Structural properties of buried conducting layers formed by very low energy ion implantation of gold into polymer

We have investigated the fundamental structural properties of conducting thin films formed by implanting gold ions into polymethylmethacrylate (PMMA) polymer at 49 eV using a repetitively pulsed cathodic arc plasma gun. Transmission electron microscopy images of these composites show that the implanted ions form gold clusters of diameter similar to 2-12 nm distributed throughout a shallow, buried layer of average thickness 7 nm, and small angle x-ray scattering (SAXS) reveals the structural properties of the PMMA-gold buried layer. The SAXS data have been interpreted using a theoretical model that accounts for peculiarities of disordered systems.

High performance magnetic separation of gold nanoparticles for catalytic oxidation of alcohols

We present the magnetic separation approach to facilitate the recovery of gold nanoparticle (AuNP) catalysts. The use of magnetically recoverable supports for the immobilization of AuNPs instead of traditional oxides, polymers or carbon based solids guarantees facile, clean, fast and efficient separation of the catalyst at the end of the reaction cycle. Magnetic separation can be considered an environmentally benign separation approach, since it minimizes the use of auxiliary substances and energy for achieving catalyst recovery. The catalyst preparation is based on the immobilization of Au(3+) on the surface of core-shell silica-coated magnetite nanoparticles, followed by metal reduction using two different methods. AuNPs were prepared by thermal reduction in air and by hydrogen reduction at mild temperature. Interestingly, the mean particle size of the supported AuNPs was similar (ca. 5.9 nm), but the polydispersity of the samples is quite different. The catalytic activity of both catalysts in the aerobic oxidation of alcohols was investigated and a distinct selectivity for benzyl alcohol oxidation was observed.

Limit on the diffuse flux of ultrahigh energy tau neutrinos with the surface detector of the Pierre Auger Observatory

Data collected at the Pierre Auger Observatory are used to establish an upper limit on the diffuse flux of tau neutrinos in the cosmic radiation. Earth-skimming nu(tau) may interact in the Earth's crust and produce a tau lepton by means of charged-current interactions. The tau lepton may emerge from the Earth and decay in the atmosphere to produce a nearly horizontal shower with a typical signature, a persistent electromagnetic component even at very large atmospheric depths. The search procedure to select events induced by tau decays against the background of normal showers induced by cosmic rays is described. The method used to compute the exposure for a detector continuously growing with time is detailed. Systematic uncertainties in the exposure from the detector, the analysis, and the involved physics are discussed. No tau neutrino candidates have been found. For neutrinos in the energy range 2x10(17) eV < E(nu)< 2x10(19) eV, assuming a diffuse spectrum of the form E(nu)(-2), data collected between 1 January 2004 and 30 April 2008 yield a 90% confidence-level upper limit of E(nu)(2)dN(nu tau)/dE(nu)< 9x10(-8) GeV cm(-2) s(-1) sr(-1).

Synergistic interaction between gold nanoparticles and nickel phthalocyanine in layer-by-layer (LbL) films: evidence of constitutional dynamic chemistry (CDC)

The concept of constitutional dynamic chemistry (CDC) based on the control of non-covalent interactions in supramolecular structures is promising for having a large impact on nanoscience and nanotechnology if adequate nanoscale manipulation methods are used. In this study, we demonstrate that the layer-by-layer (LbL) technique may be used to produce electroactive electrodes with ITO coated by tetrasulfonated nickel phthalocyanine (NiTsPc) alternated with poly(allylamine hydrochloride) (PAH) incorporating gold nanoparticles (AuNP), in which synergy has been achieved in the interaction between the nanoparticles and NiTsPc. The catalytic activity toward hydrogen peroxide (H(2)O(2)) in multilayer films was investigated using cyclic voltammetry, where oxidation of H(2)O(2) led to increased currents in the PAH-AuNP/NiTsPc films for the electrochemical processes associated with the phthalocyanine ring and nickel at 0.52 and 0.81 V vs. SCE, respectively, while for PAH/NiTsPc films (without AuNP) only the first redox process was affected. In control experiments we found out that the catalytic activity was not solely due to the presence of AuNP, but rather to the nanoparticles inducing NiTsPc supramolecular structures that favored access to their redox sites, thus yielding strong charge transfer. The combined effects of NiTsPc and AuNP, which could only be observed in nanostructured LbL films, point to another avenue to pursue within the CDC paradigm.

Surface Plasmon-Induced Band Gap in the Photocurrent Response of Organic Solar Cells

A 260 nm layer of organic bulk heterojunction blend of the polymer poly(3-hexylthiophene) (P3HT) and the fullerene [6,6]-phenyl C(61)-butyric (PCBM) was spin-coated in between aluminum and gold electrodes, respectively, on top of a laser inscribed azo polymer surface-relief diffraction grating. Angle-dependent surface plasmons (SPs) with a large band gap were observed in the normalized photocurrent by the P3HT-PCBM layer as a function of wavelength. The SP-induced photocurrents were also investigated as a function of the grating depth and spacing.

Reconstruction of core and surface nanoparticles: The example of Pt(55) and Au(55)

Cuboctahedron (CUB) and icosahedron (ICO) model structures are widely used in the study of transition-metal (TM) nanoparticles (NPs), however, it might not provide a reliable description for small TM NPs such as the Pt(55) and Au(55) systems in gas phase. In this work, we combined density-functional theory calculations with atomic configurations generated by the basin hopping Monte Carlo algorithm within the empirical Sutton-Chen embedded atom potential. We identified alternative lower energy configurations compared with the ICO and CUB model structures, e. g., our lowest energy structures are 5.22 eV (Pt(55)) and 2.01 eV (Au(55)) lower than ICO. The energy gain is obtained by the Pt and Au diffusion from the ICO core region to the NP surface, which is driven by surface compression (only 12 atoms) on the ICO core region. Therefore, in the lowest energy configurations, the core size reduces from 13 atoms (ICO, CUB) to about 9 atoms while the NP surface increases from 42 atoms (ICO, CUB) to about 46 atoms. The present mechanism can provide an improved atom-level understanding of small TM NPs reconstructions.

Nanogravimetric and voltammetric studies of a Pt-Rh alloy surface and its behavior for methanol oxidation

This paper describes the preparation of a Pt-Rh alloy surface electrodeposited on Pt electrodes and its electrocatalytic characterization for methanol oxidation. The X-ray photoelectronic spectroscopy ( XPS) results demonstrate that the surface composition is approximately 24 at-% Rh and 76 % Pt. The cyclic voltammetry (CV) and electrochemical quartz crystal (EQCN) results for the alloy were associated, for platinum, to the well known profile in acidic medium. For Rh, on the alloy, the generation of rhodium hydroxide species (Rh(OH)(3) and RhO(OH)(3)) was measured. During the successive oxidation-reduction cycles the mass returns to its original value, indicating the reversibility of the processes. It was not observed rhodium dissolution during the cycling. The 76/24 at % Pt-Rh alloy presented singular electrocatalytic activity for methanol electrooxidation, which started at more negative potentials compared to pure Pt (70 mV). During the sweep towards more negative potentials, there is only weak CO re-adsorption on both Rh and Pt-Rh alloy surfaces, which can be explained by considering the interaction energy between Rh and CO.

Nanostructured diamond-like carbon films characterization

In this work, we have studied the influence of the substrate surface condition on the roughness and the structure of the nanostructured DLC films deposited by high-density plasma chemical vapor deposition Four methods were used to modify the silicon wafers surface before starting the deposition processes of the nanostructured DLC films. micro-diamond powder dispersion, micro-graphite powder dispersion, and roughness generation by wet chemical etching and roughness generation by plasma etching. The reference wafer was only submitted to a chemical cleaning. It was possible to see that the final roughness and the sp(3) hybridization degree (that is related with the structure and chemical composition) strongly depend on the substrate surface conditions The surface roughness was observed by AFM and SEM and the hybridization degree of the DLC films was analyzed by Raman Spectroscopy Thus, the effects of the substrate surface on the DLC film structure were confirmed. These phenomena can be explained by the fact that the locally higher surface energy and the sharp edges may induce local defects promoting the nanostructured characteristics in the DLC films. (C) 2009 Elsevier B.V. All rights reserved.

Production and characterization of RF-sputtered PbO-GeO(2) amorphous thin films containing silver and gold nanoparticles

In the present work we report the characterization of PbO-GeO(2) films containing silver nanoparticles (NPs). Radio Frequency (RF) co-sputtering was used for deposition of amorphous films on glass substrates. Targets of 60PbO-40GeO(2) (in wt%) and bulk silver with purity of 99.99% were RF-sputtered using 3.5 m Torr of argon. The concentration of silver and gold NPs in the films was controlled varying the RF-power applied to the targets (40-50W for the PbO-GeO(2) target; 6-8 W for the metallic target). The films obtained were annealed in air at different temperatures and various periods of time. Absorption measurements have shown strong NPs surface plasmon bands. Different widths and peak wavelengths were observed, indicating that size, shape and distribution of the silver NPs are dependent on the deposition process parameters and on the annealing of the samples. X-Ray Fluorescence and Transmission Electron Microscopy were also used to characterize the samples. (C) 2010 Elsevier B.V. All rights reserved.

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

This work investigates the formation of self-assembled monolayers (SAMs) of cystamine and cystamine-glutaraldehyde on a screen-printed electrode, and the immobilization of the Tc85 protein (from Trypanosoma cruzi) on these monolayers. The methods used included infrared techniques, cyclic voltammetry, and electrochemical impedance spectroscopy. The electrochemical studies were performed at pH 6.9 in 0.1 mol L(-1) phosphate buffer solution containing Fe(CN)(6)(-3/-4) redox species. The surface coverage (0) of the electrode was 0.10 (cystamine), 0.35 (cystamine-glutaraldehyde) and 0.84 (Tc85). Interpretation of electrochemical impedance spectroscopy results was based on a charge-transfer reaction involving Fe(CN)(6)(-3/-4) species at high frequencies, followed by a diffusion through the monolayers at lower frequencies. Estimates of the electrode surface coverage, active site radius, and distance between two adjacent sites assumed that charge transfer occurred at the active sites, and that there was a planar diffusion of redox species to these sites. (C) 2009 Elsevier B.V. All rights reserved.

Impedimetric immunosensor for electronegative low density lipoprotein (LDL(-)) based on monoclonal antibody adsorbed on (polyvinyl formal)-gold nanoparticles matrix

Monoclonal antibodies (MAb) have been commonly applied to measure LDL in vivo and to characterize modifications of the lipids and apoprotein of the LDL particles. The electronegative low density lipoprotein (LDL(-)) has an apolipoprotein B-100 modified at oxidized events in vivo. In this work, a novel LDL-electrochemical biosensor was developed by adsorption of anti-LDL(-) MAb on an (polyvinyl formal)-gold nanoparticles (PVF-AuNPs)-modified gold electrode. Electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV) were used to characterize the recognition of LDL-. The interaction between MAb-LDL(-) leads to a blockage in the electron transfer of the [Fe(CN)(6)](4-)/K(4)[Fe(CN)(6)](3-) redox couple, which may could result in high change in the electron transfer resistance (R(CT)) and decrease in the amperometric responses in CV analysis. The compact antibody-antigen complex introduces the insulating layer on the assembled surface, which increases the diameter of the semicircle, resulting in a high R(CT), and the charge transferring rate constant k(0) decreases from 18.2 x 10(-6) m/s to 4.6 x 10(-6) m/s. Our results suggest that the interaction between MAb and lipoprotein can be quantitatively assessed by the modified electrode. The PVF-AuNPs-MAb system exhibited a sensitive response to LDL(-), which could be used as a biosensor to quantify plasmatic levels of LDL(-). (C) 2011 Elsevier B.V. All rights reserved.

Towards an understanding of the age and origin of mesothermal gold mineralisation in the Etheridge Goldfield, Georgetown region, north Queensland

Small mesothermal vein quam-gold-base-metal sulfide deposits from which some 20 t of Au-Ag bullion have been extracted, are the most common gold deposits in the Georgetown region of north Queensland-several hundred were mined or prospected between 1870 and 1950. These deposits are mostly hosted by Proterozoic granitic and metamorphic rocks and are similar to the much larger Charters Towers deposits such as Day Dawn and Brilliant, and in some respects to the Motherlode deposits of California. The largest deposit in the region-Kidston (> 138 t of Au and Ag since 1985)- is substantially different. It is hosted by sheeted quartz veins and cavities in brecciated Silurian granite and Proterozoic metamorphics above nested high-level Carboniferous intrusives associated with a nearby cauldron subsidence structure. This paper provides new information (K-Ar and Rb-Sr isotopic ages, preliminary oxygen isotope and fluid-inclusion data) from some of the mesothermal deposits and compares it with the Kidston deposit. All six dated mesothermal deposits have Siluro-Devonian (about 425 to 400 Ma) ages. All nine of such deposits analysed have delta(18)O quartz values in the range 8.4 to 15.7 parts per thousand, Fluid-inclusion data indicate homogenisation temperatures in the range 230-350 degrees C. This information, and a re-interpretation of the spatial relationships of the deposits with various elements of the updated regional geology, is used to develop a preliminary metallogenic model of the mesothermal Etheridge Goldfield. The model indicates how the majority of deposits may have formed from hydrothermal systems initiated during the emplacement of granitic batholiths that were possibly, but not clearly, associated with Early Palaeozoic subduction, and that these fluid systems were dominated by substantially modified meteoric and/or magmatic fluids. The large Kidston deposit and a few small relatives are of Carboniferous age and formed more directly from magmatic systems much closer to the surface.

Development of nanostructured bioanodes containing dendrimers and dehydrogenases enzymes for application in ethanol biofuel cells

This paper describes the use of the electrostatic layer-by-layer (LbL) technique for the preparation of bioanodes with potential application in ethanol/O(2) biofuel cells. More specifically, the LbL technique was employed for immobilization of dehydrogenase enzymes and polyamidoamine (PAMAM) dendrimers onto carbon paper support. Both mono (anchoring only the enzyme alcohol dehydrogenase, ADH) and bienzymatic (anchoring both ADH and aldehyde dehydrogenase, AldDH) systems were tested. The amount of ADH deposited onto the Toray (R) paper was 95 ng cm(-2) per bilayer. Kinetic studies revealed that the LbL technique enables better control of enzyme disposition on the bioanode, as compared with the results obtained with the bioanodes prepared by the passive adsorption technique. The power density values achieved for the mono-enzymatic system as a function of the enzyme load ranged from 0.02 to 0.063 mW cm(-2) for the bioanode containing 36 ADH bilayers. The bioanodes containing a gas diffusion layer (GDL) displayed enhanced performance, but their mechanical stability must be improved. The bienzymatic system generated a power density of 0.12 mW cm(-2). In conclusion, the LbL technique is a very attractive approach for enzyme immobilization onto carbon platform, since it enables strict control of enzyme disposition on the bioanode surface with very low enzyme consumption. (C) 2010 Elsevier B.V. All rights reserved.

Influence of thermal and mechanical cycling on the flexural strength of ceramics with titanium or gold alloy frameworks

Objectives. The aim of this study was to evaluate the effect of thermal and mechanical cycling alone or in combination, on the flexural strength of ceramic and metallic frameworks cast in gold alloy or titanium. Methods. Metallic frameworks (25 mm x 3 mm x 0.5 mm) (N = 96) cast in gold alloy or commercial pure titanium (Ti cp) were obtained using acrylic templates. They were airborne particle-abraded with 150 mu m aluminum oxide at the central area of the frameworks (8 mm x 3 mm). Bonding agent and opaque were applied on the particle-abraded surfaces and the corresponding ceramic for each metal was fired onto them. The thickness of the ceramic layer was standardized by positioning the frameworks in a metallic template (height: I mm). The specimens from each ceramic-metal combination (N = 96, n = 12 per group) were randomly assigned into four experimental fatigue conditions, namely water storage at 37 degrees C for 24 h (control group), thermal cycling (3000 cycles, between 4 and 55 degrees C, dwell time: 10 s), mechanical cycling (20,000 cycles under 10 N load, immersion in distilled water at 37 degrees C) and, thermal and mechanical cycling. A flexural strength test was performed in a universal testing machine (crosshead speed: 1.5 mm/min). Data were statistically analyzed using two-way ANOVA and Tukey`s test (alpha = 0.05). Results. The mean flexural strength values for the ceramic-gold alloy combination (55 +/- 7.2MPa) were significantly higher than those of the ceramic-Ti cp combination (32 +/- 6.7 MPa) regardless of the fatigue conditions performed (p < 0.05). Mechanical and thermo-mechanical fatigue decreased the flexural strength results significantly for both ceramic-gold alloy (52 +/- 6.6 and 53 +/- 5.6 MPa, respectively) and ceramic-Ti cp combinations (29 +/- 6.8 and 29 +/- 6.8 MPa, respectively) compared to the control group (58 +/- 7.8 and 39 SA MPa, for gold and Ti cp, respectively) (p < 0.05) (Tukey`s test). While ceramic-Ti cp combinations failed adhesively at the metal-opaque interface, gold alloy frameworks exhibited a residue of ceramic material on the surface in all experimental groups. Significance. Mechanical and thermo-mechanical fatigue conditions decreased the flexural strength values for both ceramic-gold alloy and ceramic-Ti cp combinations with the results being significantly lower for the latter in all experimental conditions. (C) 2007 Academy of Dental Materials. Published by Elsevier Ltd. All rights reserved.

Synthesis, spectroscopic characterization, DFT studies and biological assays of a novel gold(I) complex with 2-mercaptothiazoline

A new gold(I) complex with 2-mercaptothiazoline (MTZ) with the coordination formula [AuCN(C(3)H(5)NS(2))] was synthesized and characterized by chemical and spectroscopic measurements, OFT studies and biological assays. Infrared (IR) and (1)H, (13)C and (15)N nuclear magnetic resonance (NMR) spectroscopic measurements indicate coordination of the ligand to gold(I) through the nitrogen atom. Studies based on OFT confirmed nitrogen coordination to gold(I) as a minimum of the potential energy surface with calculations of the hessians showing no imaginary frequencies. Thermal decomposition starts at temperatures near 160 degrees C, leading to the formation of Au as the final residue at 1000 degrees C. The gold(I) complex with 2-mercaptothiazoline (Au-MTZ) is soluble in dimethyl sulfoxide (DMSO), and is insoluble in water, methanol, ethanol, acetonitrile and hexane. The antibacterial activities of the Au-MTZ complex were evaluated by an antibiogram assay using the disc diffusion method. The compound showed an effective antibacterial activity against Staphylococcus aureus (Gram-positive) and Escherichia coli and Pseudomonas aeruginosa (Gram-negative) bacterial cells. Biological analysis for evaluation of the cytotoxic effect of the Au-MTZ complex was performed using HeLa cells derived from human cervical adenocarcinoma. The complex presented a potent cytotoxic activity, inducing 85% of cell death at a concentration of 2.0 mu mol L(-1). (C) 2011 Elsevier Ltd. All rights reserved.