible capacity, excellent cycling stability and good rate capability. All the results demonstrate that this sandwich structure can be a promising option for high performance Si thin film lithium ion batteries.

Role of scaffold network in controlling strain and functionalities of nanocomposite films

PubMed Central

Chen, Aiping; Hu, Jia-Mian; Lu, Ping; Yang, Tiannan; Zhang, Wenrui; Li, Leigang; Ahmed, Towfiq; Enriquez, Erik; Weigand, Marcus; Su, Qing; Wang, Haiyan; Zhu, Jian-Xin; MacManus-Driscoll, Judith L.; Chen, Long-Qing; Yarotski, Dmitry; Jia, Quanxi

2016-01-01

Strain is a novel approach to manipulating functionalities in correlated complex oxides. However, significant epitaxial strain can only be achieved in ultrathin layers. We show that, under direct lattice matching framework, large and uniform vertical strain up to 2% can be achieved to significantly modify the magnetic anisotropy, magnetism, and magnetotransport properties in heteroepitaxial nanoscaffold films, over a few hundred nanometers in thickness. Comprehensive designing principles of large vertical strain have been proposed. Phase-field simulations not only reveal the strain distribution but also suggest that the ultimate strain is related to the vertical interfacial area and interfacial dislocation density. By changing the nanoscaffold density and dimension, the strain and the magnetic properties can be tuned. The established correlation among the vertical interface—strain—properties in nanoscaffold films can consequently be used to tune other functionalities in a broad range of complex oxide films far beyond critical thickness. PMID:27386578

Organometallic ruthenium anticancer complexes inhibit human glutathione-S-transferase π.

PubMed

Lin, Yu; Huang, Yongdong; Zheng, Wei; Wang, Fuyi; Habtemariam, Abraha; Luo, Qun; Li, Xianchan; Wu, Kui; Sadler, Peter J; Xiong, Shaoxiang

2013-11-01

The organometallic ruthenium(II) anticancer complexes [(η(6)-arene)Ru(en)Cl](+) (arene = p-cymene (1), biphenyl (2) or 9,10-dihydrophenanthrene (3); en = ethylenediamine), exhibit in vitro and in vivo anticancer activities. In the present work, we show that they inhibit human glutathione-S-transferase π (GSTπ) with IC50 values of 59.4 ± 1.3, 63.2 ± 0.4 and 37.2 ± 1.1 μM, respectively. Mass spectrometry revealed that complex 1 binds to the S-donors of Cys15, Cys48 within the G-site and Cys102 at the interface of the GSTπ dimer, while complex 2 binds to Cys48 and Met92 at the dimer interface and complex 3 to Cys15, Cys48 and Met92. Moreover, the binding of complex 1 to Cys15 and Cys102, complex 2 to Cys48 and complex 3 to Cys15 induces the irreversible oxidation of the coordinated thiolates to sulfenates. Molecular modeling studies indicate that the coordination of the {(arene)Ru(en)}(2+) fragment to Cys48 blocks the hydrophilic G-site sterically, perhaps preventing substrate from proper positioning and accounting for the reduction in enzymatic activity of ruthenated GSTπ. The binding of the ruthenium arene complexes to Cys102 or Met92 disrupts the dimer interface which is an essential structural feature for the proper functioning of GSTπ, perhaps also contributing to the inhibition of GSTπ. © 2013.

Metallomics for drug development: a further insight into intracellular activation chemistry of a ruthenium(III)-based anticancer drug gained using a multidimensional analytical approach.

PubMed

Matczuk, Magdalena; Prządka, Monika; Aleksenko, Svetlana S; Czarnocki, Zbigniew; Pawlak, Katarzyna; Timerbaev, Andrei R; Jarosz, Maciej

2014-01-01

The mechanism by which the most relevant ruthenium anticancer drugs are activated in tumors to commence their tumor-inhibiting action remains one of the challenging research tasks of present-day metallomics. This contribution aims to capture and identify eventually more reactive species of one of two bis-indazole tetrachloridoruthenate(III) compounds that are progressing in clinical trials. In view of the fact that the transport of ruthenium into cancer cells is governed by transferrin receptors, the susceptibility of the Ru drug adduct with holo-transferrin to exposure by glutathione and ascorbic acid (at their cancer cytosol concentrations) was studied by inductively coupled plasma mass spectrometry (ICP-MS), following isolation of the reaction products by ultrafiltration. Next, capillary electrophoresis coupled to ICP-MS was applied to monitor changes in the Ru speciation both under simulated cancer cytosol conditions and in real cytosol and to assign the charge state of novel metal species. The latter were identified by using tandem electrospray ionization MS in the respective ion mode. The formation of ruthenium(II) species was for the first time revealed, in which the central metal is coordinated by the reduced (GSH) or the oxidized (GSSG) form of glutathione, i.e. [Ru(II)HindCl4(GSH)](2-) and [Ru(II)HindCl4(GSSG)](2-), respectively (Hind = indazole). Ascorbic acid released the ruthenium functionality from the protein-bound form in a different way, the products of adduct cleavage containing aqua ligands. Distribution of low-molecular mass species of Ru in human cytosol was found to have very much in common with the ruthenium speciation assayed under simulated cytosol conditions.

Fabrication and Characterization of ZnO Langmuir-Blodgett Film and Its Use in Metal-Insulator-Metal Tunnel Diode.

PubMed

Azad, Ibrahim; Ram, Manoj K; Goswami, D Yogi; Stefanakos, Elias

2016-08-23

Metal-insulator-metal tunnel diodes have great potential for use in infrared detection and energy harvesting applications. The quantum based tunneling mechanism of electrons in MIM (metal-insulator-metal) or MIIM (metal-insulator-insulator-metal) diodes can facilitate rectification at THz frequencies. In this study, the required nanometer thin insulating layer (I) in the MIM diode structure was fabricated using the Langmuir-Blodgett technique. The zinc stearate LB film was deposited on Au/Cr coated quartz, FTO, and silicon substrates, and then heat treated by varying the temperature from 100 to 550 °C to obtain nanometer thin ZnO layers. The thin films were characterized by XRD, AFM, FTIR, and cyclic voltammetry methods. The final MIM structure was fabricated by depositing chromium/nickel over the ZnO on Au/Cr film. The current voltage (I-V) characteristics of the diode showed that the conduction mechanism is electron tunneling through the thin insulating layer. The sensitivity of the diodes was as high as 32 V(-1). The diode resistance was ∼80 Ω (at a bias voltage of 0.78 V), and the rectification ratio at that bias point was about 12 (for a voltage swing of ±200 mV). The diode response exhibited significant nonlinearity and high asymmetry at the bias point, very desirable diode performance parameters for IR detection applications.

Origin of thickness dependence of structural phase transition temperatures in BiFeO 3 thin films

DOE PAGES

Yang, Yongsoo; Beekman, Christianne; Siemons, Wolter; ...

2016-03-28

In this study, two structural phase transitions are investigated in highly strained BiFeO 3 thin films grown on LaAlO 3 substrates, as a function of film thickness and temperature via synchrotron x-ray diffraction. Both transition temperatures (upon heating: monoclinic MC to monoclinic MA, and MA to tetragonal) decrease as the film becomes thinner. The existence of an interface layer at the film-substrate interface, deduced from half-order peak intensities, contributes to this behavior only for the thinnest samples; at larger thicknesses (above a few nanometers) the temperature dependence can be understood in terms of electrostatic considerations akin to size effects inmore » ferroelectric phase transitions, but observed here for structural phase transitions within the ferroelectric phase and related to the rearrangement rather than the formation of domains. For ultra-thin films, the tetragonal structure is stable at all investigated temperatures (down to 30 K).« less

Carbon deposition in the Bosch process with ruthenium and ruthenium-iron alloy catalysts. M.S. Thesis. Final Report, Jan. 1981 - Jul. 1982

NASA Technical Reports Server (NTRS)

Manning, M. P.; Reid, R. C.; Sophonpanich, C.

1982-01-01

The effectiveness of ruthenium and the alloys 50Ru50Fe and 33Ru67Fe as alternatives to iron, nickel, and cobalt catalysts in recovering oxygen from metabolic carbon dioxide was investigated. Carbon deposition boundaries over the unsupported alloys are reported. Experiments were also carried out over 50Ru50Fe and 97Ru3Fe3 catalysts supported on gamma-alumina to determine their performance in the synthesis of low molecular weight olefins. High production of ethylene and propylene would be beneficial for an improvement of an overall Bosch process, as a gas phase containing high olefin content would enhance carbon deposition in a Bosch reactor.

Guest-Induced Two-Way Structural Transformation in a Layered Metal-Organic Framework Thin Film.

PubMed

Haraguchi, Tomoyuki; Otsubo, Kazuya; Sakata, Osami; Fujiwara, Akihiko; Kitagawa, Hiroshi

2016-12-28

Fabrication of thin films made of metal-organic frameworks (MOFs) has been intensively pursued for practical applications that use the structural response of MOFs. However, to date, only physisorption-induced structural response has been studied in these films. Chemisorption can be expected to provide a remarkable structural response because of the formation of bonds between guest molecules and reactive metal sites in host MOFs. Here, we report that chemisorption-induced two-way structural transformation in a nanometer-sized MOF thin film. We prepared a two-dimensional layered-type MOF Fe[Pt(CN) 4 ] thin film using a step-by-step approach. Although the as-synthesized film showed poor crystallinity, the dehydrated form of this thin film had a highly oriented crystalline nature (Film-D) as confirmed by synchrotron X-ray diffraction (XRD). Surprisingly, under water and pyridine vapors, Film-D showed chemisorption-induced dynamic structural transformations to Fe(L) 2 [Pt(CN) 4 ] thin films [L = H 2 O (Film-H), pyridine (Film-P)], where water and pyridine coordinated to the open Fe 2+ site. Dynamic structural transformations were also confirmed by in situ XRD, sorption measurement, and infrared reflection absorption spectroscopy. This is the first report of chemisorption-induced dynamic structural response in a MOF thin film, and it provides useful insights, which would lead to future practical applications of MOFs utilizing chemisorption-induced structural responses.

Ruthenium oxide ion selective thin-film electrodes for engine oil acidity monitoring

NASA Astrophysics Data System (ADS)

Maurya, D. K.; Sardarinejad, A.; Alameh, K.

2015-06-01

We demonstrate the concept of a low-cost, rugged, miniaturized ion selective electrode (ISE) comprising a thin film RuO2 on platinum sensing electrode deposited using RF magnetron sputtered in conjunction with an integrated Ag/AgCl and Ag reference electrodes for engine oil acidity monitoring. Model oil samples are produced by adding nitric acid into fresh fully synthetic engine oil and used for sensor evaluation. Experimental results show a linear potential-versus-acid-concentration response for nitric acid concentration between 0 (fresh oil) to 400 ppm, which demonstrate the accuracy of the RuO2 sensor in real-time operation, making it attractive for use in cars and industrial engines.

Porous Architecture of SPS Thick YSZ Coatings Structured at the Nanometer Scale (~50 nm)

NASA Astrophysics Data System (ADS)

Bacciochini, Antoine; Montavon, Ghislain; Ilavsky, Jan; Denoirjean, Alain; Fauchais, Pierre

2010-01-01

Suspension plasma spraying (SPS) is a fairly recent technology that is able to process sub-micrometer-sized or nanometer-sized feedstock particles and permits the deposition of coatings thinner (from 20 to 100 μm) than those resulting from conventional atmospheric plasma spraying (APS). SPS consists of mechanically injecting within the plasma flow a liquid suspension of particles of average diameter varying between 0.02 and 1 μm. Due to the large volume fraction of the internal interfaces and reduced size of stacking defects, thick nanometer- or sub-micrometer-sized coatings exhibit better properties than conventional micrometer-sized ones (e.g., higher coefficients of thermal expansion, lower thermal diffusivity, higher hardness and toughness, better wear resistance, among other coating characteristics and functional properties). They could hence offer pertinent solutions to numerous emerging applications, particularly for energy production, energy saving, etc. Coatings structured at the nanometer scale exhibit nanometer-sized voids. Depending upon the selection of operating parameters, among which plasma power parameters (operating mode, enthalpy, spray distance, etc.), suspension properties (particle size distribution, powder mass percentage, viscosity, etc.), and substrate characteristics (topology, temperature, etc.), different coating architectures can be manufactured, from dense to porous layers, from connected to non-connected network. Nevertheless, the discrimination of porosity in different classes of criteria such as size, shape, orientation, specific surface area, etc., is essential to describe the coating architecture. Moreover, the primary steps of the coating manufacturing process affect significantly the coating porous architecture. These steps need to be further understood. Different types of imaging experiments were performed to understand, describe and quantify the pore level of thick finely structured ceramics coatings.

Progress on glass ceramic ZERODUR enabling nanometer precision

NASA Astrophysics Data System (ADS)

Jedamzik, Ralf; Kunisch, Clemens; Nieder, Johannes; Weber, Peter; Westerhoff, Thomas

2016-03-01

The Semiconductor Industry is making continuous progress in shrinking feature size developing technologies and process to achieve < 10 nm feature size. The required Overlay specification for successful production is in the range one nanometer or even smaller. Consequently, materials designed into metrology systems of exposure or inspection tools need to fulfill ever tighter specification on the coefficient of thermal expansion (CTE). The glass ceramic ZERODUR® is a well-established material in critical components of microlithography wafer stepper and offered with an extremely low coefficient of thermal expansion, the tightest tolerance available on market. SCHOTT is continuously improving manufacturing processes and it's method to measure and characterize the CTE behavior of ZERODUR®. This paper is focusing on the "Advanced Dilatometer" for determination of the CTE developed at SCHOTT in the recent years and introduced into production in Q1 2015. The achievement for improving the absolute CTE measurement accuracy and the reproducibility are described in detail. Those achievements are compared to the CTE measurement accuracy reported by the Physikalische Technische Bundesanstalt (PTB), the National Metrology Institute of Germany. The CTE homogeneity is of highest importance to achieve nanometer precision on larger scales. Additionally, the paper presents data on the short scale CTE homogeneity and its improvement in the last two years. The data presented in this paper will explain the capability of ZERODUR® to enable the extreme precision required for future generation of lithography equipment and processes.

Grinding model and material removal mechanism of medical nanometer zirconia ceramics.

PubMed

Zhang, Dongkun; Li, Changhe; Jia, Dongzhou; Wang, Sheng; Li, Runze; Qi, Xiaoxiao

2014-01-01

Many patents have been devoted to developing medical nanometer zirconia ceramic grinding techniques that can significantly improve both workpiece surface integrity and grinding quality. Among these patents is a process for preparing ceramic dental implants with a surface for improving osseo-integration by sand abrasive finishing under a jet pressure of 1.5 bar to 8.0 bar and with a grain size of 30 µm to 250 µm. Compared with other materials, nano-zirconia ceramics exhibit unmatched biomedical performance and excellent mechanical properties as medical bone tissue and dentures. The removal mechanism of nano-zirconia materials includes brittle fracture and plastic removal. Brittle fracture involves crack formation, extension, peeling, and chipping to completely remove debris. Plastic removal is similar to chip formation in metal grinding, including rubbing, ploughing, and the formation of grinding debris. The materials are removed in shearing and chipping. During brittle fracture, the grinding-led transverse and radial extension of cracks further generate local peeling of blocks of the material. In material peeling and removal, the mechanical strength and surface quality of the workpiece are also greatly reduced because of crack extension. When grinding occurs in the plastic region, plastic removal is performed, and surface grinding does not generate grinding fissures and surface fracture, producing clinically satisfactory grinding quality. With certain grinding conditions, medical nanometer zirconia ceramics can be removed through plastic flow in ductile regime. In this study, we analyzed the critical conditions for the transfer of brittle and plastic removal in nano-zirconia ceramic grinding as well as the high-quality surface grinding of medical nanometer zirconia ceramics by ELID grinding.

Graphene doped ZnO films for photoelectrowetting on microchannels

NASA Astrophysics Data System (ADS)

Al-Aribe, Khaled; Knopf, George K.

2017-02-01

Photoelectrowetting on dielectric surfaces can be used to drive droplets of liquid along reconfigurable paths on a microfluidic chip using controlled optical signals. These electrostatically activated surfaces along the desired path eliminate the need for precision molded channels and discrete functional components such as microvalves and micropumps. The photoelectrowetting effect exploits the surface tension of the droplet to maintain its volume during the transportation pathway and the photoelectric properties of the substrate surface are used to induce reversible fluidic flow. The active light-driven substrate is structured from graphene doped zinc-oxide (ZnO-G) films deposited on ITO coated glass. This substrate is coated from the ZnO-G side with Ruthenium-based dye (N719) to maximize its absorbability. The light triggers two forces that enable the droplet to be transported along the substrate. The first arises from the induced hydrophobicity gradient formed across the droplet contact area with the substrate surface. Exposing the ZnO-G film to a broad spectrum white light source alters the surface's electric potential which induces a change in the droplet's contact angle and the associated hydrophobicity. Once the hydrophobicity gradient is generated the droplet will start to move in the direction of the wetting zone. The second force is also created by the optical input when the absorbed light generates a photoelectric potential that produces a piezo-electrical effect on the ZnO-G film. The light triggered piezo-electrical behavior of the ZnO-G film can be used to generate the erasable microchannels that can guide droplet movement through a microfluidic chip. Preliminary experiments are performed to investigate the photoelectric potential of light activated ZnO-G films.

Chemical solution synthesis and ferromagnetic resonance of epitaxial thin films of yttrium iron garnet

NASA Astrophysics Data System (ADS)

Lucas, Irene; Jiménez-Cavero, Pilar; Vila-Fungueiriño, J. M.; Magén, Cesar; Sangiao, Soraya; de Teresa, José Maria; Morellón, Luis; Rivadulla, Francisco

2017-12-01

We report the fabrication of epitaxial Y3F e5O12 (YIG) thin films on G d3G a5O12 (111) using a chemical solution method. Cubic YIG is a ferrimagnetic material at room temperature, with excellent magneto-optical properties, high electrical resistivity, and a very narrow ferromagnetic resonance, which makes it particularly suitable for applications in filters and resonators at microwave frequencies. But these properties depend on the precise stoichiometry and distribution of F e3 + ions among the octahedral/tetrahedral sites of a complex structure, which hampered the production of high-quality YIG thin films by affordable chemical methods. Here we report the chemical solution synthesis of YIG thin films, with excellent chemical, crystalline, and magnetic homogeneity. The films show a very narrow ferromagnetic resonance (long spin relaxation time), comparable to that obtained from high-vacuum physical deposition methods. These results demonstrate that chemical methods can compete to develop nanometer-thick YIG films with the quality required for spintronic devices and other high-frequency applications.

Enantioselective synthesis of allylic esters via asymmetric allylic substitution with metal carboxylates using planar-chiral cyclopentadienyl ruthenium catalysts.

PubMed

Kanbayashi, Naoya; Onitsuka, Kiyotaka

2010-02-03

An asymmetric allylic substitution with sodium carboxylate using a planar-chiral cyclopentadienyl ruthenium complex has been developed. Optically active allylic esters were prepared in good yields with high regio- and enantioselectivities.

Ruthenium(II) carbonyl complexes bearing CCC-pincer bis-(carbene) ligands: synthesis, structures and activities toward recycle transfer hydrogenation reactions.

PubMed

Naziruddin, Abbas Raja; Huang, Zhao-Jiunn; Lai, Wei-Chih; Lin, Wan-Jung; Hwang, Wen-Shu

2013-09-28

A new series of ruthenium(II) carbonyl complexes with benzene-based CCC-pincer bis-(carbene) ligands, [((R)CCC(R))Ru(CO)2(X)](0/+) and [((R)CCC(R))Ru(CO)(NN)](+) ((R)CCC(R) = 2,6-bis-(1-alkylimidazolylidene)benzene, R = Me or (n)Bu; X = I, Br, CH3CN, or 6-(aminomethyl)pyridine (ampy); NN = 2·CH3CN, or chelating ampy or bipyridine), was synthesized and fully characterized. X-Ray structure determinations revealed that these eight complexes have pseudo-octahedral configurations around the ruthenium center with the pincer ligand occupying three meridional sites. These complexes prove to be efficient precatalysts demonstrating very good activity and reusability for the transfer hydrogenation of ketones.

Biophysics: Breaking the Nanometer Barrier

DOE Office of Scientific and Technical Information (OSTI.GOV)

Block, Steven

2006-03-20

A new field of scientific exploration – single molecule biophysics – is currently reshaping and redefining our understanding of the mechanochemistry of life. The development of laser-based optical traps, or ‘optical tweezers,’ has allowed for physiological assessments of such precision that bio-molecules can now be measured and studied one at a time. In this colloquium, Professor Block will present findings based on his group’s construction of optical trapping instrumentation that has broken the nanometer barrier, allowing researchers to study single-molecule displacements on the Angstrom level. Focusing on RNA polymerase, the motor enzyme responsible for transcribing the genetic code contained inmore » DNA, Block’s group has been able to measure, in real time, the motion of a single molecule of RNA polymerase as it moves from base to base along the DNA template. A remarkable opportunity to gain insight into one of the most fundamental biological processes of life, this colloquium can not be missed!« less

Microstructural Evolution of Nanocrystalline Diamond Films Due to CH4/Ar/H2 Plasma Post-Treatment Process.

PubMed

Lin, Sheng-Chang; Yeh, Chien-Jui; Manoharan, Divinah; Leou, Keh-Chyang; Lin, I-Nan

2015-10-07

Plasma post-treatment process was observed to markedly enhance the electron field emission (EFE) properties of ultrananocrystalline diamond (UNCD) films. TEM examinations reveal that the prime factor which improves the EFE properties of these films is the coalescence of ultrasmall diamond grains (∼5 nm) forming large diamond grains about hundreds of nanometers accompanied by the formation of nanographitic clusters along the grain boundaries due to the plasma post-treatment process. OES studies reveal the presence of large proportion of atomic hydrogen and C2 (or CH) species, which are the main ingredients that altered the granular structure of the UNCD films. In the post-treatment process, the plasma interacts with the diamond films by a diffusion process. The recrystallization of diamond grains started at the surface region of the material, and the interaction zone increased with the post-treatment period. The entire diamond film can be converted into a nanocrystalline granular structure when post-treated for a sufficient length of time.

Heteroleptic monometallic and trimetallic ruthenium(II) complexes incorporating a π-extended dipyrrin ligand: Light-activated reactions with the A549 lung cancer cell line.

PubMed

Swavey, Shawn; Morford, Krista; Tsao, Max; Comfort, Kristen; Kilroy, Mary Kate

2017-10-01

A heteroleptic monometallic ruthenium(II) and a heteroleptic trimetallic ruthenium(II) complex have been synthesized and characterized. Both complexes have an overall 3+ charge, with the charge density greater for the monometallic complex. The electronic spectra of the monometallic ruthenium(II) complex exhibits intense π-π* transitions associated with the bipyridyl groups along with overlapping metal to ligand charge transfer (MLCT) and ligand centered π-π* transitions ranging from 520nm to approximately 600nm. The trimetallic ruthenium(II) complex, on the other hand, displays more well defined transitions with the expected π-π* transition of the bipyridyl groups at 294nm and Ru(dπ) to bpy(π*) MLCT transitions at 355nm and 502nm. In addition to these absorption bands an intense transition, 578nm, resulting from overlapping dipyrrin (π-π*) and Ru(dπ) to dipyrrin(π*) transitions is observed. Electrochemical and spectroelectrochemical experiments were used to help in assigning these transitions. Irradiation of the complexes in the presence of plasmid DNA within the photodynamic therapy window (600nm to 850nm) reveal, using electrophoresis, that both complexes are capable of causing photo-damage to the DNA backbone. The trimetallic ruthenium(II) complex; however, also shows the ability to generate photoinduced DNA damage in the absence of oxygen, suggesting a photo-oxidative process. Studies of the complexes toward lung cancer cells (A549 cell line) in the absence of light indicate little cytotoxicity up to 50μM. Upon irradiation of the cells with a low power 420nm light source the trimetallic complex showed considerably greater photo-cytotoxicity compared to the monometallic analog. A dose-dependent response curve gives an IC50 of 92μM for complex B. Copyright © 2017 Elsevier Inc. All rights reserved.

Electronic Interplay between TTF and Extended-TCNQ Electrophores along a Ruthenium Bis(acetylide) Linker.

PubMed

Vacher, Antoine; Auffray, Morgan; Barrière, Frédéric; Roisnel, Thierry; Lorcy, Dominique

2017-11-17

A bis(TTF-butadiynyl) ruthenium D-D'-D complex, with intramolecular electronic interplay between the three electron-donating electrophores, was easily converted through a cycloaddition-retroelectrocyclization with TCNQ into a D-A-D'-A-D pentad complex, which exhibits an intense intramolecular charge transfer together with an electronic interplay between the two acceptors along the conjugated organometallic bridge.

Real-Time Imaging of Plant Cell Wall Structure at Nanometer Scale, with Respect to Cellulase Accessibility and Degradation Kinetics (Presentation)

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ding, S. Y.

Presentation on real-time imaging of plant cell wall structure at nanometer scale. Objectives are to develop tools to measure biomass at the nanometer scale; elucidate the molecular bases of biomass deconstruction; and identify factors that affect the conversion efficiency of biomass-to-biofuels.

Surface effects on ionic Coulomb blockade in nanometer-size pores

NASA Astrophysics Data System (ADS)

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V.; Di Ventra, Massimiliano

2018-01-01

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying ‘crystal-like’ structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Surface effects on ionic Coulomb blockade in nanometer-size pores.

PubMed

Tanaka, Hiroya; Iizuka, Hideo; Pershin, Yuriy V; Ventra, Massimiliano Di

2018-01-12

Ionic Coulomb blockade in nanopores is a phenomenon that shares some similarities but also differences with its electronic counterpart. Here, we investigate this phenomenon extensively using all-atom molecular dynamics of ionic transport through nanopores of about one nanometer in diameter and up to several nanometers in length. Our goal is to better understand the role of atomic roughness and structure of the pore walls in the ionic Coulomb blockade. Our numerical results reveal the following general trends. First, the nanopore selectivity changes with its diameter, and the nanopore position in the membrane influences the current strength. Second, the ionic transport through the nanopore takes place in a hopping-like fashion over a set of discretized states caused by local electric fields due to membrane atoms. In some cases, this creates a slow-varying 'crystal-like' structure of ions inside the nanopore. Third, while at a given voltage, the resistance of the nanopore depends on its length, the slope of this dependence appears to be independent of the molarity of ions. An effective kinetic model that captures the ionic Coulomb blockade behavior observed in MD simulations is formulated.

Size-controllable APTS stabilized ruthenium(0) nanoparticles catalyst for the dehydrogenation of dimethylamine-borane at room temperature.

PubMed

Zahmakıran, Mehmet; Philippot, Karine; Özkar, Saim; Chaudret, Bruno

2012-01-14

Dimethylamine-borane, (CH(3))(2)NHBH(3), has been considered as one of the attractive materials for the efficient storage of hydrogen, which is still one of the key issues in the "Hydrogen Economy". In a recent communication we have reported the synthesis and characterization of 3-aminopropyltriethoxysilane stabilized ruthenium(0) nanoparticles with the preliminary results for their catalytic performance in the dehydrogenation of dimethylamine-borane at room temperature. Herein, we report a complete work including (i) effect of initial [APTS]/[Ru] molar ratio on both the size and the catalytic activity of ruthenium(0) nanoparticles, (ii) collection of extensive kinetic data under non-MTL conditions depending on the substrate and catalyst concentrations to define the rate law of Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane at room temperature, (iii) determination of activation parameters (E(a), ΔH(#) and ΔS(#)) for Ru(0)/APTS-catalyzed dehydrogenation of dimethylamine-borane; (iv) demonstration of the catalytic lifetime of Ru(0)/APTS nanoparticles in the dehydrogenation of dimethylamine-borane at room temperature, (v) testing the bottlability and reusability of Ru(0)/APTS nanocatalyst in the room-temperature dehydrogenation of dimethylamine-borane, (vi) quantitative carbon disulfide (CS(2)) poisoning experiments to find a corrected TTO and TOF values on a per-active-ruthenium-atom basis, (vii) a summary of extensive literature review for the catalysts tested in the catalytic dehydrogenation of dimethylamine-borane as part of the results and discussions.

Nanometer-Scale Epitaxial Strain Release in Perovskite Heterostructures Using 'SrAlOx' Sliding Buffer Layers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Bell, Christopher

2011-08-11

We demonstrate the strain release of LaAlO{sub 3} epitaxial film on SrTiO{sub 3} (001) by inserting ultra-thin 'SrAlO{sub x}' buffer layers. Although SrAlO{sub x} is not a perovskite, nor stable as a single phase in bulk, epitaxy stabilizes the perovskite structure up to a thickness of 2 unit cells (uc). At a critical thickness of 3 uc of SrAlO{sub x}, the interlayer acts as a sliding buffer layer, and abruptly relieves the lattice mismatch between the LaAlO{sub 3} filmand the SrTiO{sub 3} substrate, while maintaining crystallinity. This technique may provide a general approach for strain relaxation of perovskite film farmore » below the thermodynamic critical thickness. A central issue in heteroepitaxial filmgrowth is the inevitable difference in lattice constants between the filmand substrate. Due to this lattice mismatch, thin film are subjected to microstructural strain, which can have a significan effect on the filmproperties. This challenge is especially prominent in the rapidly developing fiel of oxide electronics, where much interest is focused on incorporating the emergent physical properties of oxides in devices. Although strain can be used to great effect to engineer unusual ground states, it is often deleterious for bulk first-orde phase transitions, which are suppressed by the strain and symmetry constraints of the substrate. While there are some reports discussing the control of the lattice mismatch in oxides using thick buffer layers, the materials choice, lattice-tunable range, and control of misfit dislocations are still limited. In this Letter, we report the fabrication of strain-relaxed LaAlO{sub 3} (LAO) thin film on SrTiO{sub 3} (STO) (001) using very thin 'SrAlO{sub x}' (SAO) buffer layers. Whereas for 1 or 2 pseudo-perovskite unit cells (uc) of SAO, the subsequent LAO filmis strained to the substrate, at a critical thickness of 3 uc the SAO interlayer abruptly relieves the lattice mismatch between the LAO and the STO, although maintaining

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study

PubMed Central

Jiang, Jin-yang; Wang, Danqian; Chu, Hong-yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-01-01

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed. PMID:28772772

The Passive Film Growth Mechanism of New Corrosion-Resistant Steel Rebar in Simulated Concrete Pore Solution: Nanometer Structure and Electrochemical Study.

PubMed

Jiang, Jin-Yang; Wang, Danqian; Chu, Hong-Yan; Ma, Han; Liu, Yao; Gao, Yun; Shi, Jinjie; Sun, Wei

2017-04-14

An elaborative study was carried out on the growth mechanism and properties of the passive film for a new kind of alloyed corrosion-resistant steel (CR steel). The passive film naturally formed in simulated concrete pore solutions (pH = 13.3). The corrosion resistance was evaluated by various methods including open circuit potential (OCP), linear polarization resistance (LPR) measurements, and electrochemical impedance spectroscopy (EIS). Meanwhile, the 2205 duplex stainless steel (SS steel) was evaluated for comparison. Moreover, the passive film with CR steel was studied by means of X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), Atomic Force Microscope (AFM), and the Mott‑Schottky approach. The results showed that the excellent passivity of CR steel could be detected in a high alkaline environment. The grain boundaries between the fine passive film particles lead to increasing Cr oxide content in the later passivation stage. The filling of cation vacancies in the later passivation stage as well as the orderly crystalized inner layer contributed to the excellent corrosion resistance of CR steel. A passive film growth model for CR steel was proposed.

A simple growth method for Nb 2O 5 films and their optical properties

DOE PAGES

Dash, J. K.; Chen, L.; Topka, Michael R.; ...

2015-04-13

A simple method for the synthesis of Nb₂O₅ films of thicknesses ranging from tens to several hundreds of nanometers on amorphous silicon dioxide or quartz substrates is presented. Nb₂O₅ films were formed by annealing the sputter deposited Nb films under an Ar flow and without oxygen plasma in a quartz tube within a furnace at 850 °C. The structural, compositional, optical, and vibrational properties were characterized by grazing incidence X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, ultraviolet visible spectroscopy, and Raman scattering. Each of the Nb₂O₅ films is polycrystalline with an orthorhombic crystal structure. We observed vibrational modes includingmore » longitudinal optical, transverse optical, and triply degenerate modes, and measured the indirect optical band gap to be ~3.65 eV. The transmittance spectrum of the ~20 nm thick Nb₂O₅ film shows over 90% transmittance below the band gap energy in the visible wavelength range and decreases to less than 20% in the ultraviolet regime. As a result, the optical properties of the films in the UV-vis range show potential applications as UV detectors.« less

Interfacing superhydrophobic silica nanoparticle films with graphene and thermoplastic polyurethane for wear/abrasion resistance.

PubMed

Naderizadeh, Sara; Athanassiou, Athanassia; Bayer, Ilker S

2018-06-01

Nanoparticle films are one of the most suitable platforms for obtaining sub-micrometer and nanometer dual-scale surface texture required for liquid repellency. The assembly of superhydrophobic nanoparticles into conformal and strongly adherent films having abrasion-induced wear resistance still poses a significant challenge. Various techniques have been developed over the years to render nanoparticle films with good liquid repellent properties and transparency. However, forming abrasion resistant superhydrophobic nanoparticle films on hard surfaces is challenging. One possibility is to partially embed or weld nanoparticles in thin thermoplastic primers applied over metals. Hexamethyldisilazane-functionalized fumed silica nanoparticle films spray deposited on aluminum surfaces were rendered abrasion resistant by thermally welding them into thermoplastic polyurethane (TPU) primer applied a priori over aluminum. Different solvents, nanoparticle concentrations and annealing temperatures were studied to optimize nanoparticle film morphology and hydrophobicity. Thermal annealing at 150 °C enhanced stability and wear resistance of nanoparticle films. A thin thermal interface layer of graphene nanoplatelets (GnPs) between the primer and the nanoparticle film significantly improved superhydrophobic wear resistance after annealing. As such, superhydrophobic nanocomposite films with the GnPs thermal interface layer displayed superior abrasion-induced wear resistance under 20 kPa compared to films having no GnPs-based thermal interface. Copyright © 2018 Elsevier Inc. All rights reserved.

A hybrid ruthenium alkynyl/zinc porphyrin "Cross Fourchée" with large cubic NLO properties.

PubMed

Merhi, Areej; Grelaud, Guillaume; Green, Katy A; Minh, Ngo Hoang; Reynolds, Michael; Ledoux, Isabelle; Barlow, Adam; Wang, Genmiao; Cifuentes, Marie P; Humphrey, Mark G; Paul, Frédéric; Paul-Roth, Christine O

2015-05-07

A new Zn(ii) porphyrin-cored ruthenium alkynyl dendrimer (2) containing twelve Ru(κ(2)-dppe)2 bis-alkynyl fragments has been prepared in two steps from 5,10,15,20-tetra(4-ethynylphenyl)porphyrinatozinc(ii) and shown to be highly active for third-harmonic generation (THG) at 1907 nm.

Role of scaffold network in controlling strain and functionalities of nanocomposite films

DOE PAGES

Chen, Aiping; Hu, Jia -Mian; Lu, Ping; ...

2016-06-10

One novel approach to manipulating functionalities in correlated complex oxides is strain. However, significant epitaxial strain can only be achieved in ultrathin layers. We show that, under direct lattice matching framework, large and uniform vertical strain up to 2% can be achieved to significantly modify the magnetic anisotropy, magnetism, and magnetotransport properties in heteroepitaxial nanoscaffold films, over a few hundred nanometers in thickness. Comprehensive designing principles of large vertical strain have been proposed. Phase-field simulations not only reveal the strain distribution but also suggest that the ultimate strain is related to the vertical interfacial area and interfacial dislocation density. Moreover,more » by changing the nanoscaffold density and dimension, the strain and the magnetic properties can be tuned. The established correlation among the vertical interface—strain—properties in nanoscaffold films can consequently be used to tune other functionalities in a broad range of complex oxide films far beyond critical thickness.« less

Photoresponsive Molecular Memory Films Composed of Sequentially Assembled Heterolayers Containing Ruthenium Complexes.

PubMed

Nagashima, Takumi; Ozawa, Hiroaki; Suzuki, Takashi; Nakabayashi, Takuya; Kanaizuka, Katsuhiko; Haga, Masa-Aki

2016-01-26

Photoresponsive molecular memory films were fabricated by a layer-by-layer (LbL) assembling of two dinuclear Ru complexes with tetrapodal phosphonate anchors, containing either 2,3,5,6-tetra(2-pyridyl)pyrazine or 1,2,4,5-tetra(2-pyridyl)benzene as a bridging ligand (Ru-NP and Ru-CP, respectively), using zirconium phosphonate to link the layers. Various types of multilayer homo- and heterostructures were constructed. In the multilayer heterofilms such as ITO||(Ru-NP)m |(Ru-CP)n , the difference in redox potentials between Ru-NP and Ru-CP layers was approximately 0.7 V, which induced a potential gradient determined by the sequence of the layers. In the ITO||(Ru-NP)m |(Ru-CP)n multilayer heterofilms, the direct electron transfer (ET) from the outer Ru-CP layers to the ITO were observed to be blocked for m>2, and charge trapping in the outer Ru-CP layers became evident from the appearance of an intervalence charge transfer (IVCT) band at 1140 nm from the formation of the mixed-valent state of Ru-CP units, resulting from the reductive ET mediation of the inner Ru-NP layers. Therefore, the charging/discharging ("1"and "0") states in the outer Ru-CP layers could be addressed and interconverted by applying potential pulses between -0.5 and +0.7 V. The two states could be read out by the direction of the photocurrent (anodic or cathodic). The molecular heterolayer films thus represent a typical example of a photoresponsive memory device; that is, the writing process may be achieved by the applied potential (-0.5 or +0.7 V), while the readout process is achieved by measuring the direction of the photocurrent (anodic or cathodic). Sequence-sensitive multilayer heterofilms, using redox-active complexes as building blocks, thus demonstrate great potential for the design of molecular functional devices. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Magnesium phthalocyanine(MgPc) thin films as nanomaterials

NASA Astrophysics Data System (ADS)

Puri, Munish; Bedi, R. K.; Prakash, G. V.

2006-05-01

MgPc is a promising candidate for photovoltaic applications. It can be easily synthesized and is non-toxic to the envioronment. It is a self assembly molecule developed from deep-blue-green pigment. It exhibits a characteristic structural self organization which is reflected in an efficient energy migration in the form of extinction transport. MgPc relates to the similarity with chlorophyll. In the present work thin films of MgPc have been prepared on glass substrate under strict vacuum conditions(10 Â6 torr), thickness of few nanometers. Absorption spectra in Visible and IR regions have been observed which is good for fabrication of Photovoltaic cells and Nanostructures for Photodynamic Cancer Therapy. Appreciable amount of cytotoxicity can be observed while using MgPc as photosensitizers which is a promising PDT agent. The films thus prepared have been studied for their electrical and optical characterizations. Investigations have been made from different stacking positions of molecular MgPc thin films for studying their self-assembling nature that can be useful for their applications as Molecular-Recognition in Drug delivery and sensors which is one of the key features of Nanotechnology.

All-optical lithography process for contacting nanometer precision donor devices

NASA Astrophysics Data System (ADS)

Ward, D. R.; Marshall, M. T.; Campbell, D. M.; Lu, T. M.; Koepke, J. C.; Scrymgeour, D. A.; Bussmann, E.; Misra, S.

2017-11-01

We describe an all-optical lithography process that can make electrical contact to nanometer-precision donor devices fabricated in silicon using scanning tunneling microscopy (STM). This is accomplished by implementing a cleaning procedure in the STM that allows the integration of metal alignment marks and ion-implanted contacts at the wafer level. Low-temperature transport measurements of a patterned device establish the viability of the process.

Highly repeatable nanoscale phase coexistence in vanadium dioxide films

NASA Astrophysics Data System (ADS)

Huffman, T. J.; Lahneman, D. J.; Wang, S. L.; Slusar, T.; Kim, Bong-Jun; Kim, Hyun-Tak; Qazilbash, M. M.

2018-02-01

It is generally believed that in first-order phase transitions in materials with imperfections, the formation of phase domains must be affected to some extent by stochastic (probabilistic) processes. The stochasticity would lead to unreliable performance in nanoscale devices that have the potential to exploit the transformation of physical properties in a phase transition. Here we show that stochasticity at nanometer length scales is completely suppressed in the thermally driven metal-insulator transition (MIT) in sputtered vanadium dioxide (V O2 ) films. The nucleation and growth of domain patterns of metallic and insulating phases occur in a strikingly reproducible way. The completely deterministic nature of domain formation and growth in films with imperfections is a fundamental and unexpected finding about the kinetics of this material. Moreover, it opens the door for realizing reliable nanoscale devices based on the MIT in V O2 and similar phase-change materials.

Unravelling the structural-electronic impact of arylamine electron-donating antennas on the performances of efficient ruthenium sensitizers for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Chen, Wang-Chao; Kong, Fan-Tai; Ghadari, Rahim; Li, Zhao-Qian; Guo, Fu-Ling; Liu, Xue-Peng; Huang, Yang; Yu, Ting; Hayat, Tasawar; Dai, Song-Yuan

2017-04-01

We report a systematic research to understand the structural-electronic impact of the arylamine electron-donating antennas on the performances of the ruthenium complexes for dye-sensitized solar cells. Three ruthenium complexes functionalized with different arylamine electron-donating antennas (N,N-diethyl-aniline in RC-31, julolidine in RC-32 and N,N-dibenzyl-aniline in RC-36) are designed and synthesized. The photoelectric properties of RC dyes exhibit apparent discrepancy, which are ascribed to different structural nature and electronic delocalization ability of these arylamine electron-donating system. In conjunction with TiO2 microspheres photoanode and a typical coadsorbent DPA, the devices sensitized by RC-36 achieve the best conversion efficiency of 10.23%. The UV-Vis absorption, electrochemical measurement, incident photon-to-current conversion efficiency and transient absorption spectra confirm that the excellent performance of RC-36 is induced by synergistically structural-electronic impacts from enhanced absorption capacity and well-tuned electronic characteristics. These observations provide valuable insights into the molecular engineering methodology based on fine tuning structural-electronic impact of electron-donating antenna in efficient ruthenium sensitizers.

Nanometer resolution optical coherence tomography using broad bandwidth XUV and soft x-ray radiation

DOE PAGES

Fuchs, Silvio; Rödel, Christian; Blinne, Alexander; ...

2016-02-10

Optical coherence tomography (OCT) is a non-invasive technique for cross-sectional imaging. It is particularly advantageous for applications where conventional microscopy is not able to image deeper layers of samples in a reasonable time, e.g. in fast moving, deeper lying structures. However, at infrared and optical wavelengths, which are commonly used, the axial resolution of OCT is limited to about 1 μm, even if the bandwidth of the light covers a wide spectral range. Here, we present extreme ultraviolet coherence tomography (XCT) and thus introduce a new technique for non-invasive cross-sectional imaging of nanometer structures. XCT exploits the nanometerscale coherence lengthsmore » corresponding to the spectral transmission windows of, e.g., silicon samples. The axial resolution of coherence tomography is thus improved from micrometers to a few nanometers. Tomographic imaging with an axial resolution better than 18 nm is demonstrated for layer-type nanostructures buried in a silicon substrate. Using wavelengths in the water transmission window, nanometer-scale layers of platinum are retrieved with a resolution better than 8 nm. As a result, XCT as a nondestructive method for sub-surface tomographic imaging holds promise for several applications in semiconductor metrology and imaging in the water window.« less

Synergistic oxygen atom transfer by ruthenium complexes with non-redox metal ions.

PubMed

Lv, Zhanao; Zheng, Wenrui; Chen, Zhuqi; Tang, Zhiming; Mo, Wanling; Yin, Guochuan

2016-07-28

Non-redox metal ions can affect the reactivity of active redox metal ions in versatile biological and heterogeneous oxidation processes; however, the intrinsic roles of these non-redox ions still remain elusive. This work demonstrates the first example of the use of non-redox metal ions as Lewis acids to sharply improve the catalytic oxygen atom transfer efficiency of a ruthenium complex bearing the classic 2,2'-bipyridine ligand. In the absence of Lewis acid, the oxidation of ruthenium(ii) complex by PhI(OAc)2 generates the Ru(iv)[double bond, length as m-dash]O species, which is very sluggish for olefin epoxidation. When Ru(bpy)2Cl2 was tested as a catalyst alone, only 21.2% of cyclooctene was converted, and the yield of 1,2-epoxycyclooctane was only 6.7%. As evidenced by electronic absorption spectra and EPR studies, both the oxidation of Ru(ii) by PhI(OAc)2 and the reduction of Ru(iv)[double bond, length as m-dash]O by olefin are kinetically slow. However, adding non-redox metal ions such as Al(iii) can sharply improve the oxygen transfer efficiency of the catalyst to 100% conversion with 89.9% yield of epoxide under identical conditions. Through various spectroscopic characterizations, an adduct of Ru(iv)[double bond, length as m-dash]O with Al(iii), Ru(iv)[double bond, length as m-dash]O/Al(iii), was proposed to serve as the active species for epoxidation, which in turn generated a Ru(iii)-O-Ru(iii) dimer as the reduced form. In particular, both the oxygen transfer from Ru(iv)[double bond, length as m-dash]O/Al(iii) to olefin and the oxidation of Ru(iii)-O-Ru(iii) back to the active Ru(iv)[double bond, length as m-dash]O/Al(iii) species in the catalytic cycle can be remarkably accelerated by adding a non-redox metal, such as Al(iii). These results have important implications for the role played by non-redox metal ions in catalytic oxidation at redox metal centers as well as for the understanding of the redox mechanism of ruthenium catalysts in the oxygen atom

Synthesis and Characterization of Novel Ruthenium(III) Complexes with Histamine

PubMed Central

Kljun, Jakob; Petriček, Saša; Žigon, Dušan; Hudej, Rosana; Miklavčič, Damijan; Turel, Iztok

2010-01-01

Novel ruthenium(III) complexes with histamine [RuCl4(dmso-S)(histamineH)] · H2O (1a) and [RuCl4(dmso-S)(histamineH)] (1b) have been prepared and characterized by X-ray structure analysis. Their crystal structures are similar and show a protonated amino group on the side chain of the ligand which is not very common for a simple heterocyclic derivative such as histamine. Biological assays to test the cytotoxicity of the compound 1b combined with electroporation were performed to determine its potential for future medical applications in cancer treatment. PMID:20631838

Polycrystalline silicon thin-film transistors with location-controlled crystal grains fabricated by excimer laser crystallization

NASA Astrophysics Data System (ADS)

Tsai, Chun-Chien; Lee, Yao-Jen; Chiang, Ko-Yu; Wang, Jyh-Liang; Lee, I.-Che; Chen, Hsu-Hsin; Wei, Kai-Fang; Chang, Ting-Kuo; Chen, Bo-Ting; Cheng, Huang-Chung

2007-11-01

In this paper, location-controlled silicon crystal grains are fabricated by the excimer laser crystallization method which employs amorphous silicon spacer structure and prepatterned thin films. The amorphous silicon spacer in nanometer-sized width formed using spacer technology is served as seed crystal to artificially control superlateral growth phenomenon during excimer laser irradiation. An array of 1.8-μm-sized disklike silicon grains is formed, and the n-channel thin-film transistors whose channels located inside the artificially-controlled crystal grains exhibit higher performance of field-effect-mobility reaching 308cm2/Vs as compared with the conventional ones. This position-manipulated silicon grains are essential to high-performance and good uniformity devices.

In situ formed catalytically active ruthenium nanocatalyst in room temperature dehydrogenation/dehydrocoupling of ammonia-borane from Ru(cod)(cot) precatalyst.

PubMed

Zahmakiran, Mehmet; Ayvalı, Tuğçe; Philippot, Karine

2012-03-20

The development of simply prepared and effective catalytic materials for dehydrocoupling/dehydrogenation of ammonia-borane (AB; NH(3)BH(3)) under mild conditions remains a challenge in the field of hydrogen economy and material science. Reported herein is the discovery of in situ generated ruthenium nanocatalyst as a new catalytic system for this important reaction. They are formed in situ during the dehydrogenation of AB in THF at 25 °C in the absence of any stabilizing agent starting with homogeneous Ru(cod)(cot) precatalyst (cod = 1,5-η(2)-cyclooctadiene; cot = 1,3,5-η(3)-cyclooctatriene). The preliminary characterization of the reaction solutions and the products was done by using ICP-OES, ATR-IR, TEM, XPS, ZC-TEM, GC, EA, and (11)B, (15)N, and (1)H NMR, which reveal that ruthenium nanocatalyst is generated in situ during the dehydrogenation of AB from homogeneous Ru(cod)(cot) precatalyst and B-N polymers formed at the initial stage of the catalytic reaction take part in the stabilization of this ruthenium nanocatalyst. Moreover, following the recently updated approach (Bayram, E.; et al. J. Am. Chem. Soc.2011, 133, 18889) by performing Hg(0), CS(2) poisoning experiments, nanofiltration, time-dependent TEM analyses, and kinetic investigation of active catalyst formation to distinguish single metal or in the present case subnanometer Ru(n) cluster-based catalysis from polymetallic Ru(0)(n) nanoparticle catalysis reveals that in situ formed Ru(n) clusters (not Ru(0)(n) nanoparticles) are kinetically dominant catalytically active species in our catalytic system. The resulting ruthenium catalyst provides 120 total turnovers over 5 h with an initial turnover frequency (TOF) value of 35 h(-1) at room temperature with the generation of more than 1.0 equiv H(2) at the complete conversion of AB to polyaminoborane (PAB; [NH(2)BH(2)](n)) and polyborazylene (PB; [NHBH](n)) units.

A Smart Europium-Ruthenium Complex as Anticancer Prodrug: Controllable Drug Release and Real-Time Monitoring under Different Light Excitations.

PubMed

Li, Hongguang; Xie, Chen; Lan, Rongfeng; Zha, Shuai; Chan, Chi-Fai; Wong, Wing-Yan; Ho, Ka-Lok; Chan, Brandon Dow; Luo, Yuxia; Zhang, Jing-Xiang; Law, Ga-Lai; Tai, William C S; Bünzli, Jean-Claude G; Wong, Ka-Leung

2017-11-09

A unique, dual-function, photoactivatable anticancer prodrug, RuEuL, has been tailored that features a ruthenium(II) complex linked to a cyclen-europium chelate via a π-conjugated bridge. Under irradiation at 488 nm, the dark-inactive prodrug undergoes photodissociation, releasing the DNA-damaging ruthenium species. Under evaluation-window irradiation (λ irr = one-photon 350 nm or two-photon 700 nm), the drug delivery process can be quantitatively monitored in real-time because of the long-lived red europium emission. Linear relationships between released drug concentration and ESI-MS or luminescence responses are established. Finally, the efficiency of the new prodrug is demonstrated both in vitro RuEuL anticancer prodrug over some existing ones and open the way for decisive improvements in multipurpose prodrugs.

Electrochemical DNA biosensor for detection of porcine oligonucleotides using ruthenium(II) complex as intercalator label redox

DOE Office of Scientific and Technical Information (OSTI.GOV)

Halid, Nurul Izni Abdullah; Hasbullah, Siti Aishah; Heng, Lee Yook

2014-09-03

A DNA biosensor detection of oligonucleotides via the interactions of porcine DNA with redox active complex based on the electrochemical transduction is described. A ruthenium(II) complex, [Ru(bpy){sub 2}(PIP)]{sup 2+}, (bpy = 2,2′bipyridine, PIP = 2-phenylimidazo[4,5-f[[1,10-phenanthroline]) as DNA label has been synthesized and characterized by 1H NMR and mass spectra. The study was carried out by covalent bonding immobilization of porcine aminated DNA probes sequences on screen printed electrode (SPE) modified with succinimide-acrylic microspheres and [Ru(bpy){sub 2}(PIP)]{sup 2+} was used as electrochemical redox intercalator label to detect DNA hybridization event. Electrochemical detection was performed by cyclic voltammetry (CV) and differential pulsemore » voltammetry (DPV) over the potential range where the ruthenium (II) complex was active. The results indicate that the interaction of [Ru(bpy){sub 2}(PIP)]{sup 2+} with hybridization complementary DNA has higher response compared to single-stranded and mismatch complementary DNA.« less

Asymmetric hydrogenation of aromatic ketones by new recyclable ionic tagged ferrocene-ruthenium catalyst system.

PubMed

Xu, Di; Zhou, Zhi-Ming; Dai, Li; Tang, Li-Wei; Zhang, Jun

2015-05-01

Newly developed ferrocene-oxazoline-phosphine ligands containing quaternary ammonium ionic groups exhibited excellent catalytic performance for the ruthenium-catalyzed hydrogenation of aromatic ketonic substrates to give chiral secondary alcohols with high levels of conversions and enantioselectivities. Simple manipulation process, water tolerance, high activity and good recyclable property make this catalysis practical and appealing. Copyright © 2015 Elsevier Ltd. All rights reserved.

Functional nanometer-scale structures

NASA Astrophysics Data System (ADS)

Chan, Tsz On Mario

Nanometer-scale structures have properties that are fundamentally different from their bulk counterparts. Much research effort has been devoted in the past decades to explore new fabrication techniques, model the physical properties of these structures, and construct functional devices. The ability to manipulate and control the structure of matter at the nanoscale has made many new classes of materials available for the study of fundamental physical processes and potential applications. The interplay between fabrication techniques and physical understanding of the nanostructures and processes has revolutionized the physical and material sciences, providing far superior properties in materials for novel applications that benefit society. This thesis consists of two major aspects of my graduate research in nano-scale materials. In the first part (Chapters 3--6), a comprehensive study on the nanostructures based on electrospinning and thermal treatment is presented. Electrospinning is a well-established method for producing high-aspect-ratio fibrous structures, with fiber diameter ranging from 1 nm--1 microm. A polymeric solution is typically used as a precursor in electrospinning. In our study, the functionality of the nanostructure relies on both the nanostructure and material constituents. Metallic ions containing precursors were added to the polymeric precursor following a sol-gel process to prepare the solution suitable for electrospinning. A typical electrospinning process produces as-spun fibers containing both polymer and metallic salt precursors. Subsequent thermal treatments of the as-spun fibers were carried out in various conditions to produce desired structures. In most cases, polymer in the solution and the as-spun fibers acted as a backbone for the structure formation during the subsequent heat treatment, and were thermally removed in the final stage. Polymers were also designed to react with the metallic ion precursors during heat treatment in some

A Micro-Resonant Gas Sensor with Nanometer Clearance between the Pole Plates

PubMed Central

Xu, Lizhong

2018-01-01

In micro-resonant gas sensors, the capacitive detection is widely used because of its simple structure. However, its shortcoming is a weak signal output caused by a small capacitance change. Here, we reduced the initial clearance between the pole plates to the nanometer level, and increased the capacitance between the pole plates and its change during resonator vibration. We propose a fabricating process of the micro-resonant gas sensor by which the initial clearance between the pole plates is reduced to the nanometer level and a micro-resonant gas sensor with 200 nm initial clearance is fabricated. With this sensor, the resonant frequency shifts were measured when they were exposed to several different vapors, and high detection accuracies were obtained. The detection accuracy with respect to ethanol vapor was 0.4 ppm per Hz shift, and the detection accuracy with respect to hydrogen and ammonias vapors was 3 ppm and 0.5 ppm per Hz shift, respectively. PMID:29373546

A Micro-Resonant Gas Sensor with Nanometer Clearance between the Pole Plates.

PubMed

Fu, Xiaorui; Xu, Lizhong

2018-01-26

In micro-resonant gas sensors, the capacitive detection is widely used because of its simple structure. However, its shortcoming is a weak signal output caused by a small capacitance change. Here, we reduced the initial clearance between the pole plates to the nanometer level, and increased the capacitance between the pole plates and its change during resonator vibration. We propose a fabricating process of the micro-resonant gas sensor by which the initial clearance between the pole plates is reduced to the nanometer level and a micro-resonant gas sensor with 200 nm initial clearance is fabricated. With this sensor, the resonant frequency shifts were measured when they were exposed to several different vapors, and high detection accuracies were obtained. The detection accuracy with respect to ethanol vapor was 0.4 ppm per Hz shift, and the detection accuracy with respect to hydrogen and ammonias vapors was 3 ppm and 0.5 ppm per Hz shift, respectively.

All-optical lithography process for contacting nanometer precision donor devices

DOE PAGES

Ward, Daniel Robert; Marshall, Michael Thomas; Campbell, DeAnna Marie; ...

2017-11-06

In this article, we describe an all-optical lithography process that can make electrical contact to nanometer-precision donor devices fabricated in silicon using scanning tunneling microscopy (STM). This is accomplished by implementing a cleaning procedure in the STM that allows the integration of metal alignment marks and ion-implanted contacts at the wafer level. Low-temperature transport measurements of a patterned device establish the viability of the process.

All-optical lithography process for contacting nanometer precision donor devices

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ward, Daniel Robert; Marshall, Michael Thomas; Campbell, DeAnna Marie

In this article, we describe an all-optical lithography process that can make electrical contact to nanometer-precision donor devices fabricated in silicon using scanning tunneling microscopy (STM). This is accomplished by implementing a cleaning procedure in the STM that allows the integration of metal alignment marks and ion-implanted contacts at the wafer level. Low-temperature transport measurements of a patterned device establish the viability of the process.

Thiolate-bridged dinuclear ruthenium and iron complexes as robust and efficient catalysts toward oxidation of molecular dihydrogen in protic solvents.

PubMed

Yuki, Masahiro; Sakata, Ken; Hirao, Yoshifumi; Nonoyama, Nobuaki; Nakajima, Kazunari; Nishibayashi, Yoshiaki

2015-04-01

Thiolate-bridged dinuclear ruthenium and iron complexes are found to work as efficient catalysts toward oxidation of molecular dihydrogen in protic solvents such as water and methanol under ambient reaction conditions. Heterolytic cleavage of the coordinated molecular dihydrogen at the dinuclear complexes and the sequential oxidation of the produced hydride complexes are involved as key steps to promote the present catalytic reaction. The catalytic activity of the dinuclear complexes toward the chemical oxidation of molecular dihydrogen achieves up to 10000 TON (turnover number), and electrooxidation of molecular dihydrogen proceeds quite rapidly. The result of the density functional theory (DFT) calculation on the reaction pathway indicates that a synergistic effect between the two ruthenium atoms plays an important role to realize the catalytic oxidation of molecular dihydrogen efficiently. The present dinuclear ruthenium complex is found to work as an efficient organometallic anode catalyst for the fuel cell. It is noteworthy that the present dinuclear complex worked not only as an effective catalyst toward chemical and electrochemical oxidation of molecular dihydrogen but also as a good anode catalyst for the fuel cell. We consider that the result described in this paper provides useful and valuable information to develop highly efficient and low-cost transition metal complexes as anode catalysts in the fuel cell.

Evaluation of Ruthenium Capture Methods for Tritium Pretreatment Off-Gas Streams

DOE Office of Scientific and Technical Information (OSTI.GOV)

Spencer, Barry B.; Jubin, Robert Thomas; Bruffey, Stephanie H.

2017-07-01

In the reprocessing of used nuclear fuel, radioactive elements are released into various plant off-gas streams. While much research and development has focused on the abatement of the volatile nuclides 3H, 14C, 85Kr, and 129I, the potential release of semivolatile isotopes that could also report to the off-gas streams in a reprocessing facility has been examined. Ruthenium (as 106Ru) has been identified as one of the semivolatile nuclides requiring the greatest degree of abatement prior to discharging the plant off-gas to the environment.

Flow-injection chemiluminescent determination of estrogen benzoate using the tris(1,10-phenanthroline) ruthenium(II)-permanganate system.

PubMed

Ma, Yan; Cao, Wei; Qiao, Shuang; Liu, Wenwen; Yang, Jinghe

2011-01-01

Chemiluminescence (CL) detection for the determination of estrogen benzoate, using the reaction of tris(1,10-phenanthroline)ruthenium(II)-Na(2)SO(3)-permanganate, is described. This method is based on the CL reaction of estrogen benzoate (EB) with acidic potassium permanganate and tris(1,10-phenanthroline)ruthenium(II). The CL intensity is greatly enhanced when Na(2)SO(3) is added. After optimization of the different experimental parameters, a calibration graph for estrogen benzoate is linear in the range 0.05-10 µg/mL. The 3 s limit of detection is 0.024 µg/mL and the relative standard deviation was 1.3% for 1.0 µg/mL estrogen benzoate (n = 11). This proposed method was successfully applied to commercial injection samples and emulsion cosmetics. The mechanism of CL reaction was also studied. Copyright © 2011 John Wiley & Sons, Ltd.

Nanometer-Scale Force Detected Nuclear Magnetic Resonance Imaging

DTIC Science & Technology

2013-01-01

different crystallographic orientation. Single crystal thin films should thus minimize the stray electric fields by reducing the number of grain ...from epitaxial Ag films, rather than polycrystalline Ag films. It is thought that grain boundaries in polycrystalline metal films give rise to stray...electric fields near the surface of the film. The electric fields are produced as a consequence of the work func- tion difference between grains of

Subatomic deformation driven by vertical piezoelectricity from CdS ultrathin films

PubMed Central

Wang, Xuewen; He, Xuexia; Zhu, Hongfei; Sun, Linfeng; Fu, Wei; Wang, Xingli; Hoong, Lai Chee; Wang, Hong; Zeng, Qingsheng; Zhao, Wu; Wei, Jun; Jin, Zhong; Shen, Zexiang; Liu, Jie; Zhang, Ting; Liu, Zheng

2016-01-01

Driven by the development of high-performance piezoelectric materials, actuators become an important tool for positioning objects with high accuracy down to nanometer scale, and have been used for a wide variety of equipment, such as atomic force microscopy and scanning tunneling microscopy. However, positioning at the subatomic scale is still a great challenge. Ultrathin piezoelectric materials may pave the way to positioning an object with extreme precision. Using ultrathin CdS thin films, we demonstrate vertical piezoelectricity in atomic scale (three to five space lattices). With an in situ scanning Kelvin force microscopy and single and dual ac resonance tracking piezoelectric force microscopy, the vertical piezoelectric coefficient (d33) up to 33 pm·V−1 was determined for the CdS ultrathin films. These findings shed light on the design of next-generation sensors and microelectromechanical devices. PMID:27419234

Subatomic deformation driven by vertical piezoelectricity from CdS ultrathin films.

PubMed

Wang, Xuewen; He, Xuexia; Zhu, Hongfei; Sun, Linfeng; Fu, Wei; Wang, Xingli; Hoong, Lai Chee; Wang, Hong; Zeng, Qingsheng; Zhao, Wu; Wei, Jun; Jin, Zhong; Shen, Zexiang; Liu, Jie; Zhang, Ting; Liu, Zheng

2016-07-01

Driven by the development of high-performance piezoelectric materials, actuators become an important tool for positioning objects with high accuracy down to nanometer scale, and have been used for a wide variety of equipment, such as atomic force microscopy and scanning tunneling microscopy. However, positioning at the subatomic scale is still a great challenge. Ultrathin piezoelectric materials may pave the way to positioning an object with extreme precision. Using ultrathin CdS thin films, we demonstrate vertical piezoelectricity in atomic scale (three to five space lattices). With an in situ scanning Kelvin force microscopy and single and dual ac resonance tracking piezoelectric force microscopy, the vertical piezoelectric coefficient (d 33) up to 33 pm·V(-1) was determined for the CdS ultrathin films. These findings shed light on the design of next-generation sensors and microelectromechanical devices.

Effects of working pressure and annealing on bulk density and nanopore structures in amorphous In-Ga-Zn-O thin-film transistors

NASA Astrophysics Data System (ADS)

Ide, Keisuke; Kikuchi, Mitsuho; Ota, Masato; Sasase, Masato; Hiramatsu, Hidenori; Kumomi, Hideya; Hosono, Hideo; Kamiya, Toshio

2017-03-01

Microstructures of amorphous In-Ga-Zn-O (a-IGZO) thin films of different densities were analyzed. Device-quality a-IGZO films were deposited under optimum conditions, e.g., the total pressure P tot = 0.55 Pa produced high film densities of ˜6.1 g/cm3, while a very high P tot = 5.0 Pa produced low film densities of 5.5 g/cm3. Both films formed uniform high-density layers in the vicinity of the glass substrate, 10-20 nm in thickness depending on P tot, while their growth mode changed to a sparse columnar structure in thicker regions. X-ray reflectivity and in situ spectroscopic ellipsometry provided different results on densification by post deposition thermal annealing; i.e., the latter has a higher sensitivity. High-Z-contrast images obtained by high-angle annular dark-field scanning transmission electron microscopy were also useful for detecting nanometer-size non uniformity even in device-quality a-IGZO films.

Fluorescence emission and polarization analyses for evaluating binding of ruthenium metalloglycocluster to lectin and tetanus toxin c-fragment

NASA Astrophysics Data System (ADS)

Okada, Tomoko; Minoura, Norihiko

2010-02-01

We have developed a fluorescent ruthenium metalloglycocluster as a powerful molecular probe for evaluating a binding event between carbohydrates and lectins by fluorescence emission (FE) and fluorescence polarization (FP) analysis. The fluorescent ruthenium metalloglycoclusters, [Ru(bpy-2Gal)3] and [Ru(bpy-2Glc)3], possess clustered galactose and glucose surrounding the ruthenium center. Changes in FE and FP of these metalloglycoclusters were measured by adding each lectin (Peanut agglutinin (PNA), Ricinus communis agglutinin 120 (RCA), Concanavalin A (ConA), or Wheat germ agglutinin (WGA)) or tetanus toxin c-fragment (TCF). Following the addition of PNA, the FE spectrum of [Ru(bpy- 2Gal)3] showed new emission peak and the FP value of [Ru(bpy-2Gal)3] increased. Similarly, the FE spectrum of [Ru(bpy-2Glc)3] showed new emission peak and the FP value increased following the addition of ConA. Since other combinations of the metalloglycoclusters and lectin caused little change, specific bindings of galactose to PNA and glucose to ConA were proved by the FE and FP measurement. From nonlinear least-squares fitting, dissociation constants (Kd) of [Ru(bpy-2Gal)3] to PNA was 6.1 μM, while the Kd values of [Ru(bpy)2(bpy-2Gal)] to PNA was ca. 10-4 M. Therefore, the clustered carbohydrates were proved to increase affinity to lectins. Furthermore, the FP measurements proved specific binding of [Ru(bpy-2Gal)3] to TCF.

4d Electronic structure analysis of ruthenium in the perovskite oxides by Ru K- and L-edge XAS.

PubMed

Kim, J Y; Hwang, S H; Kim, S J; Demazeau, G; Choy, J H; Shimada, H

2001-03-01

The 4d electronic structure of ruthenium in the perovskite oxides, La2MRuIVO6 (M = Zn, Mg, and Li) and Ba2YRuVO6, has been investigated by the Ru K-and L-edge XANES and EXAFS analyses. Such X-ray absorption spectroscopic results clarify that the RuIV (d4) and RuV (d3) ions are stabilized in nearly regular Oh site. Comparing the Ru L-edge XANES spectra of perovskites containing isovalent ruthenium, it has been found that the t2g state is mainly influenced by A site cation, whereas the eg is mainly affected by neighboring B site cation. The experimental EXAFS spectra in the range of R < or = approximately 4.5 A are well reproduced by ab-initio calculation based on crystallographic data, which supports the long-range structure presented by Rietveld refinement.

Optical Properties of Ar Ions Irradiated Nanocrystalline ZrC and ZrN Thin Films

NASA Technical Reports Server (NTRS)

Martin, C.; Miller, K. H.; Makino, H.; Craciun, D.; Simeone, D.; Craciun, V.

2017-01-01

Thin nanocrystalline ZrC and ZrN films (less than 400 nanometers), grown on (100) Si substrates at a substrate temperature of 500 degrees Centigrade by the pulsed laser deposition (PLD) technique, were irradiated by 800 kiloelectronvolts Ar ion irradiation with fluences from 1 times 10(sup 14) atoms per square centimeter up to 2 times 10(sup 15) atoms per square centimeter. Optical reflectance data, acquired from as-deposited and irradiated films, in the range of 500-50000 per centimeter (0.06–6 electronvolts), was used to assess the effect of irradiation on the optical and electronic properties. Both in ZrC and ZrN films we observed that irradiation affects the optical properties of the films mostly at low frequencies, which is dominated by the free carriers response. In both materials, we found a significant reduction in the free carriers scattering rate, i.e. possible increase in mobility, at higher irradiation flux. This is consistent with our previous findings that irradiation affects the crystallite size and the micro-strain, but it does not induce major structural changes.

Spray pyrolysed Ru:TiO2 thin film electrodes prepared for electrochemical supercapacitor

NASA Astrophysics Data System (ADS)

Fugare, B. Y.; Thakur, A. V.; Kore, R. M.; Lokhande, B. J.

2018-04-01

Ru doped TiO2 thin films are prepared by using 0.06 M aqueous solution of potassium titanium oxalate (pto), and 0.005 M aqueous solution of ruthenium tri chloride (RuCl3) precursors. The deposition was carried on stainless steel (SS) by using well known ultrasonic spray pyrolysis technique (USPT) at 723° K by maintaining the spray rate 12 cc/min and compressed air flow rate 10 Lmin-1. Prepared Ru:TiO2 thin films were characterized by structurally, morphologically and electrochemically. Deposited RuO2 shows amorphous structure and TiO2 shows tetragonal crystal structure with rutile as prominent phase at very low decomposition temperature. SEM micrographs of RuO2 exhibits porous, interconnected, spherical grains type morphology and TiO2 shows porous, nanorods and nanoplates like morphology and also Ru doped TiO2 shows porous, spherical, granular and nanorods type morphology. The electrochemical cyclic voltammetery shows mixed capacitive behavior. The achieved highest value of specific capacitance 2692 F/g was Ru doped TiO2 electrode in 0.5 M H2SO4.

Synthesis, Structure and Antitumour Properties of a New 1,2-Propylenediaminetetraacetate-Ruthenium(III) Compound

PubMed Central

Vilaplana, R.; Romero, M. A.; Quirós, M.; Salas, J. M.

1995-01-01

A novel complex formed by ruthenium (III) and the sequestering ligand 1,2-propylenediaminetetraacetic acid (PDTA) has been synthetized and characterized. The structure of the monomeric compound, studied by X-ray diffraction , shows an almost symmetric octahedral geometry around the metal ion, with two chlorine atoms in a cis conformation. The antitumour activity against a variety of murine and human cancers is reported. PMID:18472768

Micrometer- and nanometer-sized platinum group nuggets in micrometeorites from deep-sea sediments of the Indian Ocean

NASA Astrophysics Data System (ADS)

Rudraswami, N. G.; Parashar, K.; Shyam Prasad, M.

2011-03-01

We examined 378 micrometeorites collected from deep-sea sediments of the Indian Ocean of which 175, 180, and 23 are I-type, S-type, and G-type, respectively. Of the 175 I-type spherules, 13 contained platinum group element nuggets (PGNs). The nuggets occur in two distinct sizes and have distinctly different elemental compositions: micrometer (μm)-sized nuggets that are >3 μm contain dominantly Ir, Os, and Ru (iridium-platinum group element or IPGE) and sub-μm (or nanometer)-sized (<1 μm) nuggets, which contain dominantly Pt, Rh, and Pd (palladium—PGE or PPGE). The μm-sized nuggets are found only one per spherule in the cross section observed and are usually found at the edge of the spherule. By contrast, there are hundreds of nanometer-sized nuggets distributed dominantly in the magnetite phases of the spherules, and rarely in the wüstite phases. Both the nugget types are found as separate entities in the same spherule and apparently, nugget formation is a common phenomenon among I-type micrometeorites. However, the μm-sized nuggets are seen in fewer specimens (˜2.5% of the observed I-type spherules). In all, we analyzed four nuggets of μm size and 213 nanometer-sized nuggets from 13 I-type spherules for platinum group elements. Chemically, the μm-sized PGNs contain chondritic ratios of Os/Ir, but are depleted in the more volatile PGE (Pt, Rh, and Pd) relative to chondritic ratios. On the other hand, the nanometer-sized nuggets contain dominantly Pt and Rh. Importantly, the refractory PGEs are conspicuous by their absence in these nanometer nuggets. Palladium, the most volatile PGE is highly depleted (<1.1%) with respect to chondritic ratios in the μm-sized PGNs, and is observed in only 17 of 213 nanometer nuggets with concentrations that are just above the detection limit (≥0.2%). Distinct fractionation of the PGE into IPGE (Ir, Os, Ru) and PPGE seems to take place during the short span of atmospheric entry. These observations suggest several

Universal Method for Creating Hierarchical Wrinkles on Thin-Film Surfaces.

PubMed

Jung, Woo-Bin; Cho, Kyeong Min; Lee, Won-Kyu; Odom, Teri W; Jung, Hee-Tae

2018-01-10

One of the most interesting topics in physical science and materials science is the creation of complex wrinkled structures on thin-film surfaces because of their several advantages of high surface area, localized strain, and stress tolerance. In this study, a significant step was taken toward solving limitations imposed by the fabrication of previous artificial wrinkles. A universal method for preparing hierarchical three-dimensional wrinkle structures of thin films on a multiple scale (e.g., nanometers to micrometers) by sequential wrinkling with different skin layers was developed. Notably, this method was not limited to specific materials, and it was applicable to fabricating hierarchical wrinkles on all of the thin-film surfaces tested thus far, including those of metals, two-dimensional and one-dimensional materials, and polymers. The hierarchical wrinkles with multiscale structures were prepared by sequential wrinkling, in which a sacrificial layer was used as the additional skin layer between sequences. For example, a hierarchical MoS 2 wrinkle exhibited highly enhanced catalytic behavior because of the superaerophobicity and effective surface area, which are related to topological effects. As the developed method can be adopted to a majority of thin films, it is thought to be a universal method for enhancing the physical properties of various materials.

Giant asymmetric self-phase modulation in superconductor thin films

NASA Astrophysics Data System (ADS)

Robson, Charles W.; Biancalana, Fabio

2018-04-01

Self-phase modulation (SPM) of light pulses is found to occur strongly, at low incident intensities, in the coupling of light with superconductors. We develop a theory from a synthesis of the time-dependent Ginzburg-Landau (TDGL) equation and basic electrodynamics which shows the strongly non-linear phase accumulated in the interaction. Unusually, the SPM of the pulse in this system is found to be highly asymmetric, producing a strongly redshifted spectrum when interacting with a superconducting thin film, and it develops in just a few nanometers of propagation. In this paper we present theoretical results and simulations in the THz regime, for both hyperbolic secant and supergaussian-shaped pulses.

Ruthenium(II)-Catalyzed C-H Activation of Imidamides and Divergent Couplings with Diazo Compounds: Substrate-Controlled Synthesis of Indoles and 3H-Indoles.

PubMed

Li, Yunyun; Qi, Zisong; Wang, He; Yang, Xifa; Li, Xingwei

2016-09-19

Indoles are an important structural motif that is commonly found in biologically active molecules. In this work, conditions for divergent couplings between imidamides and acceptor-acceptor diazo compounds were developed that afforded NH indoles and 3H-indoles under ruthenium catalysis. The coupling of α-diazoketoesters afforded NH indoles by cleavage of the C(N2 )-C(acyl) bond whereas α-diazomalonates gave 3H-indoles by C-N bond cleavage. This reaction constitutes the first intermolecular coupling of diazo substrates with arenes by ruthenium-catalyzed C-H activation. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hydration behavior of casein micelles in thin film geometry: a GISANS study?

PubMed

Metwalli, E; Moulin, J F; Gebhardt, R; Cubitt, R; Tolkach, A; Kulozik, U; Müller-Buschbaum, P

2009-04-07

The water content of casein micelle films in water vapor atmosphere is investigated using time-resolved grazing incidence small-angle neutron scattering (GISANS). Initial dry casein films are prepared with a spin-coating method. At 30 degrees C, the formation of a water-equilibrated casein protein film is reached after 11 min with a total content of 0.36 g of water/g of protein. With increasing water vapor temperature up to 70 degrees C, an increase in the water content is found. With GISANS, lateral structures on the nanometer scale are resolved during the swelling experiment at different temperatures and modeled using two types of spheres: micelles and mini-micelles. Upon water uptake, molecular assemblies in the size range of 15 nm (mini-micelles) are attributed to the formation of a high-contrast D2O outer shell on the small objects that already exist in the protein film. For large objects (>100 nm), the mean size increases at high D2O vapor temperature because of possible aggregation between hydrated micelles. These results are discussed and compared with various proposed models for casein micelle structures.

Self organized striping in ultra thin polymer films near melt: An investigation using Monte Carlo simulation

NASA Astrophysics Data System (ADS)

Singh, Satya Pal

2018-05-01

This paper work presents the results of Monte Carlo simulation performed for ultra thin short chained polymer films near melt, under strong confinement. Thin polymer films get ruptured when annealed above their glass transition temperatures. The pattern formations are generally explained on the basis of spinodal mechanism, if the thickness of the film is of the order of few tens of nanometers i.e. <100 nm. In this case, the film seems to tear apart in strips. The free end segments of the chains are more dynamic and coalescence into one another. This process seems to dominate over the spinodal waves resulting into a different type of dynamics. Polymer chains with 30 monomers are taken. 160, 200 and 240 chains are taken for three different cases of the studies. The three cases correspond to three different thickness of the films with 8, 10 and 12 layers of chains along direction perpendicular to the confining substrates. The bottom surface has affinity to monomers, whereas the upper surface has hard wall interaction with the monomers. Different time micrographs of the films are plotted along with density distributions of the monomers to explore the process.

The solubility of hydrogen in rhodium, ruthenium, iridium and nickel.

NASA Technical Reports Server (NTRS)

Mclellan, R. B.; Oates, W. A.

1973-01-01

The temperature variation of the solubility of hydrogen in rhodium, ruthenium, iridium, and nickel in equilibrium with H2 gas at 1 atm pressure has been measured by a technique involving saturating the solvent metal with hydrogen, quenching, and analyzing in resultant solid solutions. The solubilities determined are small (atom fraction of H is in the range from 0.0005 to 0.00001, and the results are consistent with the simple quasi-regular model for dilute interstitial solid solutions. The relative partial enthalpy and excess entropy of the dissolved hydrogen atoms have been calculated from the solubility data and compared with well-known correlations between these quantities.

Extensive Penetration of Evaporated Electrode Metals into Fullerene Films: Intercalated Metal Nanostructures and Influence on Device Architecture.

PubMed

Zhang, Guangye; Hawks, Steven A; Ngo, Chilan; Schelhas, Laura T; Scholes, D Tyler; Kang, Hyeyeon; Aguirre, Jordan C; Tolbert, Sarah H; Schwartz, Benjamin J

2015-11-18

Although it is known that evaporated metals can penetrate into films of various organic molecules that are a few nanometers thick, there has been little work aimed at exploring the interaction of the common electrode metals used in devices with fullerene derivatives, such as organic photovoltaics (OPVs) or perovskite solar cells that use fullerenes as electron transport layers. In this paper, we show that when commonly used electrode metals (e.g., Au, Ag, Al, Ca, etc.) are evaporated onto films of fullerene derivatives (such as [6,6]-phenyl-C61-butyric acid methyl ester (PCBM)), the metal penetrates many tens of nanometers into the fullerene layer. This penetration decreases the effective electrical thickness of fullerene-based sandwich structure devices, as measured by the device's geometric capacitance, and thus significantly alters the device physics. For the case of Au/PCBM, the metal penetrates a remarkable 70 nm into the fullerene, and we see penetration of similar magnitude in a wide variety of fullerene derivative/evaporated metal combinations. Moreover, using transmission electron microscopy to observed cross-sections of the films, we show that when gold is evaporated onto poly(3-hexylthiophene) (P3HT)/PCBM sequentially processed OPV quasi-bilayers, Au nanoparticles with diameters of ∼3-20 nm are formed and are dispersed entirely throughout the fullerene-rich overlayer. The plasmonic absorption and scattering from these nanoparticles are readily evident in the optical transmission spectrum, demonstrating that the interpenetrated metal significantly alters the optical properties of fullerene-rich active layers. This opens a number of possibilities in terms of contact engineering and light management so that metal penetration in devices that use fullerene derivatives could be used to advantage, making it critical that researchers are aware of the electronic and optical consequences of exposing fullerene-derivative films to evaporated electrode metals.

Carbon Nanotubules: Building Blocks for Nanometer-Scale Engineering

NASA Technical Reports Server (NTRS)

Sinnott, Susan B.

1999-01-01

The proposed work consisted of two projects: the investigation of fluid permeation and diffusion through ultrafiltration membranes composed of carbon nanotubules and the design and study of molecular transistors composed of nanotubules. The progress made on each project is summarized and also discussion about additional projects, one of which is a continuation of work supported by another grant, is included. The first project was Liquid Interactions within a Nanotubule Membrane. The second was the design of nanometer-scale hydrocarbon electronic devices. The third was the investigation of Mechanical properties of Nanotubules and Nanotubule bundles. The fourth project was to investigate the growth mechanisms of Carbon Nanotubules.

Investigation of Ruthenium Dissolution in Advanced Membrane Electrode Assemblies for Direct Methanol Based Fuel Cells Stacks

NASA Technical Reports Server (NTRS)

Valdez, T. I.; Firdosy, S.; Koel, B. E.; Narayanan, S. R.

2005-01-01

This viewgraph presentation gives a detailed review of the Direct Methanol Based Fuel Cell (DMFC) stack and investigates the Ruthenium that was found at the exit of the stack. The topics include: 1) Motivation; 2) Pathways for Cell Degradation; 3) Cell Duration Testing; 4) Duration Testing, MEA Analysis; and 5) Stack Degradation Analysis.

NANOMETER DIESEL EXHAUST PARTICLES ARE NEUROTOXIC TO DOPAMINERGIC NEURONS THROUGH MICROGLIAL ACTIVATION.

EPA Science Inventory

NANOMETER DIESEL EXHAUST PARTICLES ARE NEUROTOXIC TO DOPAMINERGIC NEURONS THROUGH MICROGLIAL ACTIVATION. M.L. Block1,2, X. Wu1, P. Zhong1, G. Li1, T. Wang1, J.S. Hong1 & B.Veronesi.2
1The Laboratory of Pharmacology and Chemistry, NIEHS, RTP, NC and 2 National Health and Envi...

Dynamics of coupled plasmon polariton wave packets excited at a subwavelength slit in optically thin metal films

NASA Astrophysics Data System (ADS)

Wang, Lei-Ming; Zhang, Lingxiao; Seideman, Tamar; Petek, Hrvoje

2012-10-01

We study by numerical simulations the excitation and propagation dynamics of coupled surface plasmon polariton (SPP) wave packets (WPs) in optically thin Ag films and a bulk Ag/vacuum interface under the illumination of a subwavelength slit by 400 nm continuous wave (cw) and femtosecond pulsed light. The generated surface fields include contributions from both SPPs and quasicylindrical waves, which dominate in different regimes. We explore aspects of the coupled SPP modes in Ag thin films, including symmetry, propagation, attenuation, and the variation of coupling with incident angle and film thickness. Simulations of the electromagnetic transients initiated with femtosecond pulses reveal new features of coupled SPP WP generation and propagation in thin Ag films. Our results show that, under pulsed excitation, the SPP modes in an Ag thin film break up into two distinct bound surface wave packets characterized by marked differences in symmetries, group velocities, attenuation lengths, and dispersion properties. The nanometer spatial and femtosecond temporal scale excitation and propagation dynamics of the coupled SPP WPs are revealed in detail by movies recording the evolution of their transient field distributions.

Liquid crystal films as on-demand, variable thickness (50–5000 nm) targets for intense lasers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Poole, P. L., E-mail: poole.134@osu.edu; Andereck, C. D.; Schumacher, D. W.

2014-06-15

We have developed a new type of target for intense laser-matter experiments that offers significant advantages over those currently in use. The targets consist of a liquid crystal film freely suspended within a metal frame. They can be formed rapidly on-demand with thicknesses ranging from nanometers to micrometers, where the particular value is determined by the liquid crystal temperature and initial volume as well as by the frame geometry. The liquid crystal used for this work, 8CB (4′-octyl-4-cyanobiphenyl), has a vapor pressure below 10{sup −6} Torr, so films made at atmospheric pressure maintain their initial thickness after pumping to high vacuum.more » Additionally, the volume per film is such that each target costs significantly less than one cent to produce. The mechanism of film formation and relevant physics of liquid crystals are described, as well as ion acceleration data from the first shots on liquid crystal film targets at the Ohio State University Scarlet laser facility.« less

Nanostructuring and texturing of pulsed laser deposited hydroxyapatite thin films

NASA Astrophysics Data System (ADS)

Kim, Hyunbin; Catledge, Shane; Vohra, Yogesh; Camata, Renato; Lacefield, William

2003-03-01

Hydroxyapatite (HA) [Ca_10(PO_4)_6(OH)_2] is commonly deposited onto orthopedic and dental metallic implants to speed up bone formation around devices, allowing earlier stabilization in a patient. Pulsed laser deposition (PLD) is a suitable means of placing thin HA films on these implants because of its control over stoichiometry, crystallinity, and nanostructure. These characteristics determine the mechanical properties of the films that must be optimized to improve the performance of load-bearing implants and other devices that undergo bone insertion. We have used PLD to produce nanostructured and preferentially oriented HA films and evaluated their mechanical properties. Pure, highly crystalline HA films on Ti-6Al-4V substrates were obtained using a KrF excimer laser (248nm) with energy density of 4-8 J/cm^2 and deposition temperature of 500-700^rcC. Scanning electron and atomic force microscopies reveal that our careful manipulation of energy density and substrate temperature has led to films made up of HA grains in the nanometer scale. Broadening of x-ray diffraction peaks as a function of deposition temperature suggests it may be possible to control the film nanostructure to a great extent. X-ray diffraction also shows that as the laser energy density is increased in the 4-8 J/cm^2 range, the hexagonal HA films become preferentially oriented along the c-axis perpendicular to the substrate. Texture, nanostructure, and phase make-up all significantly influence the mechanical properties. We will discuss how each of these factors affects hardness and Young's modulus of the HA films as measured by nanoindentation.

Inductively Coupled Plasma Mass Spectrometry: Sample Analysis of Zirconium and Ruthenium in Metal Organic Frameworks

DTIC Science & Technology

2018-02-01

international proficiency testing sponsored by the Organisation for the Prohibition of Chemical Weapons (The Hague, Netherlands). Traditionally...separate batch of standards at each level for a total of six analyses at each calibration level. Concentrations of the tested calibration levels are...and ruthenium at each calibration level. 11 REFERENCES 1. General Requirements for the Competence of Testing and Calibration Laboratories

Spontaneous formation of multiple land-and-groove structures of silica thin films

NASA Astrophysics Data System (ADS)

Takeda, Yasuhiko; Matsuoka, Yoriko; Motohiro, Tomoyoshi

1999-05-01

We found spontaneous formation of microscopic multiple land-and-groove structures of silica thin films. Silica and nickel were simultaneously deposited onto glass substrates from two opposite oblique directions to form columnar structures of silica among which nickel nanoparticles were embedded. Then nickel was dissolved in hydrochloric acid solution. After the dissolution of the nickel particles the columns of silica became very unstable and coalesced to form the multiple land-and-groove structures. The grooves are oriented to the direction perpendicular to the two deposition directions. The distances between the neighboring grooves are fairly uniform, and can be controlled between several hundred nanometers and several microns by changing the film thickness and the ratio of the nickel deposition rate to the silica deposition rate. The process found here may propose a new class of micro fabrication techniques in contrast to the artificial photolithography.

Nanometer-scale modification and welding of silicon and metallic nanowires with a high-intensity electron beam.

PubMed

Xu, Shengyong; Tian, Mingliang; Wang, Jinguo; Xu, Jian; Redwing, Joan M; Chan, Moses H W

2005-12-01

We demonstrate that a high-intensity electron beam can be applied to create holes, gaps, and other patterns of atomic and nanometer dimensions on a single nanowire, to weld individual nanowires to form metal-metal or metal-semiconductor junctions, and to remove the oxide shell from a crystalline nanowire. In single-crystalline Si nanowires, the beam induces instant local vaporization and local amorphization. In metallic Au, Ag, Cu, and Sn nanowires, the beam induces rapid local surface melting and enhanced surface diffusion, in addition to local vaporization. These studies open up a novel approach for patterning and connecting nanomaterials in devices and circuits at the nanometer scale.

Tribology-Structure Relationships in Silicon Oxycarbide Thin Films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ryan, Joseph V.; Colombo, Paolo; Howell, Jane A.

Silicon oxycarbide is a versatile material system that is attractive for many applications because of its ability to tune properties such as chemical compatibility, refractive index, electrical conductivity, and optical band gap through changes in composition. One particularly intriguing application lies in the production of biocompatible coatings with good mechanical properties. In this paper, we report on the wide range of mechanical and tribological property values exhibited by silicon oxycarbide thin films deposited by reactive radio frequency magnetron sputtering. Through a change in oxygen partial pressure in the sputtering plasma, the composition of the films was controlled to produce relativelymore » pure SiO2, carbon-doped SiC, and compositions between these limits. Hardness values were 8-20 GPa over this range and the elastic modulus was measured to be between 60 and 220 GPa. We call attention to the fit of the mechanical data to a simple additive bond-mixture model for property prediction. Tribological parameters were measured using a ball-on-disk apparatus and the samples exhibited the same general trends for friction coefficient and wear rate. One film is shown to produce variable low friction behavior and low wear rate, which suggests a solid-state self-lubrication process because of heterogeneity on the nanometer scale.« less

Flow injection chemiluminescent determination of tetracycline using a tris(2,2'-bipyridine)ruthenium(II)-cerium(IV) sulphate system.

PubMed

Guo, Liangqia; Xie, Zenghong; Lin, Xucong; Liu, Xiaohua; Zhang, Weilin; Chen, Guonan

2004-01-01

A flow-injection chemiluminescence method for the determination of tetracycline was developed. The method is based on an enhancement by tetracycline of the chemiluminescence light emission of tris(2,2'-bipyridine)ruthenium(II). In sulphuric acid medium, the chemiluminescence is generated by the continuous oxidation of tris(2,2'-bipyridine)ruthenium(II) by cerium (IV) sulphate. The light-emission intensity is greatly enhanced in the presence of tetracycline. Under the optimum conditions, the calibration curve is linear over the range 3.75 x 10(-8) g/mL-1.5 x 10(-5) g/mL for tetracycline with the linear equation: deltaINT = 205.898 x C - 20.442 (R2 = 0.9974). The detection limit is 3.27 x 10(-8) g/mL. The proposed method was also successfully used to determine tetracycline in pharmaceutical formulation (mean recovery of tetracycline, 100.7%). Copyright 2004 John Wiley & Sons, Ltd.

Highly Regioselective Synthesis of Substituted Isoindolinones via Ruthenium-Catalyzed Alkyne Cyclotrimerizations

PubMed Central

Foster, Robert W; Tame, Christopher J; Hailes, Helen C; Sheppard, Tom D

2013-01-01

(Cyclooctadiene)(pentamethylcyclopentadiene)ruthenium chloride [Cp*RuCl(cod)] has been used to catalyze the regioselective cyclization of amide-tethered diynes with monosubstituted alkynes to give polysubstituted isoindolinones. Notably, the presence of a trimethylsilyl group on the diyne generally led to complete control over the regioselectivity of the alkyne cyclotrimerization. The cyclization reaction worked well in a sustainable non-chlorinated solvent and was tolerant of moisture. The optimized conditions were effective with a diverse range of alkynes and diynes. The 7-silylisoindolinone products could be halogenated, protodesilylated or ring opened to access a range of usefully functionalized products. PMID:24124414

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition

NASA Astrophysics Data System (ADS)

Gill, Martin R.; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A.; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A.

2016-08-01

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)]2+ (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)]2+ before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

A ruthenium polypyridyl intercalator stalls DNA replication forks, radiosensitizes human cancer cells and is enhanced by Chk1 inhibition.

PubMed

Gill, Martin R; Harun, Siti Norain; Halder, Swagata; Boghozian, Ramon A; Ramadan, Kristijan; Ahmad, Haslina; Vallis, Katherine A

2016-08-25

Ruthenium(II) polypyridyl complexes can intercalate DNA with high affinity and prevent cell proliferation; however, the direct impact of ruthenium-based intercalation on cellular DNA replication remains unknown. Here we show the multi-intercalator [Ru(dppz)2(PIP)](2+) (dppz = dipyridophenazine, PIP = 2-(phenyl)imidazo[4,5-f][1,10]phenanthroline) immediately stalls replication fork progression in HeLa human cervical cancer cells. In response to this replication blockade, the DNA damage response (DDR) cell signalling network is activated, with checkpoint kinase 1 (Chk1) activation indicating prolonged replication-associated DNA damage, and cell proliferation is inhibited by G1-S cell-cycle arrest. Co-incubation with a Chk1 inhibitor achieves synergistic apoptosis in cancer cells, with a significant increase in phospho(Ser139) histone H2AX (γ-H2AX) levels and foci indicating increased conversion of stalled replication forks to double-strand breaks (DSBs). Normal human epithelial cells remain unaffected by this concurrent treatment. Furthermore, pre-treatment of HeLa cells with [Ru(dppz)2(PIP)](2+) before external beam ionising radiation results in a supra-additive decrease in cell survival accompanied by increased γ-H2AX expression, indicating the compound functions as a radiosensitizer. Together, these results indicate ruthenium-based intercalation can block replication fork progression and demonstrate how these DNA-binding agents may be combined with DDR inhibitors or ionising radiation to achieve more efficient cancer cell killing.

Femtosecond laser ablation-based mass spectrometry. An ideal tool for stoichiometric analysis of thin films

DOE PAGES

LaHaye, Nicole L.; Kurian, Jose; Diwakar, Prasoon K.; ...

2015-08-19

An accurate and routinely available method for stoichiometric analysis of thin films is a desideratum of modern materials science where a material’s properties depend sensitively on elemental composition. We thoroughly investigated femtosecond laser ablation-inductively coupled plasma-mass spectrometry (fs-LA-ICP-MS) as an analytical technique for determination of the stoichiometry of thin films down to the nanometer scale. The use of femtosecond laser ablation allows for precise removal of material with high spatial and depth resolution that can be coupled to an ICP-MS to obtain elemental and isotopic information. We used molecular beam epitaxy-grown thin films of LaPd (x)Sb 2 and T´-La 2CuOmore » 4 to demonstrate the capacity of fs-LA-ICP-MS for stoichiometric analysis and the spatial and depth resolution of the technique. Here we demonstrate that the stoichiometric information of thin films with a thickness of ~10 nm or lower can be determined. Furthermore, our results indicate that fs-LA-ICP-MS provides precise information on the thin film-substrate interface and is able to detect the interdiffusion of cations.« less

Melting behavior of nanometer sized gold isomers

NASA Astrophysics Data System (ADS)

Liu, H. B.; Ascencio, J. A.; Perez-Alvarez, M.; Yacaman, M. J.

2001-09-01

In the present work, the melting behavior of nanometer sized gold isomers was studied using a tight-binding potential with a second momentum approximation. The cases of cuboctahedra, icosahedra, Bagley decahedra, Marks decahedra and star-like decahedra were considered. We calculated the temperature dependence of the total energy and volume during melting and the melting point for different types and sizes of clusters. In addition, the structural evolutions of the nanosized clusters during the melting transition were monitored and revealed. It is found that the melting process has three characteristic time periods for the intermediate nanosized clusters. The whole process includes surface disordering and reordering, followed by surface melting and a final rapid overall melting. This is a new observation, which it is in contrast with previous reports where surface melting is the dominant step.

DSPI technique for nanometer vibration mode measurement

NASA Astrophysics Data System (ADS)

Yue, Kaiduan; Jia, Shuhai; Tan, Yushan

2000-05-01

A time-average DSPI method for nanometer vibration mode measurement is presented in this paper. The phase continuous scan technique is combined with the Bessel fringe-shifting technique to quantitatively analyze the vibration mode by time-average DSPI is used in measurement system. Through the phase continuous scan, the background and speckle items are completely eliminated, which improves the fringe quality and enhances the signal-to-noise ratio of interferogram. There is no need to calibrate the optical phase-shifter exactly in this method. The anti-disturbance capability of this method is higher than that of the phase-stepping technique, so it is robust and easy to be used. In the vibration measurement system, the speckle average technology is used, so the high quality measuring results are obtained.

Nanoscale deformation mechanism of TiC/a-C nanocomposite thin films

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, C. Q.; Pei, Y. T.; Shaha, K. P.

2009-06-01

This paper concentrates on the deformation behavior of amorphous diamondlike carbon composite materials. Combined nanoindentation and ex situ cross-sectional transmission electron microscopy investigations are carried out on TiC/a-C nanocomposite films, with and without multilayered structures deposited by pulse dc magnetron sputtering. It is shown that by controlling the distribution of nanocrystallites forming nanoscale multilayers, the system can be used as a 'microstructural ruler' that is able to distinguish various deformation patterns, which can be hardly detected otherwise in a homogeneous structure. It is shown that rearrangement of nanocrystallites and displacement of a-C matrix occur at length scales from tens ofmore » nanometer down to 1 nm. At submicrometer scale homogeneous nucleation of multiple shear bands has been observed within the nanocomposites. The multilayered structure in the TiC/a-C nanocomposite film contributes to an enhanced toughness.« less

Continuous planar phospholipid bilayer supported on porous silicon thin film reflector.

PubMed

Cunin, Frédérique; Milhiet, Pierre-Emmanuel; Anglin, Emily; Sailor, Michael J; Espenel, Cédric; Le Grimellec, Christian; Brunel, Daniel; Devoisselle, Jean-Marie

2007-10-01

Reconstituting artificial membranes for in vitro studies of cell barrier mechanisms and properties is of major interest in biology. Here, artificial membranes supported on porous silicon photonic crystal reflectors are prepared and investigated. The materials are of interest for label-free probing of supported membrane events such as protein binding, molecular recognition, and transport. The porous silicon substrates are prepared as multilayered films consisting of a periodically varying porosity, with pore dimensions of a few nanometers in size. Planar phospholipid bilayers are deposited on the topmost surface of the oxidized hydrophilic mesoporous silicon films. Atomic force microscopy provides evidence of continuous bilayer deposition at the surface, and optical measurements indicate that the lipids do not significantly infiltrate the porous region. The presence of the supported bilayer does not obstruct the optical spectrum from the porous silicon layer, suggesting that the composite structures can act as effective optical biosensors.

Size-controlled synthesis of nanocrystalline CdSe thin films by inert gas condensation

NASA Astrophysics Data System (ADS)

Sharma, Jeewan; Singh, Randhir; Kumar, Akshay; Singh, Tejbir; Agrawal, Paras; Thakur, Anup

2018-02-01

Size, shape and structure are considered to have significant influence on various properties of semiconducting nanomaterials. Different properties of these materials can be tailored by controlling the size. Size-controlled CdSe crystallites ranging from ˜ 04 to 95 nm were deposited by inert gas-condensation technique (IGC). In IGC method, by controlling the inert gas pressure in the condensation chamber and the substrate temperature or both, it was possible to produce nanoparticles with desired size. Structure and crystallite size of CdSe thin films were determined from Hall-Williamson method using X-ray diffraction data. The composition of CdSe samples was estimated by X-ray microanalysis. It was confirmed that CdSe thin film with different nanometer range crystallite sizes were synthesized with this technique, depending upon the synthesis conditions. The phase of deposited CdSe thin films also depend upon deposition conditions and cubic to hexagonal phase transition was observed with increase in substrate temperature. The effect of crystallite size on optical and electrical properties of these films was also studied. The crystallite size affects the optical band gap, electrical conductivity and mobility activation of nanocrystalline CdSe thin films. Mobility activation study suggested that there is a quasi-continuous linear distribution of three different trap levels below the conduction band.

Nanometer-scale displacement measurement with high resolution using dual cavity Fabry-Pérot interferometer for biomimetic robots.

PubMed

Lee, Jin-Hyuk; Kim, Dae-Hyun

2014-10-01

A sensor of a biomimetic robot has to measure very small environmental changes such as, nanometer scale strains or displacements. Fiber optic sensor can be also one of candidates for the biomimetic sensor because the sensor is like thread and the shape of the sensor is similar to muscle fiber. A fiber optic interferometer, which is an optical-based sensor, can measure displacement precisely, so such device has been widely studied for the measurement of displacement on a nanometer-scale. Especially, a Quadrature Phase-Shifted Fiber Fabry-Pérot interferometer (QPS-FFPI) uses phase-information for this measurement, allowing it to provide a precision result with high resolution. In theory, the QPS-FFPI generates two sinusoidal signals of which the phase difference should be 90 degrees for the exact measurement of the displacement. In order to guarantee the condition of the phase difference, the relative adjustment of the cavities of the optical fibers is required. However, with such precise adjustment it is very hard to fix the proper difference of the two cavities for quadrature-phase-shifting. In this paper, a dual-cavity FFPI is newly proposed to measure the displacement on a nanometer-scale with a specific type of signal processing. In the signal processing, a novel phase-compensation algorithm is applied to force the phase difference to be exactly 90 degrees without any physical adjustment. As a result, the paper shows that the phase-compensated dual-cavity FFPI can effectively measure nanometer-scale displacement with high resolution under dynamic conditions.

Mapping Thermal Expansion Coefficients in Freestanding 2D Materials at the Nanometer Scale

NASA Astrophysics Data System (ADS)

Hu, Xuan; Yasaei, Poya; Jokisaari, Jacob; Öǧüt, Serdar; Salehi-Khojin, Amin; Klie, Robert F.

2018-02-01

Two-dimensional materials, including graphene, transition metal dichalcogenides and their heterostructures, exhibit great potential for a variety of applications, such as transistors, spintronics, and photovoltaics. While the miniaturization offers remarkable improvements in electrical performance, heat dissipation and thermal mismatch can be a problem in designing electronic devices based on two-dimensional materials. Quantifying the thermal expansion coefficient of 2D materials requires temperature measurements at nanometer scale. Here, we introduce a novel nanometer-scale thermometry approach to measure temperature and quantify the thermal expansion coefficients in 2D materials based on scanning transmission electron microscopy combined with electron energy-loss spectroscopy to determine the energy shift of the plasmon resonance peak of 2D materials as a function of sample temperature. By combining these measurements with first-principles modeling, the thermal expansion coefficients (TECs) of single-layer and freestanding graphene and bulk, as well as monolayer MoS2 , MoSe2 , WS2 , or WSe2 , are directly determined and mapped.

Mapping Thermal Expansion Coefficients in Freestanding 2D Materials at the Nanometer Scale.

PubMed

Hu, Xuan; Yasaei, Poya; Jokisaari, Jacob; Öğüt, Serdar; Salehi-Khojin, Amin; Klie, Robert F

2018-02-02

Two-dimensional materials, including graphene, transition metal dichalcogenides and their heterostructures, exhibit great potential for a variety of applications, such as transistors, spintronics, and photovoltaics. While the miniaturization offers remarkable improvements in electrical performance, heat dissipation and thermal mismatch can be a problem in designing electronic devices based on two-dimensional materials. Quantifying the thermal expansion coefficient of 2D materials requires temperature measurements at nanometer scale. Here, we introduce a novel nanometer-scale thermometry approach to measure temperature and quantify the thermal expansion coefficients in 2D materials based on scanning transmission electron microscopy combined with electron energy-loss spectroscopy to determine the energy shift of the plasmon resonance peak of 2D materials as a function of sample temperature. By combining these measurements with first-principles modeling, the thermal expansion coefficients (TECs) of single-layer and freestanding graphene and bulk, as well as monolayer MoS_{2}, MoSe_{2}, WS_{2}, or WSe_{2}, are directly determined and mapped.

Role of mechanical stress in the resistance drift of Ge2Sb2Te5 films and phase change memories

NASA Astrophysics Data System (ADS)

Rizzi, M.; Spessot, A.; Fantini, P.; Ielmini, D.

2011-11-01

In a phase change memory (PCM), the device resistance increases slowly with time after the formation of the amorphous phase, thus affecting the stability of stored data. This work investigates the resistance drift in thin films of amorphous Ge2Sb2Te5 and in PCMs, demonstrating a common kinetic of drift in stressed/unstressed films and in the nanometer-size active volume of a PCM with different stress levels developed via stressor layers. It is concluded that stress is not the root cause of PCM drift, which is instead attributed to intrinsic structural relaxation due to the disordered, metastable nature of the amorphous chalcogenide phase.

Luminescence study of ZnSe/PVA (polyvinyl alcohol) composite film

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lahariya, Vikas

The ZnSe nanocrystals have been prepared into poly vinyl alcohol(PVA) polymer matrix on glass using ZnCl2 and Na2SeSO3 as zinc and selenium source respectively. Poly vinyl Alcohol (PVA) used as polymer matrix cum capping agent due to their high viscosity and water solubility. It is transparent for visible region and prevents Se- ions to photo oxidation. The ZnSe/PVA composite film was deposited on glass substrate. The film was characterized by X Ray Diffraction (XRD) and UV-Visible absorption Spectroscopy and Photoluminescence. The X Ray Diffraction (XRD) study confirms the nanometer size (10 nm) particle formation within PVA matrix with cubic zinc blendmore » crystal structure. The UV-Visible Absorption spectrum of ZnSe/PVA composite film shown blue shift in absorption edge indicating increased band gap due to quantum confinement. The calculated energy band gap from the absorption edge using Tauc relation is 3.4 eV. From the Photoluminescence study a broad peak at 435 nm has been observed in violet blue region due to recombination of surface states.« less

Inhomogeneity of PAGs in resist film studied by molecular-dynamics simulations for EUV lithography

NASA Astrophysics Data System (ADS)

Toriumi, Minoru; Itani, Toshiro

2014-03-01

EUV resist materials are requested simultaneously to improve the resolution, line-edge roughness (LER), and sensitivity (RLS). In a resist film inhomogeneous structures in nanometer region may have large effects on directly the resolution and LER and indirectly on sensitivity. Inhomogeneity of PAGs in a hybrid resist for EUV lithography was investigated using molecular dynamics simulations. The hybrid resist film showed the inhomogeneous positions and motions of PAG cations and anions. Free volumes in resist matrix influence the motions of PAGs. Molecular structure such as bulky phenyl groups of a PAG cation localize the positions and reduce the motion of a cation. Chemical properties such as ionic interactions and lone-pair interaction also play an important role to determine the inhomogeneity of PAGs. Fluorine interaction enables active motions of PAG anions.

Results of high dose 106-ruthenium irradiation of choroidal melanomas

DOE Office of Scientific and Technical Information (OSTI.GOV)

Mueller, R.P.B.; Busse, H.; Poetter, R.K.

The favored treatment of intraocular melanomas in Germany is 106-ruthenium eye plaque therapy. The Departments of Radiation Therapy and Ophthalmology (University of Muenster) initiated a clinical study in 1981 to reveal the effect of high-dose beta irradiation (15.000 cGy to the apex of the tumor) regarding tumor regression, treatment related side effects, visual acuity, and survival. Sixty-seven patients have been treated since 1981. In 12 patients a second course of irradiation has been performed because of insufficient tumor regression or no change after the first plaque treatment. Sixty-five percent (44/67 pts.) were over 60 years of age. Twenty-four patients hadmore » a small tumor (up to 3 mm in height), 20 patients had a medium sized tumor (3.1-5 mm in height), and 22 patients had a large tumor (more than 5.1 mm in height). Fifty-one patients had a follow-up of at least 12 months. A total tumor regression was achieved in 34/51 patients (67%), partial tumor regression occurred in 13/51 patients (25%), and in 4/51 patients (8%) there was no change after the first course. After the second course of 106-ruthenium-irradiation 5 of the 12 patients showed total tumor regression, 3 had partial regression, and in 4 patients only an increase of the tumor echogenity could be assessed by ultrasonography, but no change in height. Visual acuity, which depends mostly on the localization of the tumor, was preserved at pretreatment levels in 72% of the patients. Two patients died with documented metastatic disease, one patient died of myocardial infarction. There was only one enucleation because of neovascular glaucoma.A« less

Effects of solvent evaporation conditions on solvent vapor annealed cylinder-forming block polymer thin films

NASA Astrophysics Data System (ADS)

Grant, Meagan; Jakubowski, William; Nelson, Gunnar; Drapes, Chloe; Baruth, A.

Solvent vapor annealing is a less time and energy intensive method compared to thermal annealing, to direct the self-assembly of block polymer thin films. Periodic nanostructures have applications in ultrafiltration, magnetic arrays, or other structures with nanometer dimensions, driving its continued interest. Our goal is to create thin films with hexagonally packed, perpendicular aligned cylinders of poly(lactide) in a poly(styrene) matrix that span the thickness of the film with low anneal times and low defect densities, all with high reproducibility, where the latter is paramount. Through the use of our computer-controlled, pneumatically-actuated, purpose-built solvent vapor annealing chamber, we have the ability to monitor and control vapor pressure, solvent concentration within the film, and solvent evaporation rate with unprecedented precision and reliability. Focusing on evaporation, we report on two previously unexplored areas, chamber pressure during solvent evaporation and the flow rate of purging gas aiding the evaporation. We will report our exhaustive results following atomic force microscopy analysis of films exposed to a wide range of pressures and flow rates. Reliably achieving well-ordered films, while occurring within a large section of this parameter space, was correlated with high-flow evaporation rates and low chamber pressures. These results have significant implications on other methods of solvent annealing, including ``jar'' techniques.

Dewetting of thin polymer films: an X-ray scattering study

NASA Astrophysics Data System (ADS)

Müller-Buschbaum, P.; Stamm, M.

1998-06-01

The surface morphology of different dewetting states of thin polymer films (polystyrene) on top of silicon substrates was investigated. With diffuse X-ray scattering in the region of total external reflection a high in-plane resolution was achieved. We observe a new nano-dewetting structure which coexists with the well known mesoscopic dewetting structures of holes, cellular pattern and drops. This nano-dewetting structure consists of small dimples with a diameter in the nanometer range. It results from the dewetting of a remaining ultra-thin polymer layer and can be explained with theoretical predictions of spinodal decomposition. The experimental results of the scattering study are confirmed with scanning-force microscopy measurements.

Mechanical characterization of thin TiO2 films by means of microelectromechanical systems-based cantilevers

NASA Astrophysics Data System (ADS)

Adami, A.; Decarli, M.; Bartali, R.; Micheli, V.; Laidani, N.; Lorenzelli, L.

2010-01-01

The measurement of mechanical parameters by means of microcantilever structures offers a reliable and accurate alternative to traditional methods, especially when dealing with thin films, which are extensively used in microfabrication technology and nanotechnology. In this work, microelectromechanical systems (MEMS)-based piezoresistive cantilevers were realized and used for the determination of Young's modulus and residual stress of thin titanium dioxide (TiO2) deposited by sputtering from a TiO2 target using a rf plasma discharge. Films were deposited at different thicknesses, ranging from a few to a hundred nanometers. Dedicated silicon microcantilevers were designed through an optimization of geometrical parameters with the development of analytical as well as numerical models. Young's modulus and residual stress of sputtered TiO2 films were assessed by using both mechanical characterization based on scanning profilometers and piezoresistive sensing elements integrated in the silicon cantilevers. Results of MEMS-based characterization were combined with the tribological and morphological properties measured by microscratch test and x-ray diffraction analysis.

Techniques for 3D tracking of single molecules with nanometer accuracy in living cells

NASA Astrophysics Data System (ADS)

Gardini, Lucia; Capitanio, Marco; Pavone, Francesco S.

2013-06-01

We describe a microscopy technique that, combining wide-field single molecule microscopy, bifocal imaging and Highly Inclined and Laminated Optical sheet (HILO) microscopy, allows a 3D tracking with nanometer accuracy of single fluorescent molecules in vitro and in living cells.

Rapid Polymer Transport in a Single Nanometer-Scale Pore

NASA Astrophysics Data System (ADS)

Kasianowicz, J. J.

1998-03-01

Protein ion channels are nanometer-scale pores that control the transport of ions and polymers across cell membranes. We compared the ability of charged and nonelectrolyte linear polymers to partition into a single channel reconstituted into a planar lipid bilayer membrane. The entry of each polymer (e.g. monodisperse length single-stranded homopolymeric RNA1 or poly(ethylene glycol)2,3) into the pore caused characteristic transient decreases in the channel's ionic conductance. The ionic current blockades yield detailed information about the physical properties of the polymers and the pore. The biological and technological significance of the results will be discussed.

Biological processing of dinuclear ruthenium complexes in eukaryotic cells.

PubMed

Li, Xin; Heimann, Kirsten; Dinh, Xuyen Thi; Keene, F Richard; Collins, J Grant

2016-10-20

The biological processing - mechanism of cellular uptake, effects on the cytoplasmic and mitochondrial membranes, intracellular sites of localisation and induction of reactive oxygen species - of two dinuclear polypyridylruthenium(ii) complexes has been examined in three eukaryotic cells lines. Flow cytometry was used to determine the uptake of [{Ru(phen)2}2{μ-bb12}](4+) (Rubb12) and [Ru(phen)2(μ-bb7)Ru(tpy)Cl](3+) {Rubb7-Cl, where phen = 1,10-phenanthroline, tpy = 2,2':6',2''-terpyridine and bbn = bis[4(4'-methyl-2,2'-bipyridyl)]-1,n-alkane} in baby hamster kidney (BHK), human embryonic kidney (HEK-293) and liver carcinoma (HepG2) cell lines. The results demonstrated that the major uptake mechanism for Rubb12 and Rubb7-Cl was active transport, although with a significant contribution from carrier-assisted diffusion for Rubb12 and passive diffusion for Rubb7-Cl. Flow cytometry coupled with Annexin V/TO-PRO-3 double-staining was used to compare cell death by membrane damage or apoptosis. Rubb12 induced significant direct membrane damage, particularly with HepG2 cells, while Rubb7-Cl caused considerably less membrane damage but induced greater levels of apoptosis. Confocal microscopy, coupled with JC-1 assays, demonstrated that Rubb12 depolarises the mitochondrial membrane, whereas Rubb7-Cl had a much smaller affect. Cellular localisation experiments indicated that Rubb12 did not accumulate in the mitochondria, whereas significant mitochondrial accumulation was observed for Rubb7-Cl. The effect of Rubb12 and Rubb7-Cl on intracellular superoxide dismutase activity showed that the ruthenium complexes could induce cell death via a reactive oxygen species-mediated pathway. The results of this study demonstrate that Rubb12 predominantly kills eukaryotic cells by damaging the cytoplasmic membrane. As this dinuclear ruthenium complex has been previously shown to exhibit greater toxicity towards bacteria than eukaryotic cells, the results of the present study suggest that

A scanning tunneling microscope with a scanning range from hundreds of micrometers down to nanometer resolution.

PubMed

Kalkan, Fatih; Zaum, Christopher; Morgenstern, Karina

2012-10-01

A beetle type stage and a flexure scanning stage are combined to form a two stages scanning tunneling microscope (STM). It operates at room temperature in ultrahigh vacuum and is capable of scanning areas up to 300 μm × 450 μm down to resolution on the nanometer scale. This multi-scale STM has been designed and constructed in order to investigate prestructured metallic or semiconducting micro- and nano-structures in real space from atomic-sized structures up to the large-scale environment. The principle of the instrument is demonstrated on two different systems. Gallium nitride based micropillars demonstrate scan areas up to hundreds of micrometers; a Au(111) surface demonstrates nanometer resolution.

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE PAGES

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

2017-09-01

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

A new class of cyclometalated ruthenium sensitizers of the type ĈNN for efficient dye-sensitized solar cells.

PubMed

Kim, Jeum-Jong; Choi, Hyunbong; Paek, Sanghyun; Kim, Chulwoo; Lim, Kimin; Ju, Myung-Jong; Kang, Hong Seok; Kang, Moon-Sung; Ko, Jaejung

2011-11-21

A new class of cyclometalated ruthenium sensitizers incorporating a ĈNN ligand and conjugated 2,2'-bipyridine in the ancillary ligand have been designed and synthesized. The photovoltaic performance of JK-206 using an electrolyte containing 0.6 M 1,2-dimethyl-3-propylimidazolium iodide, 0.05 M I(2), 0.1 M LiI, and 0.5 M tert-butylpyridine in CH(3)CN gave a short-circuit photocurrent density of 19.63 mA cm(-2), an open-circuit voltage of 0.74 V, and a fill factor of 0.72, affording an overall conversion efficiency of 10.39%. The efficiency is the highest one reported for dye-sensitized solar cells based on the cyclometalated ruthenium sensitizer of the type ĈNN. Moreover, the same device using a polymer gel electrolyte exhibited a remarkable stability under 1000 h of light soaking at 60 °C, retaining 91% of the initial efficiency of 7.14%.

O–O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O–O radical coupling

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shaffer, David W.; Xie, Yan; Concepcion, Javier J.

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O–O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O–Omore » bond formation step as the key step in water oxidation catalysis. As a result, the two main pathways to accomplish this step, single-site water nucleophilic attack and O–O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.« less

O-O bond formation in ruthenium-catalyzed water oxidation: single-site nucleophilic attack vs. O-O radical coupling.

PubMed

Shaffer, David W; Xie, Yan; Concepcion, Javier J

2017-10-16

In this review we discuss at the mechanistic level the different steps involved in water oxidation catalysis with ruthenium-based molecular catalysts. We have chosen to focus on ruthenium-based catalysts to provide a more coherent discussion and because of the availability of detailed mechanistic studies for these systems but many of the aspects presented in this review are applicable to other systems as well. The water oxidation cycle has been divided in four major steps: water oxidative activation, O-O bond formation, oxidative activation of peroxide intermediates, and O 2 evolution. A significant portion of the review is dedicated to the O-O bond formation step as the key step in water oxidation catalysis. The two main pathways to accomplish this step, single-site water nucleophilic attack and O-O radical coupling, are discussed in detail and compared in terms of their potential use in photoelectrochemical cells for solar fuels generation.

Plasmon-induced optical switching of electrical conductivity in porous anodic aluminum oxide films encapsulated with silver nanoparticle arrays.

PubMed

Huang, Chen-Han; Lin, Hsing-Ying; Lau, Ben-Chao; Liu, Chih-Yi; Chui, Hsiang-Chen; Tzeng, Yonhua

2010-12-20

We report on plasmon induced optical switching of electrical conductivity in two-dimensional (2D) arrays of silver (Ag) nanoparticles encapsulated inside nanochannels of porous anodic aluminum oxide (AAO) films. The reversible switching of photoconductivity greatly enhanced by an array of closely spaced Ag nanoparticles which are isolated from each other and from the ambient by thin aluminum oxide barrier layers are attributed to the improved electron transport due to the localized surface plasmon resonance and coupling among Ag nanoparticles. The photoconductivity is proportional to the power, and strongly dependent on the wavelength of light illumination. With Ag nanoparticles being isolated from the ambient environments by a thin layer of aluminum oxide barrier layer of controlled thickness in nanometers to tens of nanometers, deterioration of silver nanoparticles caused by environments is minimized. The electrochemically fabricated nanostructured Ag/AAO is inexpensive and promising for applications to integrated plasmonic circuits and sensors.

Toward in situ x-ray diffraction imaging at the nanometer scale

NASA Astrophysics Data System (ADS)

Zatsepin, Nadia A.; Dilanian, Ruben A.; Nikulin, Andrei Y.; Gable, Brian M.; Muddle, Barry C.; Sakata, Osami

2008-08-01

We present the results of preliminary investigations determining the sensitivity and applicability of a novel x-ray diffraction based nanoscale imaging technique, including simulations and experiments. The ultimate aim of this nascent technique is non-destructive, bulk-material characterization on the nanometer scale, involving three dimensional image reconstructions of embedded nanoparticles and in situ sample characterization. The approach is insensitive to x-ray coherence, making it applicable to synchrotron and laboratory hard x-ray sources, opening the possibility of unprecedented nanometer resolution with the latter. The technique is being developed with a focus on analyzing a technologically important light metal alloy, Al-xCu (where x is 2.0-5.0 %wt). The mono- and polycrystalline samples contain crystallographically oriented, weakly diffracting Al2Cu nanoprecipitates in a sparse, spatially random dispersion within the Al matrix. By employing a triple-axis diffractometer in the non-dispersive setup we collected two-dimensional reciprocal space maps of synchrotron x-rays diffracted from the Al2Cu nanoparticles. The intensity profiles of the diffraction peaks confirmed the sensitivity of the technique to the presence and orientation of the nanoparticles. This is a fundamental step towards in situ observation of such extremely sparse, weakly diffracting nanoprecipitates embedded in light metal alloys at early stages of their growth.

Fast photo-switchable surfaces for boiling heat transfer applications

NASA Astrophysics Data System (ADS)

Hunter, C. N.; Turner, D. B.; Jespersen, M. L.; Check, M. H.; Borton, P. T.; Glavin, N. R.; Voevodin, A. A.

2012-11-01

Several milligrams of the ruthenium-centered organometallic complex, ruthenium bis-4,4'-di(thiomethyl)-2,2'-bipyridine, mono-2 -(2-pyridyl)-1,3-oxathiane ([Ru{(HS-CH2)2-bpy}2{pox}](PF6)2) were synthesized and used to produce a self assembled monolayer film on a gold substrate. X-ray photoelectron spectroscopy analysis of the film detected the presence of bound thiolate, which is an indication of a chemisorbed film. Water contact angle measurements were performed before and after 5 min of visible light irradiation using an ozone-free 1000 W Xe(Hg) arc source with a 425-680 nm long pass mirror. The contact angle changed from 52° pre-irradiation (hydrophilic state) to 95° post-irradiation (hydrophobic state).

Ruthenium-catalysed alkoxycarbonylation of alkenes with carbon dioxide.

PubMed

Wu, Lipeng; Liu, Qiang; Fleischer, Ivana; Jackstell, Ralf; Beller, Matthias

2014-01-01

Alkene carbonylations represent a major technology for the production of value-added bulk and fine chemicals. Nowadays, all industrial carbonylation processes make use of highly toxic and flammable carbon monoxide. Here we show the application of abundantly available carbon dioxide as C1 building block for the alkoxycarbonylations of industrially important olefins in the presence of a convenient and inexpensive ruthenium catalyst system. In our system, carbon dioxide works much better than the traditional combination of carbon monoxide and alcohols. The unprecedented in situ formation of carbon monoxide from carbon dioxide and alcohols permits an efficient synthesis of carboxylic acid esters, which can be used as detergents and polymer-building blocks. Notably, this transformation allows the catalytic formation of C-C bonds with carbon dioxide as C1 source and avoids the use of sensitive and/or expensive reducing agents (for example, Grignard reagents, diethylzinc or triethylaluminum).

Morphological Transition in Diamond Thin-Films Induced by Boron in a Microwave Plasma Deposition Process.

PubMed

Baker, Paul A; Goodloe, David R; Vohra, Yogesh K

2017-11-14

The purpose of this study is to understand the basic mechanisms responsible for the synthesis of nanostructured diamond films in a microwave plasma chemical vapor deposition (MPCVD) process and to identify plasma chemistry suitable for controlling the morphology and electrical properties of deposited films. The nanostructured diamond films were synthesized by MPCVD on Ti-6Al-4V alloy substrates using H₂/CH₄/N₂ precursor gases and the plasma chemistry was monitored by the optical emission spectroscopy (OES). The synthesized thin-films were characterized by x -ray diffraction and scanning electron microscopy. The addition of B₂H₆ to the feedgas during MPCVD of diamond thin-films changes the crystal grain size from nanometer to micron scale. Nanostructured diamond films grown with H₂/CH₄/N₂ gases demonstrate a broad (111) Bragg x -ray diffraction peak (Full-Width at Half-Maximum (FWHM) = 0.93° 2θ), indicating a small grain size, whereas scans show a definite sharpening of the diamond (111) peak (FWHM = 0.30° 2θ) with the addition of boron. OES showed a decrease in CN (carbon-nitrogen) radical in the plasma with B₂H₆ addition to the gas mixture. Our study indicates that CN radical plays a critical role in the synthesis of nanostructured diamond films and suppression of CN radical by boron-addition in the plasma causes a morphological transition to microcrystalline diamond.

Inactivation of bacteria under visible light and in the dark by Cu films. Advantages of Cu-HIPIMS-sputtered films.

PubMed

Ehiasarian, A; Pulgarin, Cesar; Kiwi, John

2012-11-01

The Cu polyester thin-sputtered layers on textile fabrics show an acceptable bacterial inactivation kinetics using sputtering methods. Direct current magnetron sputtering (DCMS) for 40 s of Cu on cotton inactivated Escherichia coli within 30 min under visible light and within 120 min in the dark. For a longer DCMS time of 180 s, the Cu content was 0.294% w/w, but the bacterial inactivation kinetics under light was observed within 30 min, as was the case for the 40-s sputtered sample. This observation suggests that Cu ionic species play a key role in the E. coli inactivation and these species were further identified by X-ray photoelectron spectroscopy (XPS). The 40-s sputtered samples present the highest amount of Cu sites held in exposed positions interacting on the cotton with E. coli. Cu DC magnetron sputtering leads to thin metallic semi-transparent gray-brown Cu coating composed by Cu nanoparticulate in the nanometer range as found by electron microscopy (EM). Cu cotton fabrics were also functionalized by bipolar asymmetric DCMSP. Sputtering by DCMS and DCMSP for longer times lead to darker and more compact Cu films as detected by diffuse reflectance spectroscopy and EM. Cu is deposited on the polyester in the form of Cu(2)O and CuO as quantified by XPS. The redox interfacial reactions during bacterial inactivation involve changes in the Cu oxidation states and in the oxidation intermediates and were followed by XPS. High-power impulse magnetron sputtering (HIPIMS)-sputtered films show a low rugosity indicating that the texture of the Cu nanoparticulate films were smooth. The values of R (q) and R (a) were similar before and after the E. coli inactivation providing evidence for the stability of the HIPIMS-deposited Cu films. The Cu loading percentage required in the Cu films sputtered by HIPIMS to inactivate E. coli was about three times lower compared to DCMS films. This indicates a substantial Cu metal savings within the preparation of antibacterial

Cytotoxicity Evaluation of Anatase and Rutile TiO₂ Thin Films on CHO-K1 Cells in Vitro.

PubMed

Cervantes, Blanca; López-Huerta, Francisco; Vega, Rosario; Hernández-Torres, Julián; García-González, Leandro; Salceda, Emilio; Herrera-May, Agustín L; Soto, Enrique

2016-07-26

Cytotoxicity of titanium dioxide (TiO₂) thin films on Chinese hamster ovary (CHO-K1) cells was evaluated after 24, 48 and 72 h of culture. The TiO₂ thin films were deposited using direct current magnetron sputtering. These films were post-deposition annealed at different temperatures (300, 500 and 800 °C) toward the anatase to rutile phase transformation. The root-mean-square (RMS) surface roughness of TiO₂ films went from 2.8 to 8.08 nm when the annealing temperature was increased from 300 to 800 °C. Field emission scanning electron microscopy (FESEM) results showed that the TiO₂ films' thickness values fell within the nanometer range (290-310 nm). Based on the results of the tetrazolium dye and trypan blue assays, we found that TiO₂ thin films showed no cytotoxicity after the aforementioned culture times at which cell viability was greater than 98%. Independently of the annealing temperature of the TiO₂ thin films, the number of CHO-K1 cells on the control substrate and on all TiO₂ thin films was greater after 48 or 72 h than it was after 24 h; the highest cell survival rate was observed in TiO₂ films annealed at 800 °C. These results indicate that TiO₂ thin films do not affect mitochondrial function and proliferation of CHO-K1 cells, and back up the use of TiO₂ thin films in biomedical science.

Dihydrogen Phosphate Stabilized Ruthenium(0) Nanoparticles: Efficient Nanocatalyst for The Hydrolysis of Ammonia-Borane at Room Temperature

PubMed Central

Durap, Feyyaz; Caliskan, Salim; Özkar, Saim; Karakas, Kadir; Zahmakiran, Mehmet

2015-01-01

Intensive efforts have been devoted to the development of new materials for safe and efficient hydrogen storage. Among them, ammonia-borane appears to be a promising candidate due to its high gravimetric hydrogen storage capacity. Ammonia-borane can release hydrogen on hydrolysis in aqueous solution under mild conditions in the presence of a suitable catalyst. Herein, we report the synthesis of ruthenium(0) nanoparticles stabilized by dihydrogenphosphate anions with an average particle size of 2.9 ± 0.9 nm acting as a water-dispersible nanocatalyst in the hydrolysis of ammonia-borane. They provide an initial turnover frequency (TOF) value of 80 min−1 in hydrogen generation from the hydrolysis of ammonia-borane at room temperature. Moreover, the high stability of these ruthenium(0) nanoparticles makes them long-lived and reusable nanocatalysts for the hydrolysis of ammonia-borane. They provide 56,800 total turnovers and retain ~80% of their initial activity even at the fifth catalytic run in the hydrolysis of ammonia-borane at room temperature. PMID:28793435

Methyl-cyclopentadienyl Ruthenium Compounds with 2,2'-Bipyridine Derivatives Display Strong Anticancer Activity and Multidrug Resistance Potential.

PubMed

Côrte-Real, Leonor; Teixeira, Ricardo G; Gírio, Patrícia; Comsa, Elisabeta; Moreno, Alexis; Nasr, Rachad; Baubichon-Cortay, Hélène; Avecilla, Fernando; Marques, Fernanda; Robalo, M Paula; Mendes, Paulo; Ramalho, João P Prates; Garcia, M Helena; Falson, Pierre; Valente, Andreia

2018-04-16

New ruthenium methyl-cyclopentadienyl compounds bearing bipyridine derivatives with the general formula [Ru(η 5 -MeCp)(PPh 3 )(4,4'-R-2,2'-bpy)] + (Ru1, R = H; Ru2, R = CH 3 ; and Ru3, R = CH 2 OH) have been synthesized and characterized by spectroscopic and analytical techniques. Ru1 crystallized in the monoclinic P2 1 / c, Ru2 in the triclinic P1̅, and Ru3 in the monoclinic P2 1 / n space group. In all molecular structures, the ruthenium center adopts a "piano stool" distribution. Density functional theory calculations were performed for all complexes, and the results support spectroscopic data. Ru1 and Ru3 were poor substrates of the main multidrug resistance human pumps, ABCB1, ABCG2, ABCC1, and ABCC2, while Ru2 displayed inhibitory properties of ABCC1 and ABCC2 pumps. Importantly, all compounds displayed a very high cytotoxic profile for ovarian cancer cells (sensitive and resistant) that was much more pronounced than that observed with cisplatin, making them very promising anticancer agents.

Synthesis and room temperature photo-induced electron transfer in biologically active bis(terpyridine)ruthenium(II)-cytochrome c bioconjugates and the effect of solvents on the bioconjugation of cytochrome c.

PubMed

Peterson, Joshua R; Smith, Trevor A; Thordarson, Pall

2010-01-07

Photo-active bis(terpyridine)ruthenium(ii) chromophores were synthesised and attached to the redox enzyme iso-1 cytochrome c in a mixed solvent system to form photo-induced bioconjugates in greater than 40% yield after purification. The effects of up to 20% (v/v) of acetonitrile, tetrahydrofuran, dimethylformamide, or dimethyl sulfoxide at 4, 25 and 35 degrees C on the stability and biological activity of cytochrome c and its reactivity towards the model compound 4,4'-dithiodipyridine (DTDP) was measured. The second-order rate constant for the DTDP reaction was found to range between k = 2.5-4.3 M(-1) s(-1) for reactions with 5% organic solvent added compared to k = 5.6 M(-1) s(-1) in pure water at 25 degrees C. Use of 20% solvent generally results in significant protein oxidation, and 20% acetonitrile and tetrahydrofuran in particular result in significant protein dimerization, which competes with the bioconjugation reaction. Cyclic voltammetry studies indicated that the rate of electron transfer to the heme in solution was reduced in the bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates compared to unmodified cytochrome c. Steady-state fluorescence studies on these bioconjugates showed that energy or electron transfer is taking place between the bis(terpyridine)ruthenium(ii) chromophores and cytochrome c. The bis(terpyridine)ruthenium(ii) cytochrome c bioconjugates demonstrate room temperature photo-activated electron transfer from the bis(terpyridine)ruthenium(ii) donor to the protein acceptor. Two sacrificial donors were used; in 50% glycerol, the bioconjugates were reduced in about 15 min while in 20 mM EDTA the bioconjugates were fully reduced in less than 5 min upon irradiation with a xenon lamp source. Under these conditions, the reduction of the non-covalent mixture of cytochrome c and bis(terpyridine)ruthenium(ii) mixtures took over 30 min. Control experiments showed that the photo-induced reduction of cytochrome c only occurs in the absence of

Ru-OSO coordination photogenerated at 100 K in tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-camphorsulfonate.

PubMed

Phillips, Anthony E; Cole, Jacqueline M; d'Almeida, Thierry; Low, Kian Sing

2012-02-06

The photoinduced O-bound coordination mode in RuSO(2) complexes, previously observed only at 13 K, has been generated at 100 K in tetraammineaqua(sulfur dioxide)ruthenium(II) (±)-camphorsulfonate. This coordination state, often denoted MS1, decays to the η(2)-bound MS2 state, with an estimated half-life of 3.4(8) h and a long-lived population of 2.9(4)% at 120 K.

Synergistic Interaction within Bifunctional Ruthenium Nanoparticle/SILP Catalysts for the Selective Hydrodeoxygenation of Phenols.

PubMed

Luska, Kylie L; Migowski, Pedro; El Sayed, Sami; Leitner, Walter

2015-12-21

Ruthenium nanoparticles immobilized on acid-functionalized supported ionic liquid phases (Ru NPs@SILPs) act as efficient bifunctional catalysts in the hydrodeoxygenation of phenolic substrates under batch and continuous flow conditions. A synergistic interaction between the metal sites and acid groups within the bifunctional catalyst leads to enhanced catalytic activities for the overall transformation as compared to the individual steps catalyzed by the separate catalytic functionalities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

General synthesis of (salen)ruthenium(III) complexes via N...N coupling of (salen)ruthenium(VI) nitrides.

PubMed

Man, Wai-Lun; Kwong, Hoi-Ki; Lam, William W Y; Xiang, Jing; Wong, Tsz-Wing; Lam, Wing-Hong; Wong, Wing-Tak; Peng, Shie-Ming; Lau, Tai-Chu

2008-07-07

Reaction of [Ru (VI)(N)(L (1))(MeOH)] (+) (L (1) = N, N'-bis(salicylidene)- o-cyclohexylenediamine dianion) with excess pyridine in CH 3CN produces [Ru (III)(L (1))(py) 2] (+) and N 2. The proposed mechanism involves initial equilibrium formation of [Ru (VI)(N)(L (1))(py)] (+), which undergoes rapid N...N coupling to produce [(py)(L (1))Ru (III) N N-Ru (III)(L (1))(py)] (2+); this is followed by pyridine substituion to give the final product. This ligand-induced N...N coupling of Ru (VI)N is utilized in the preparation of a series of new ruthenium(III) salen complexes, [Ru (III)(L)(X) 2] (+/-) (L = salen ligand; X = H 2O, 1-MeIm, py, Me 2SO, PhNH 2, ( t )BuNH 2, Cl (-) or CN (-)). The structures of [Ru (III)(L (1))(NH 2Ph) 2](PF 6) ( 6), K[Ru (III)(L (1))(CN) 2] ( 9), [Ru (III)(L (2))(NCCH 3) 2][Au (I)(CN) 2] ( 11) (L (2) = N, N'-bis(salicylidene)- o-phenylenediamine dianion) and [N ( n )Bu 4][Ru (III)(L (3))Cl 2] ( 12) (L (3) = N, N'-bis(salicylidene)ethylenediamine dianion) have been determined by X-ray crystallography.

Fabrications of insulator-protected nanometer-sized electrode gaps

NASA Astrophysics Data System (ADS)

Arima, Akihide; Tsutsui, Makusu; Morikawa, Takanori; Yokota, Kazumichi; Taniguchi, Masateru

2014-03-01

We developed SiO2-coated mechanically controllable break junctions for accurate tunneling current measurements in an ionic solution. By breaking the junction, we created dielectric-protected Au nanoprobes with nanometer separation. We demonstrated that the insulator protection was capable to suppress the ionic contribution to the charge transport through the electrode gap, thereby enabled reliable characterizations of liquid-mediated exponential decay of the tunneling conductance in an electrolyte solution. From this, we found distinct roles of charge points such as molecular dipoles and ion species on the tunneling decay constant, which was attributed to local structures of molecules and ions in the confined space between the sensing electrodes. The device described here would provide improved biomolecular sensing capability of tunneling current sensors.

Electron-Beam Mapping of Vibrational Modes with Nanometer Spatial Resolution.

PubMed

Dwyer, C; Aoki, T; Rez, P; Chang, S L Y; Lovejoy, T C; Krivanek, O L

2016-12-16

We demonstrate that a focused beam of high-energy electrons can be used to map the vibrational modes of a material with a spatial resolution of the order of one nanometer. Our demonstration is performed on boron nitride, a polar dielectric which gives rise to both localized and delocalized electron-vibrational scattering, either of which can be selected in our off-axial experimental geometry. Our experimental results are well supported by our calculations, and should reconcile current controversy regarding the spatial resolution achievable in vibrational mapping with focused electron beams.

Enhanced photocatalytic hydrogen production from water-ethanol solution by Ruthenium doped La-NaTaO3

NASA Astrophysics Data System (ADS)

Husin, H.; Alam, P. N.; Zaki, M.; Sofyana; Jakfar; Husaini; Hasfita, F.

2018-04-01

The photocatalytic hydrogen production from ethanol aqueous solution, with the use ruthenium doped La-NaTaO3 has been investigated. Ruthenium doped La-NaTaO3 catalysts are prepared by impregnation method. The catalysts are by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The Ru co-catalyst demonstrated from the TEM image shows a good dispersion on the surface of La-C-NaTaO3 with an average particle size between 4-5 nm. The photocatalytic reaction is carried out in a closed reactor with a gas circulation system. The catalytic activity of La-NaTaO3 improved markedly (6.6 times from pure water) when Ru is loaded onto its surface. The hydrogen production is notably enhanced in the presence of ethanol as electron donors. This result is much higher when compared with the rate of hydrogen production in the sample without co- catalysts about 9.4 times higher after Ru deposition from ethanol aqueous solution. Increasing the production of hydrogen on the Ru/La-NaTaO3 closely related to the decrease in recombination between electron-hole pairs.

Ruthenium supported on magnetic nanoparticles: An efficient and recoverable catalyst for hydrogenation of alkynes and transfer hydrogenation of carbonyl compounds

EPA Science Inventory

Ruthenium supported on surface modified magnetic nanoparticles (NiFe2O4) has been successfully synthesized and applied for hydrogenation of alkynes at room temperature as well as transfer hydrogenation of a number of carbonyl compounds under microwave irradiation conditions. The ...

Deposition of Nanostructured Thin Film from Size-Classified Nanoparticles

NASA Technical Reports Server (NTRS)

Camata, Renato P.; Cunningham, Nicholas C.; Seol, Kwang Soo; Okada, Yoshiki; Takeuchi, Kazuo

2003-01-01

Materials comprising nanometer-sized grains (approximately 1_50 nm) exhibit properties dramatically different from those of their homogeneous and uniform counterparts. These properties vary with size, shape, and composition of nanoscale grains. Thus, nanoparticles may be used as building blocks to engineer tailor-made artificial materials with desired properties, such as non-linear optical absorption, tunable light emission, charge-storage behavior, selective catalytic activity, and countless other characteristics. This bottom-up engineering approach requires exquisite control over nanoparticle size, shape, and composition. We describe the design and characterization of an aerosol system conceived for the deposition of size classified nanoparticles whose performance is consistent with these strict demands. A nanoparticle aerosol is generated by laser ablation and sorted according to size using a differential mobility analyzer. Nanoparticles within a chosen window of sizes (e.g., (8.0 plus or minus 0.6) nm) are deposited electrostatically on a surface forming a film of the desired material. The system allows the assembly and engineering of thin films using size-classified nanoparticles as building blocks.

Synthesis, structure, DNA binding and anticancer activity of mixed ligand ruthenium(II) complex

NASA Astrophysics Data System (ADS)

Gilewska, Agnieszka; Masternak, Joanna; Kazimierczuk, Katarzyna; Trynda, Justyna; Wietrzyk, Joanna; Barszcz, Barbara

2018-03-01

In order to obtain a potential chemotherapeutic which is not affected on the normal BALB/3T3 cell line, a new arene ruthenium(II) complex {[RuCl(L1)(η6-p-cymene)]PF6}2 · H2O has been synthesized by a direct reaction of precursor, [{(η6-p-cymene)Ru(μ-Cl)}2Cl2], with N,N-chelating ligand (L1 - 2,2‧-bis(4,5-dimethylimidazole). The compound has been fully characterized by elemental analysis, X-ray diffraction, IR, UV-Vis and 1H, 13C NMR spectroscopies. X-ray analysis have confirmed that the compound crystallized in the monoclinic group Cc as an inversion twin. The asymmetric unit contains two symmetrically independent cationic complexes [RuCl(L1)(η6-p-cymene)]+ whose charge is balanced by two PF6- counterions. The shape of each cationic coordination polyhedral can be described as a distorted dodecahedron and shows a typical piano-stool geometry. In addition, an analysis of the crystal structure and the Hirshfeld surface analysis were used to detect and visualize important hydrogen bonds and intermolecular interaction. Moreover, the antiproliferative behavior of the obtained complex was assayed against three human cells: MV-4-11, LoVo, MCF-7 and BALB/3T3 - normal mice fibroblast cells. To predict a binding mode, a potential interaction of ruthenium complex with calf thymus DNA (CT-DNA) has been explored using UV absorption and circular dichroism (CD).

Green synthesis of noble nanometals (Au, Pt, Pd) using glycerol under microwave irradiation conditions

EPA Science Inventory

A newer application of glycerol in the field of nanomaterials synthesis has been developed from both the economic and environmental points of view. Glycerol can act as a reducing agent for the fabrication of noble nanometals, such as Au, Pt, and Pd, under microwave irradiation. T...

Evidence for Dynamic Chemical Kinetics at Individual Molecular Ruthenium Catalysts.

PubMed

Easter, Quinn T; Blum, Suzanne A

2018-02-05

Catalytic cycles are typically depicted as possessing time-invariant steps with fixed rates. Yet the true behavior of individual catalysts with respect to time is unknown, hidden by the ensemble averaging inherent to bulk measurements. Evidence is presented for variable chemical kinetics at individual catalysts, with a focus on ring-opening metathesis polymerization catalyzed by the second-generation Grubbs' ruthenium catalyst. Fluorescence microscopy is used to probe the chemical kinetics of the reaction because the technique possesses sufficient sensitivity for the detection of single chemical reactions. Insertion reactions in submicron regions likely occur at groups of many (not single) catalysts, yet not so many that their unique kinetic behavior is ensemble averaged. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Raman spectra of ruthenium and tantalum trimers in argon matrices

NASA Astrophysics Data System (ADS)

Fang, Li; Shen, Xiaole; Chen, Xiaoyu; Lombardi, John R.

2000-12-01

The resonance Raman spectra of ruthenium trimers (Ru 3) in argon matrices have been obtained. Three resonance Raman transitions were observed between 570 and 590 nm. Two of them (303.4 and 603.7 cm -1) are assigned to the totally symmetric vibrational progression, giving k e=1.86 mdyne/ Å. The line at 581.5 cm-1 is assigned as the origin of a low-lying electronic state. We also report on the observation of a resonance Raman spectrum of tantalum trimers (Ta 3). Observed lines include 251.2 and 501.9 cm-1 which we assign to the fundamental and the first overtone of the symmetric stretch in Ta 3. This gives k e=2.25 mdyne/ Å.

A computational study of the CO dissociation in cyclopentadienyl ruthenium complexes relevant to the racemization of alcohols.

PubMed

Stewart, Beverly; Nyhlen, Jonas; Martín-Matute, Belén; Bäckvall, Jan-E; Privalov, Timofei

2013-01-28

The formation of an active 16-electron ruthenium sec-alkoxide complex via loss of the CO ligand is an important step in the mechanism of the racemization of sec-alcohols by (η(5)-Ph(5)C(5))Ru(CO)(2)X ruthenium complexes with X = Cl and O(t)Bu. Here we show with accurate DFT calculations the potential energy profile of the CO dissociation pathway for a series of relevant (η(5)-Ph(5)C(5))Ru(CO)(2)X complexes, where X = Cl, O(t)Bu, H and COO(t)Bu. We have found that the CO dissociation energy increases in the following order: O(t)Bu (lowest), Cl, COO(t)Bu and H (highest). Using the distance between ruthenium and C(CO), r = Ru-C(CO), as a constraint, and by optimizing all other degrees of freedom for a range of Ru-CO distances, we obtained relative energies, ΔE(r) and geometries of a sufficient number of transient structures with the elongated Ru-CO bond up to r = 3.4 Å. Our calculations provide a quantitative understanding of the CO ligand dissociation in (η(5)-Ph(5)C(5))Ru(CO)(2)Cl and (η(5)-Ph(5)C(5))Ru(CO)(2)(O(t)Bu) complexes, which is relevant to the mechanism of their catalytic activity in the racemization of alcohols. We recently reported that exchange of the CO ligand by isotopically labeled (13)CO in the Ru-O(t)Bu complex occurs twenty times faster than that in the Ru-Cl complex. This corresponds to a difference of 1.8 kcal mol(-1) in the CO dissociation energy (at room temperature). This is in very good agreement with the calculated difference between the two potential energy curves for Ru-O(t)Bu and Ru-Cl complexes, which is about 1.8-2 kcal mol(-1) around the corresponding transition states of the CO dissociation. The calculated difference in the total energy for CO dissociation in (η(5)-Ph(5)C(5))Ru(CO)(2)X complexes is related to the stabilization provided by the X group in the final 16-electron complexes, which are formed via product-like transition states. In addition to the calculated transition states of CO dissociation in Ru-O(t)Bu and Ru

Mitochondria are the primary target in the induction of apoptosis by chiral ruthenium(II) polypyridyl complexes in cancer cells.

PubMed

Wang, Jin-Quan; Zhang, Ping-Yu; Qian, Chen; Hou, Xiao-Juan; Ji, Liang-Nian; Chao, Hui

2014-03-01

A series of novel chiral ruthenium(II) polypyridyl complexes (Δ-Ru1, Λ-Ru1, Δ-Ru2, Λ-Ru2, Δ-Ru3, Λ-Ru3) were synthesized and evaluated to determine their antiproliferative activities. Colocalization, inductively coupled plasma mass spectrometry, and 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide assay studies showed that these ruthenium(II) complexes accumulated preferentially in the mitochondria and exhibited cytotoxicity against various cancer cells in vitro. The complex Δ-Ru1 is of particular interest because it was found to have half-maximal inhibitory concentrations comparable to those of cisplatin and better activity than cisplatin against a cisplatin-resistant cell line, A549-CP/R. Δ-Ru1 induced alterations in the mitochondrial membrane potential and triggered intrinsic mitochondria-mediated apoptosis in HeLa cells, which involved the regulation of Bcl-2 family members and the activation of caspases. Taken together, these data suggest that Δ-Ru1 may be a novel mitochondria-targeting anticancer agent.

Theoretical studies on effective metal-to-ligand charge transfer characteristics of novel ruthenium dyes for dye sensitized solar cells.

PubMed

Wang, Huei-Tang; Taufany, Fadlilatul; Nachimuthu, Santhanamoorthi; Jiang, Jyh-Chiang

2014-05-01

The development of ruthenium dye-sensitizers with highly effective metal-to-ligand charge transfer (MLCT) characteristics and narrowed transition energy gaps are essential for the new generation of dye-sensitized solar cells. Here, we designed a novel anchoring ligand by inserting the cyanovinyl-branches inside the anchoring ligands of selected highly efficient dye-sensitizers and studied their intrinsic optical properties using theoretical methods. Our calculated results show that the designed ruthenium dyes provide good performances as sensitizers compared to the selected efficient dyes, because of their red-shift in the UV-visible absorption spectra with an increase in the absorption intensity, smaller energy gaps and thereby enhancing MLCT transitions. We found that, the designed anchoring ligand acts as an efficient "electron-acceptor" which boosts electron-transfer from a -NCS ligand to this ligand via a Ru-bridge, thus providing a way to lower the transition energy gap and enhance the MLCT transitions.

Temperature dependent infrared nano-imaging of La0.67Sr0.33MnO3 thin film

NASA Astrophysics Data System (ADS)

Xu, Peng; Huffman, T. J.; Hae Kwak, In; Biswas, Amlan; Qazilbash, M. M.

2018-01-01

We investigate the temperature dependence of infrared properties at nanometer length scales in La0.67Sr0.33MnO3 (LSMO) thin film with a thickness of 47 unit cells grown on SrTiO3 substrate. The infrared nano-imaging experiments were performed using a near-field optical microscope in conjunction with a variable temperature heating stage. The near-field infrared data is consistent with the bulk of the LSMO film undergoing the thermally-driven non-percolative second-order transition from a metallic, ferromagnetic phase to an insulating, paramagnetic phase. We find persistent infrared contrast on the nanoscale that is independent of temperature and which we attribute to two novel phases with different conductivities coexisting in the vicinity of the film-substrate interface. These two coexisting phases at the film-substrate interface do not undergo the metal-insulator transition (MIT) and hence are different from the metallic, ferromagnetic and insulating, paramagnetic phases in the bulk of the film. At temperatures approaching the nominal MIT temperature, repeated scans of the same microscopic area at constant temperature reveal bimodal fluctuation of the near-field infrared amplitude. We interpret this phenomenon as slow, critical fluctuations of the conductivity in the bulk of the LSMO film.

TiO2 films with rich bulk oxygen vacancies prepared by electrospinning for dye-sensitized solar cells

NASA Astrophysics Data System (ADS)

Li, Xiaodong; Gao, Caitian; Wang, Jiangtao; Lu, Bingan; Chen, Wanjun; Song, Jie; Zhang, Shanshan; Zhang, Zhenxing; Pan, Xiaojun; Xie, Erqing

2012-09-01

Highly transparent nanocrystalline TiO2 films have been fabricated by electrospinning (ES) technique based on a transmutation process from as-spun nanofibers with an appropriate amount of tri-ethanolamine (TEOA) added to the precursor. A possible evolution mechanism of the transparent nanocrystalline TiO2 films is proposed. It is found that the films prepared via transmutation from electrospun nanofibers possess rich bulk oxygen vacancies (BOVs, PL band at 621-640 nm) by using photoluminescence (PL) spectroscopy. Contrastively, the dominant peak in PL spectrum of the spin-coated film is the emission from surface oxygen vacancies (SOVs, PL band at 537-555 nm). The electrospun TiO2 films with rich BOVs induce large open-circuit voltage (Voc) and fill factor (FF) improvements in dye-sensitized solar cells (DSCs), and thus a large improvement of energy conversion efficiency (η). In addition, these performance advantages are maintained for a double-layer cell with a doctor-bladed ˜7 μm top layer (P25 nanometer TiO2, Degussa) and an electrospun ˜3 μm bottom layer. The double-layer cell yields a high η of 6.01%, which has increased by 14% as compared with that obtained from a 10 μm thick P25 film.

Mechanics of hard films on soft substrates

NASA Astrophysics Data System (ADS)

Lu, Nanshu

2009-12-01

Flexible electronics have been developed for various applications, including paper-like electronic readers, rollable solar cells, electronic skins etc., with the merits of light weight, low cost, large area, and ruggedness. The systems may be subject to one-time or repeated large deformation during manufacturing and application. Although organic materials can be highly deformable, currently they are not able to fulfill every electronic function. Therefore flexible electronic devices are usually made as organic/inorganic hybrids, with diverse materials, complex architecture, and micro features. While the polymer substrates can recover from large deformations, thin films of electronic materials such as metals, silicon, oxides, and nitrides fracture at small strains, usually less than a few percent. Mechanics of hard films on soft substrates hence holds the key to build high-performance and highly reliable flex circuits. This thesis investigates the deformability and failure mechanisms of thin films of metallic and ceramic materials supported by soft polymeric substrates through combined experimental, theoretical, and numerical methods. When subject to tension, micron-thick metal films with stable microstructure and strong interfacial adhesion to the substrate can be stretched beyond 50% without forming cracks. They eventually rupture by a ductile transgranular fracture which involves simultaneous necking and debonding. When metal films become nanometer-thick, intergranular fracture dominates the failure mode at elongations of only a few percent. Unannealed films show unstable microstructure at room temperature when subject to mechanical loading. In this case, films also rupture at small strains but by three concurrent mechanisms: deformation-induced grain growth, strain localization at large grains, and simultaneous debonding. In contrast to metal films, ceramic films rupture by brittle mechanisms. The only way to prevent rupture of ceramic films is to reduce the

Characterization of screen-printed dye-sensitized nanocrystalline TiO2 solar cells

NASA Astrophysics Data System (ADS)

Gupta, Tapan K.; Cirignano, Leonard J.; Shah, Kanai S.; Moy, Larry P.; Kelly, David J.; Squillante, Michael R.; Entine, Gerald; Smestad, Greg P.

1999-10-01

Titanium dioxide (TiO2) films have been deposited on SnO2 coated glass substrates by screen-printing. Film morphology and structure have been characterized by scanning electron microscopy, x-ray diffraction and BET analysis. Dye-sensitized TiO2 photoelectrochemical cells have been assembled and characterized. Cells sensitized with anthocyanin and a ruthenium complex have been investigated. A 0.77 cm2 ruthenium dye sensitized cell with 6.1% power conversion efficiency under Air Mass (AM1.5) conditions was obtained. Results obtained with a pure anthocyanin dye and dye extracted from blackberries were compared. Finally, a natural gel was found to improve the stability of anthocyanin sensitized cells.

Highly efficient quenching of tris(2,2'-bipyridyl)ruthenium(II) electrochemiluminescence by ozone using formaldehyde, methylglyoxal, and glyoxalate as co-reactants and its application to ozone sensing.

PubMed

Gao, Ying; Liu, Xiaoyun; Qi, Wenjing; Gao, Wenyue; Li, Yunhui; Xu, Guobao

2015-06-21

Most electrochemiluminescence (ECL) systems require high concentrations of quencher to totally quench ECL. In this study, we found that ozone can quench tris(2,2'-bipyridyl)ruthenium(II) ECL using formaldehyde, methylglyoxal, or glyoxalate as co-reactants at a glassy carbon electrode with remarkable efficiencies even when the concentration of ozone is merely 0.25% of that of the co-reactant. The strongest quenching is observed with the tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL system. The tris(2,2'-bipyridyl)ruthenium(II)/formaldehyde ECL intensities decrease linearly with the ozone concentration over the range of 0.025-25 μM (r = 0.9947) with a limit of detection of 8 nM. The method is more sensitive and faster than most methods. It shows high selectivity in the presence of other ROS or oxidants and some metal ions, such as H2O2, ClO(-), Mg(2+), Ni(2+), etc. The method exhibits high recoveries for the detection of ozone in a ventilated photocopy room.

Use of Ruthenium-106 Brachytherapy for Iris Melanoma: The Scottish Experience.

PubMed

Agraval, Umiya; Sobti, Manvi; Russell, Heather C; Lockington, David; Ritchie, Diana; Cauchi, Paul; Kemp, Ewan G; Chadha, Vikas

2018-01-01

To analyse long-term outcomes of ruthenium-106 ( 106 Ru) plaque brachytherapy for the treatment of iris melanoma. We retrospectively reviewed medical records of 19 consecutive patients with pure iris melanoma treated with 106 Ru plaque brachytherapy between 1998 and 2016 at the Scottish Ophthalmic Oncology Service, Glasgow. The iris melanoma was treated with a ruthenium plaque placed on the corneal surface to deliver a surface dose of 555 Gy. We analysed vision preservation, local tumour control, radiation-related complications, eye retention rates, symptomatic metastasis and melanoma-related mortality. The mean largest basal diameter of the lesions was 3.50±1.42 mm (range 1.6-6.5 mm), and the mean maximum height was 1.47±0.65 mm (range 0.7-2.8 mm). The tumour control and eye retention were 100% at a mean follow-up of 62 months (range 6-195 months). A 62% reduction in tumour height was observed on ultrasonography. Complications included cataract (68%), dry eye (47%), uveitis (37%) and scleral thinning (5%). At the final follow-up visit, the mean loss of Snellen visual acuity was 1.11±2.90 lines and vision of 6/9 or better was maintained in 53% of patients. None of the patients had evidence of symptomatic metastasis (non-imaged) or melanoma-related mortality. 106 Ru plaque treatment for iris melanoma was highly effective a high tumour control, no tumour recurrences and a relatively a low complication rate. © Article author(s) (or their employer(s) unless otherwise stated in the text of the article) 2018. All rights reserved. No commercial use is permitted unless otherwise expressly granted.

Enhanced endothelial cell density on NiTi surfaces with sub-micron to nanometer roughness

PubMed Central

Samaroo, Harry D; Lu, Jing; Webster, Thomas J

2008-01-01

The shape memory effect and superelastic properties of NiTi (or Nitinol, a nickel-titanium alloy) have already attracted much attention for various biomedical applications (such as vascular stents, orthodontic wires, orthopedic implants, etc). However, for vascular stents, conventional approaches have required coating NiTi with anti-thrombogenic or anti-inflammatory drug-eluting polymers which as of late have proven problematic for healing atherosclerotic blood vessels. Instead of focusing on the use of drug-eluting anti-thrombogenic or anti-inflammatory proteins, this study focused on promoting the formation of a natural anti-thrombogenic and anti-inflammatory surface on metallic stents: the endothelium. In this study, we synthesized various NiTi substrates with different micron to nanometer surface roughness by using dissimilar dimensions of constituent NiTi powder. Endothelial cell adhesion on these compacts was compared with conventional commercially pure (cp) titanium (Ti) samples. The results after 5 hrs showed that endothelial cells adhered much better on fine grain (<60 μm) compared with coarse grain NiTi compacts (<100 μm). Coarse grain NiTi compacts and conventional Ti promoted similar levels of endothelial cell adhesion. In addition, cells proliferated more after 5 days on NiTi with greater sub-micron and nanoscale surface roughness compared with coarse grain NiTi. In this manner, this study emphasized the positive pole that NiTi with sub-micron to nanometer surface features can play in promoting a natural anti-thrombogenic and anti-inflammatory surface (the endothelium) on a vascular stent and, thus, suggests that more studies should be conducted on NiTi with sub-micron to nanometer surface features. PMID:18488418

Theoretical characterization of the surface composition of ruthenium nanoparticles in equilibrium with syngas

NASA Astrophysics Data System (ADS)

Cusinato, Lucy; Martínez-Prieto, Luis M.; Chaudret, Bruno; Del Rosal, Iker; Poteau, Romuald

2016-05-01

A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction of CO and H with the surface of the catalyst. In this context, the single- and co-adsorption of CO and H to the surface of a 1 nm ruthenium nanoparticle has been investigated with density functional theory. Using several indexes (d-band center, crystal overlap Hamilton population, density of states), a systematic analysis of the bond properties and of the electronic states has also been done, in order to bring an understanding of structure/property relationships at the nanoscale. The H : CO surface composition of this ruthenium nanoparticle exposed to syngas has been evaluated according to a thermodynamic model fed with DFT energies. Such ab initio thermodynamic calculations give access to the optimal H : CO coverage values under a wide range of experimental conditions, through the construction of free energy phase diagrams. Surprisingly, under the Fischer-Tropsch synthesis experimental conditions, and in agreement with new experiments, only CO species are adsorbed at the surface of the nanoparticle. These findings shed new light on the possible reaction pathways underlying the Fischer-Tropsch synthesis, and specifically the initiation of the reaction. It is finally shown that the joint knowledge of the surface composition and energy descriptors can help to identify possible reaction intermediates.A deeper understanding of the relationship between experimental reaction conditions and the surface composition of nanoparticles is crucial in order to elucidate mechanisms involved in nanocatalysis. In the framework of the Fischer-Tropsch synthesis, a resolution of this complex puzzle requires a detailed understanding of the interaction

Integrating Nano-patterned Ferromagnetic and Ferroelectric Thin Films for Electrically Tunable RF Applications

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Tengxing; Peng, Yujia; Jiang, Wei

Tunable radio frequency (RF) components are pivotal elements in frequency-agile and multifunctional systems. However, there is a technical barrier to achieve miniaturized fully electrically tunable RF components. This paper provides and demonstrates the efficacy of a first unique design methodology in developing fully electrically tunable RF components by integrating ferromagnetic (e.g., Permalloy) and ferroelectric (e.g., Lead Zirconate Titanate: PZT) thin films patterns. Permalloy thin film has been patterned in nanometer scale to improve its ferromagnetic resonance frequency (FMR) for RF applications. Tunable inductors are developed with the utilization of different thickness of Permalloy thin film, which show over 50% incrementmore » in inductance and over 4% in tunability with DC current. More tunability can be achieved with multiple layers of Permalloy thin film and optimized thickness. A fully electrically tunable slow wave RF transmission line with simultaneously variable inductance and capacitance density has been implemented and thoroughly investigated for the first time. Measured results show that a fixed phase shift of 90° can be achieved from 1.5 GHz to 1.85 GHz continuously by applying external DC current from 0 to 200 mA and external DC voltage from 0 to 15 Volts, respectively.« less

Integrating Nano-patterned Ferromagnetic and Ferroelectric Thin Films for Electrically Tunable RF Applications

DOE PAGES

Wang, Tengxing; Peng, Yujia; Jiang, Wei; ...

2016-10-31

Tunable radio frequency (RF) components are pivotal elements in frequency-agile and multifunctional systems. However, there is a technical barrier to achieve miniaturized fully electrically tunable RF components. This paper provides and demonstrates the efficacy of a first unique design methodology in developing fully electrically tunable RF components by integrating ferromagnetic (e.g., Permalloy) and ferroelectric (e.g., Lead Zirconate Titanate: PZT) thin films patterns. Permalloy thin film has been patterned in nanometer scale to improve its ferromagnetic resonance frequency (FMR) for RF applications. Tunable inductors are developed with the utilization of different thickness of Permalloy thin film, which show over 50% incrementmore » in inductance and over 4% in tunability with DC current. More tunability can be achieved with multiple layers of Permalloy thin film and optimized thickness. A fully electrically tunable slow wave RF transmission line with simultaneously variable inductance and capacitance density has been implemented and thoroughly investigated for the first time. Measured results show that a fixed phase shift of 90° can be achieved from 1.5 GHz to 1.85 GHz continuously by applying external DC current from 0 to 200 mA and external DC voltage from 0 to 15 Volts, respectively.« less

Nickel-foam-supported ruthenium oxide/graphene sandwich composite constructed via one-step electrodeposition route for high-performance aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Li, Meng; He, Hanwei

2018-05-01

A high-performance supercapacitor both considered high power and high energy density is needed for its applications such as portable electronics and electric vehicles. Herein, we construct a high-performance ruthenium oxide/graphene (RuO2-ERG) composite directly grown on Ni foam through cyclic voltammetric deposition process. The RuO2-ERG composite with sandwich structure is achieved effectively from a mixed solution of graphene oxide and ruthenium trichloride in the -1.4 V to 1.0 V potential range at a scan rate of 5 mV s-1. The electrochemical performance is optimized by tuning the concentration of the ruthenium trichloride. This integrative RuO2-ERG composite electrode can effectively maintains the accessible surface for redox reaction and stable channels for electrolyte penetration, leading to an improved electrochemical performance. Symmetrical aqueous supercapacitors based on RuO2-ERG electrodes exhibit a wider operational voltage window of 1.5 V. The optimized RuO2-ERG electrode displays a superior specific capacitance with 89% capacitance retention upon increasing the current density by 50 times. A high energy density of 43.8 W h kg-1 at a power density of 0.75 kW kg-1 is also obtained, and as high as 39.1 W h kg-1 can be retained at a power density of 37.5 kW kg-1. In addition, the capacitance retention is still maintained at 92.8% even after 10,000 cycles. The excellent electrochemical performance, long-term cycle stability, and the ease of preparation demonstrate that this typical RuO2-ERG electrode has great potentialities to develop high-performance supercapacitors.

The thermodynamic effects of ligand structure on the molecular recognition of mononuclear ruthenium polypyridyl complexes with B-DNA

USDA-ARS?s Scientific Manuscript database

The ruthenium(II) polypyridyl complexes (RPCs), [(phen)2Ru(tatpp)]Cl2 (3Cl2) and [(phen)2Ru (tatpp)Ru(phen)2]Cl4 (4Cl4), containing the large planar and redox-active tetraazatetrapyrido- pentacene (tatpp) ligand, cleave DNA in the presence of reducing agents in cell-free assays and show significant...

Plasma-Assisted Synthesis of Monodispersed and Robust Ruthenium Ultrafine Nanocatalysts for Organosilane Oxidation and Oxygen Evolution Reactions.

PubMed

Gnanakumar, Edwin S; Ng, Wesley; Coşkuner Filiz, Bilge; Rothenberg, Gadi; Wang, Sheng; Xu, Hualong; Pastor-Pérez, Laura; Pastor-Blas, M Mercedes; Sepúlveda-Escribano, Antonio; Yan, Ning; Shiju, N Raveendran

2017-11-23

We report a facile and general approach for preparing ultrafine ruthenium nanocatalysts by using a plasma-assisted synthesis at <100 °C. The resulting Ru nanoparticles are monodispersed (typical size 2 nm) and remain that way upon loading onto carbon and TiO 2 supports. This gives robust catalysts with excellent activities in both organosilane oxidation and the oxygen evolution reaction.

Nanoparticle-supported and magnetically recoverable ruthenium hydroxide catalyst: efficient hydration of nitriles to amides in aqueous medium.

PubMed

Polshettiwar, Vivek; Varma, Rajender S

2009-01-01

Magnetic attraction not filtration: A magnetic nanoparticle-supported ruthenium hydroxide catalyst (see figure) was readily prepared from inexpensive starting materials and shown to catalyze the hydration of nitriles with excellent yield in a benign aqueous medium. Catalyst recovery using an external magnetic field, superior activity, and the inherent stability of the catalyst system are additional sustainable attributes of this protocol.

Surface-enhanced Raman scattering of amorphous TiO2 thin films by gold nanostructures: Revealing first layer effect with thickness variation

NASA Astrophysics Data System (ADS)

Degioanni, S.; Jurdyc, A.-M.; Bessueille, F.; Coulm, J.; Champagnon, B.; Vouagner, D.

2013-12-01

In this paper, amorphous titanium dioxide (TiO2) thin films have been deposited on a commercially available Klarite substrate using the sol-gel process to produce surface-enhanced Raman scattering (SERS). The substrate consists of square arrays of micrometer-sized pyramidal pits in silicon with a gold coating. Several thin TiO2 layers have been deposited on the surface to study the influence of film thickness. Ultimately, we obtained information on SERS of an amorphous TiO2 layer by gold nanostructures, whose range is less than a few nanometers. Mechanisms responsible for the enhancement are the product of concomitant chemical and electromagnetic effects with an important contribution from plasmon-induced charge transfer.

Nanometer scale atomic structure of zirconium based bulk metallic glass

NASA Astrophysics Data System (ADS)

Hwang, Jinwoo

We have studied the nanometer scale structure of bulk metallic glass (BMG) using fluctuation electron microscopy (FEM). The nanometer scale medium range order (MRO) in BMG is of significant interest because of its possible relationship to the properties, but the experimental study of the MRO is difficult because conventional diffraction techniques are not sensitive to the MRO scale. FEM is a quantitative transmission electron microscopy technique which measures the nanoscale structural fluctuation associated with MRO in amorphous materials, and provides information about the size, distribution, and internal structure of MRO. In this work, we developed an improved method for FEM using energy-filtered STEM nanodiffraction with highly coherent probes with size up to 11nm in a state-of-the-art Cs- corrected STEM. We also developed an effective way to eliminate the effect of sample thickness variation to the FEM data by using Z-contrast images as references. To study the detailed structure of MRO, we developed a hybrid reverse Monte Carlo (H-RMC) simulation which combines an empirical atomic potential and the FEM data. H-RMC generated model structures that match the experimental data at short and medium range. In addition, the subtle rotational symmetries in the FEM nanodiffraction patterns were analyzed by angular correlation function to reveal more details of the internal structure of MRO. Our experiments and simulations show that Zr-based BMG contains pseudo-planar, crystal-like MRO as well as icosahedral clusters in its nanoscale structure. We found that some icosahedral clusters may be connected, and that structural relaxation by annealing increases the population of icosahedral clusters.

Synthesis of m-Alkylphenols via a Ruthenium-Catalyzed C-H Bond Functionalization of Phenol Derivatives.

PubMed

Li, Gang; Gao, Panpan; Lv, Xulu; Qu, Chen; Yan, Qingkai; Wang, Ya; Yang, Suling; Wang, Junjie

2017-05-19

The first example of the synthesis of m-alkylphenols via a ruthenium-catalyzed C Ar -H bond functionalization of phenol derivatives with sec/tert-alkyl bromides is reported. Mechanistic studies indicated that the m-C Ar -H bond alkylation may involve a radical process and that a six-membered ruthenacycle complex was the active catalyst. Moreover, this approach can provide an expedited strategy for the atom-/step-economical synthesis of many noteworthy pharmaceuticals and other functional molecules.

Ruthenium-based, inert oxide electrodes for impregnating active materials in nickel plaques

NASA Astrophysics Data System (ADS)

Manoharan, R.; Uma, M.

Titanium electrodes coated with mixed ruthenium-iridium-titanium oxides are tested as inert counter electrodes for impregnating active materials in porous nickel plaques. The latter are to be used as the positive electrodes in nickel/cadmium cells. Weight losses and variations in bath voltage have been monitored while using these electrodes in the impregnation bath. A 2.85 Ah nickel/cadmium cell has been constructed using nickel electrodes developed by employing the coated electrodes of this study. The performances of these coated electrodes are compared with those of platinum electrodes that are currently employed by nickel/cadmium battery manufacturers. The results are found to be satisfactory.

Nanopore Measurements of Filamentous Viruses Reveal a Sub-nanometer-Scale Stagnant Fluid Layer.

PubMed

McMullen, Angus J; Tang, Jay X; Stein, Derek

2017-11-28

We report measurements and analyses of nanopore translocations by fd and M13, two related strains of filamentous virus that are identical except for their charge densities. The standard continuum theory of electrokinetics greatly overestimates the translocation speed and the conductance associated with counterions for both viruses. Furthermore, fd and M13 behave differently from one another, even translocating in opposite directions under certain conditions. This cannot be explained by Manning-condensed counterions or a number of other proposed models. Instead, we argue that these anomalous findings are consequences of the breakdown of the validity of continuum hydrodynamics at the scale of a few molecular layers. Next to a polyelectrolyte, there exists an extra-viscous, sub-nanometer-thin boundary layer that has a giant influence on the transport characteristics. We show that a stagnant boundary layer captures the essential hydrodynamics and extends the validity of the electrokinetic theory beyond the continuum limit. A stagnant layer with a thickness of about half a nanometer consistently improves predictions of the ionic current change induced by virus translocations and of the translocation velocity for both fd and M13 over a wide range of nanopore dimensions and salt concentrations.

Polyelectrolyte-mediated assembly of copper-phthalocyanine tetrasulfonate multilayers and the subsequent production of nanoparticulate copper oxide thin films.

PubMed

Chickneyan, Zarui Sara; Briseno, Alejandro L; Shi, Xiangyang; Han, Shubo; Huang, Jiaxing; Zhou, Feimeng

2004-07-01

An approach to producing films of nanometer-sized copper oxide particulates, based on polyelectrolyte-mediated assembly of the precursor, copper(II)phthalocyanine tetrasulfonate (CPTS), is described. Multilayered CPTS and polydiallyldimethylammonium chloride (PDADMAC) were alternately assembled on different planar substrates via the layer-by-layer (LbL) procedure. The growth of CPTS multilayers was monitored by UV-visible spectrometry and quartz crystal microbalance (QCM) measurements. Both the UV-visible spectra and the QCM data showed that a fixed amount of CPTS could be attached to the substrate surface for a given adsorption cycle. Cyclic voltammograms at the CPTS/PDADMAC-covered gold electrode exhibited a decrease in peak currents with the layer number, indicating that the permeability of CPTS multilayers on the electrodes had diminished. When these CPTS multilayered films were calcined at elevated temperatures, uniform thin films composed of nanoparticulate copper oxide could be produced. Ellipsometry showed that the thickness of copper oxide nanoparticulate films could be precisely tailored by varying the thickness of CPTS multilayer films. The morphology and roughness of CPTS multilayer and copper oxide thin films were characterized by atomic force microscopy. X-ray diffraction (XRD) measurements indicated that these thin films contained both CuO and Cu2O nanoparticles. The preparation of such copper oxide thin films with the use of metal complex precursors represents a new route for the synthesis of inorganic oxide films with a controlled thickness.

Intervalence transfer of ferrocene moieties adsorbed on electrode surfaces by a conjugated linkage

NASA Astrophysics Data System (ADS)

Chen, Wei; Brown, Lauren E.; Konopelski, Joseph P.; Chen, Shaowei

2009-03-01

Effective intervalence transfer occurred between the metal centers of ferrocene moieties that were adsorbed onto a ruthenium thin film surface by ruthenium-carbene π bonds, a direct verification of Hush's four-decade-old prediction. Electrochemical measurements showed two pairs of voltammetric peaks where the separation of the formal potentials suggested a Class II behavior. Additionally, the potential spacing increased with increasing ferrocene surface coverage, most probably as a consequence of the enhanced contribution from through-space electronic interactions between the metal centers. In contrast, the incorporation of a sp 3 carbon spacer into the ferrocene-ruthenium linkage led to the diminishment of interfacial electronic communication.

Tribological properties of self-assembled monolayers of catecholic imidazolium and the spin-coated films of ionic liquids.

PubMed

Liu, Jianxi; Li, Jinlong; Yu, Bo; Ma, Baodong; Zhu, Yangwen; Song, Xinwang; Cao, Xulong; Yang, Wu; Zhou, Feng

2011-09-20

A novel compound of an imidazolium type of ionic liquid (IL) containing a biomimetic catecholic functional group normally seen in mussel adhesive proteins was synthesized. The IL can be immobilized on a silicon surface and a variety of other engineering material surfaces via the catecholic anchor, allowing the tribological protection of these substrates for engineering applications. The surface wetting and adhesive properties and the tribological property of the synthesized self-assembled monolayers (SAMs) are successfully modulated by altering the counteranions. The chemical composition and wettability of the IL SAMs were characterized by means of X-ray photoelectron spectroscopy (XPS) and contact angle (CA) measurements. The adhesive and friction forces were measured with an atomic force microscope (AFM) on the nanometer scale. IL composite films were prepared by spin coating thin IL films on top of the SAMs. The macrotribological properties of these IL composite films were investigated with a pin-on-disk tribometer. The results indicate that the presence of IL SAMs on a surface can improve the wettability of spin-coated ionic liquids and thus the film quality and the tribological properties. These films registered a reduced friction coefficient and a significantly enhanced durability and load-carrying capacity. The tribological properties of the composite films are better than those of pure IL films because the presence of the monolayers improves the adhesion and compatibility of spin-coated IL films with substrates. © 2011 American Chemical Society

Coordination behavior of ligand based on NNS and NNO donors with ruthenium(III) complexes and their catalytic and DNA interaction studies

NASA Astrophysics Data System (ADS)

Manikandan, R.; Viswnathamurthi, P.

2012-11-01

Reactions of 2-acetylpyridine-thiosemicarbazone HL1, 2-acetylpyridine-4-methyl-thiosemicarbazone HL2, 2-acetylpyridine-4-phenyl-thiosemicarbazone HL3 and 2-acetylpyridine-semicarbazone HL4 with ruthenium(III) precursor complexes were studied and the products were characterized by analytical and spectral (FT-IR, electronic, EPR and EI-MS) methods. The ligands coordinated with the ruthenium(III) ion via pyridine nitrogen, azomethine nitrogen and thiolate sulfur/enolate oxygen. An octahedral geometry has been proposed for all the complexes based on the studies. All the complexes are redox active and display an irreversible and quasireversible metal centered redox processes. Further, the catalytic activity of the new complexes has been investigated for the transfer hydrogenation of ketones in the presence of isopropanol/KOH and the Kumada-Corriu coupling of aryl halides with aryl Grignard reagents. The DNA cleavage efficiency of new complexes has also been tested.

Towards a rational design of ruthenium CO2 hydrogenation catalysts by Ab initio metadynamics.

PubMed

Urakawa, Atsushi; Iannuzzi, Marcella; Hutter, Jürg; Baiker, Alfons

2007-01-01

Complete reaction pathways relevant to CO2 hydrogenation by using a homogeneous ruthenium dihydride catalyst ([Ru(dmpe)2H2], dmpe=Me2PCH2CH2PMe2) have been investigated by ab initio metadynamics. This approach has allowed reaction intermediates to be identified and free-energy profiles to be calculated, which provide new insights into the experimentally observed reaction pathway. Our simulations indicate that CO2 insertion, which leads to the formation of formate complexes, proceeds by a concerted insertion mechanism. It is a rapid and direct process with a relatively low activation barrier, which is in agreement with experimental observations. Subsequent H2 insertion into the formate--Ru complex, which leads to the formation of formic acid, instead occurs via an intermediate [Ru(eta2-H2)] complex in which the molecular hydrogen coordinates to the ruthenium center and interacts weakly with the formate group. This step has been identified as the rate-limiting step. The reaction completes by hydrogen transfer from the [Ru(eta2-H2)] complex to the formate oxygen atom, which forms a dihydrogen-bonded Ru--HHO(CHO) complex. The activation energy for the H2 insertion step is lower for the trans isomer than for the cis isomer. A simple measure of the catalytic activity was proposed based on the structure of the transition state of the identified rate-limiting step. From this measure, the relationship between catalysts with different ligands and their experimental catalytic activities can be explained.

Carbon Nanotubules: Building Blocks for Nanometer-Scale Engineering

NASA Technical Reports Server (NTRS)

Sinnott, Susan B.

1997-01-01

Proximal probe technology has provided researchers with new ways to investigate and manipulate matter on the nanometer scale. We have studied, through molecular dynamics simulations, using a many-body empirical potential, the indentation of a hydrogen-terminated, diamond (111 ) surface, with a proximal probe tip that consists of an open, hydrogen-terminated, (10,10) carbon nanotubule. The simulations showed that upon indenting 1.8 A, the tubule deforms but returns to its original shape upon retraction. The Young's modulus of the tubule was determined using the predicted Euler buckling force and was found to be comparable to measured and calculated values. In a second series of simulations, an open (10, 10) nanotubule was heated to 4500 K and allowed to close. We find that at this temperature the resulting cap contains numerous imperfections, including some not mentioned previously in the literature.

Electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices

NASA Astrophysics Data System (ADS)

Hung, Chen-Jen

This dissertation presents an investigation of the electrocrystallization and scanning probe microscopy of ceramic thin films and superlattices. All of the films were deposited from aqueous solution at room temperature with no subsequent heat treatment needed to effect crystallization. Thallium(III) oxide defect chemistry superlattices were electrodeposited by pulsing the applied overpotential during deposition. The defect chemistry of the oxide is dependent on the applied overpotential. High overpotentials favor oxygen vacancies, while low overpotentials favor cation interstitials. Nanometer-scale holes were formed in thin thallium(III) oxide films using the scanning tunneling microscope in humid ambient conditions. Both cathodic and anodic etching reactions were performed on this metal oxide surface. The hole formation was attributed to localized electrochemical etching reactions beneath the STM tip. The scanning tunneling microscope (STM) was also used to both induce local surface modifications and image cleaved Pb-Tl-O superlattices. A trench of 100 nm in width, 32 nm in depth, and over 1 μm in length was formed after sweeping a bias voltage of ±2.5 V for 1 minute using a fixed STM tip. It has been suggested that STM results obtained under ambient conditions must be evaluated with great care because of the possibility of localized electrochemcial reactions. A novel synthesis method for the production of Cu(II) oxide from an alkaline solution containing Cu(II) tartrate was developed. Rietveld refinement of the cupric oxide films reveals pure Cu(II) oxide with no Cu(I) oxide present in the film.