Redox regulation of protein damage in plasma

The presence and concentrations of modified proteins circulating in plasma depend on rates of protein synthesis, modification and clearance. In early studies, the proteins most frequently analysed for damage were those which were more abundant in plasma (e.g. albumin and immunoglobulins) which exist at up to 10 orders of magnitude higher concentrations than other plasma proteins e.g. cytokines. However, advances in analytical techniques using mass spectrometry and immuno-affinity purification methods, have facilitated analysis of less abundant, modified proteins and the nature of modifications at specific sites is now being characterised. The damaging reactive species that cause protein modifications in plasma principally arise from reactive oxygen species (ROS) produced by NADPH oxidases (NOX), nitric oxide synthases (NOS) and oxygenase activities; reactive nitrogen species (RNS) from myeloperoxidase (MPO) and NOS activities; and hypochlorous acid from MPO. Secondary damage to proteins may be caused by oxidized lipids and glucose autooxidation.In this review, we focus on redox regulatory control of those enzymes and processes which control protein maturation during synthesis, produce reactive species, repair and remove damaged plasma proteins. We have highlighted the potential for alterations in the extracellular redox compartment to regulate intracellular redox state and, conversely, for intracellular oxidative stress to alter the cellular secretome and composition of extracellular vesicles. Through secreted, redox-active regulatory molecules, changes in redox state may be transmitted to distant sites. © 2014 The Authors.

High rate growth of nanocrystalline diamond films using high microwave power and pure nitrogen/methane/hydrogen plasma

In this work, we investigate the impact of minute amounts of pure nitrogen addition into conventional methane/hydrogen mixtures on the growth characteristics of nanocrystalline diamond (NCD) films by microwave plasma assisted chemical vapour deposition (MPCVD), under high power conditions. The NCD films were produced from a gas mixture of 4% CH4/H2 with two different concentrations of N2 additive and microwave power ranging from 3.0 kW to 4.0 kW, while keeping all the other operating parameters constant. The morphology, grain size, microstructure and texture of the resulting NCD films were characterized by using scanning electron microscope (SEM), micro-Raman spectroscopy and X-ray diffraction (XRD) techniques. N2 addition was found to be the main parameter responsible for the formation and for the key change in the growth characteristics of NCD films under the employed conditions. Growth rates ranging from 5.4 μm/h up to 9.6 μm/h were achieved for the NCD films, much higher than those usually reported in the literature. The enhancing factor of nitrogen addition on NCD growth rate was obtained by comparing with the growth rate of large-grained microcrystalline diamond films grown without nitrogen and discussed by comparing with that of single crystal diamond through theoretical work in the literature. This achievement on NCD growth rate makes the technology interesting for industrial applications where fast coating of large substrates is highly desirable.

Etching and microstructure of engineering ceramics

Engineering ceramics are often difficult to prepare metallographically because of their hardness, wear resistance and chemical inertness. Two silicon carbides, a silicon nitride and a sialon, are prepared and etched using several different techniques. The most efficient methods are identified. © 1995.

Pore confinement effects and stabilization of carbon nitride oligomers in macroporous silica for photocatalytic hydrogen production

An ordered macroporous host (mac-SiO2) has been used to prevent aggregation of layered photocatalysts based on carbon nitride. Using typical carbon nitride synthesis conditions, cyanamide was condensed at 550 °C in the presence and absence of mac-SiO2. Condensation in the absence of mac-SiO2 results in materials with structural characteristics consistent with the carbon nitride, melon, accompanied by ca. 2 wt% carbonization. For mac-SiO2 supported materials, condensation occurs with greater carbonization (ca. 6 wt%). On addition of 3 wt% Pt cocatalyst photocatalytic hydrogen production under visible light is found to be up to 10 times greater for the supported composites. Time-resolved photoluminescence spectroscopy shows that excited state relaxation is more rapid for the mac-SiO2 supported materials suggesting faster electron-hole recombination and that supported carbon nitride does not exhibit improved charge separation. CO2 temperature programmed desorption indicates that enhanced photoactivity of supported carbon nitride is attributable to an increased surface area compared to bulk carbon nitride and an increase in the concentration of weakly basic catalytic sites, consistent with carbon nitride oligomers.

Growth, Characterization, and Properties of Hybrid Graphene-Carbon Nanotube Films and Related Carbon Nanostructures

Graphene, first isolated in 2004 and the subject of the 2010 Nobel Prize in physics, has generated a tremendous amount of research interest in recent years due to its incredible mechanical and electrical properties. However, difficulties in large-scale production and low as-prepared surface area have hindered commercial applications. In this dissertation, a new material is described incorporating the superior electrical properties of graphene edge planes into the high surface area framework of carbon nanotube forests using a scalable and reproducible technology.

The objectives of this research were to investigate the growth parameters and mechanisms of a graphene-carbon nanotube hybrid nanomaterial termed “graphenated carbon nanotubes” (g-CNTs), examine the applicability of g-CNT materials for applications in electrochemical capacitors (supercapacitors) and cold-cathode field emission sources, and determine materials characteristics responsible for the superior performance of g-CNTs in these applications. The growth kinetics of multi-walled carbon nanotubes (MWNTs), grown by plasma-enhanced chemical vapor deposition (PECVD), was studied in order to understand the fundamental mechanisms governing the PECVD reaction process. Activation energies and diffusivities were determined for key reaction steps and a growth model was developed in response to these findings. Differences in the reaction kinetics between CNTs grown on single-crystal silicon and polysilicon were studied to aid in the incorporation of CNTs into microelectromechanical systems (MEMS) devices. To understand processing-property relationships for g-CNT materials, a Design of Experiments (DOE) analysis was performed for the purpose of determining the importance of various input parameters on the growth of g-CNTs, finding that varying temperature alone allows the resultant material to transition from CNTs to g-CNTs and finally carbon nanosheets (CNSs): vertically oriented sheets of few-layered graphene. In addition, a phenomenological model was developed for g-CNTs. By studying variations of graphene-CNT hybrid nanomaterials by Raman spectroscopy, a linear trend was discovered between their mean crystallite size and electrochemical capacitance. Finally, a new method for the calculation of nanomaterial surface area, more accurate than the standard BET technique, was created based on atomic layer deposition (ALD) of titanium oxide (TiO2).

Chemical approaches for doping nanodevice architectures

Advanced doping technologies are key for the continued scaling of semiconductor devices and the maintenance of device performance beyond the 14 nm technology node. Due to limitations of conventional ion-beam implantation with thin body and 3D device geometries, techniques which allow precise control over dopant diffusion and concentration, in addition to excellent conformality on 3D device surfaces, are required. Spin-on doping has shown promise as a conventional technique for doping new materials, particularly through application with other dopant methods, but may not be suitable for conformal doping of nanostructures. Additionally, residues remain after most spin-on-doping processes which are often difficult to remove. In-situ doping of nanostructures is especially common for bottom-up grown nanostructures but problems associated with concentration gradients and morphology changes are commonly experienced. Monolayer doping (MLD) has been shown to satisfy the requirements for extended defect-free, conformal and controllable doping on many materials ranging from traditional silicon and germanium devices to emerging replacement materials such as III-V compounds but challenges still remain, especially with regard to metrology and surface chemistry at such small feature sizes. This article summarises and critically assesses developments over the last number of years regarding the application of gas and solution phase techniques to dope silicon-, germanium- and III-V-based materials and nanostructures to obtain shallow diffusion depths coupled with high carrier concentrations and abrupt junctions.

Geochemistry of sediment samples from ODP Leg 135 holes

The results of inductively coupled argon plasma (ICAP) chemical analyses carried out on some 300 core samples from Ocean Drilling Program Sites 834, 835, 838, and 839 are presented. These sites were drilled during Leg 135 in the Lau Basin. The data are compared with total gamma (SGR) wireline logs at Sites 834 and 835. Pliocene (Piacenzian) nannofossil Zone CN12, which has been identified at Sites 834 and 835, is examined in detail using spectral analyses on core and wireline logs. The potassium and calcium concentrations from the core material were used to calculate an objective depth-to-geological time stretching function, which improved the stratigraphic correlation between sites. The integrated use of chemical analyses, wireline-log data and paleomagnetic results improved confidence in the correlations obtained. Although no significant sedimentation periodicities were obtained from the two sites, a common concentration of energy between 30 and 60 k.y. was recorded.

Spatial and temporal measurements using polyoxometalate, enzymatic and biofilm layers on a CMOS 0.35 μm 64 X 64-pixel I.S.F.E.T. array sensor

This thesis presents the achievements and scientific work conducted using a previously designed and fabricated 64 x 64-pixel ion camera with the use of a 0.35 μm CMOS technology. We used an array of Ion Sensitive Field Effect Transistors (ISFETs) to monitor and measure chemical and biochemical reactions in real time. The area of our observation was a 4.2 x 4.3 mm silicon chip while the actual ISFET array covered an area of 715.8 x 715.8 μm consisting of 4096 ISFET pixels in total with a 1 μm separation space among them. The ion sensitive layer, the locus where all reactions took place was a silicon nitride layer, the final top layer of the austriamicrosystems 0.35 μm CMOS technology used. Our final measurements presented an average sensitivity of 30 mV/pH. With the addition of extra layers we were able to monitor a 65 mV voltage difference during our experiments with glucose and hexokinase, whereas a difference of 85 mV was detected for a similar glucose reaction mentioned in literature, and a 55 mV voltage difference while performing photosynthesis experiments with a biofilm made from cyanobacteria, whereas a voltage difference of 33.7 mV was detected as presented in literature for a similar cyanobacterial species using voltamemtric methods for detection. To monitor our experiments PXIe-6358 measurement cards were used and measurements were controlled by LabVIEW software. The chip was packaged and encapsulated using a PGA-100 chip carrier and a two-component commercial epoxy. Printed circuit board (PCB) has also been previously designed to provide interface between the chip and the measurement cards.

Analysis methods for meso- and macroporous silicon etching baths

Analysis methods for electrochemical etching baths consisting of various concentrations of hydrofluoric acid (HF) and an additional organic surface wetting agent are presented. These electrolytes are used for the formation of meso- and macroporous silicon. Monitoring the etching bath composition requires at least one method each for the determination of the HF concentration and the organic content of the bath. However, it is a precondition that the analysis equipment withstands the aggressive HF. Titration and a fluoride ion-selective electrode are used for the determination of the HF and a cuvette test method for the analysis of the organic content, respectively. The most suitable analysis method is identified depending on the components in the electrolyte with the focus on capability of resistance against the aggressive HF.

Estudo da sinterabilidade de ligas de níquel obtidas por meio dos portadores de liga sic, si3n4 ou si metálico com grafita

Nickel alloys are frequently used in applications that require resistance at high temperatures associated with resistance to corrosion. Alloys of Ni-Si-C can be obtained by means of powder metallurgy in which powder mixtures are made of metallic nickel powders with additions of various alloying carriers for such were used in this study SiC, Si3N4 or Si metal with graphite. Carbonyl Ni powder with mean particle size of 11 mM were mixed with 3 wt% of SiC powders with an average particle size of 15, 30 and 50 μm and further samples were obtained containing 4 to 5% by mass of SiC with average particle size of 15 μm. Samples were also obtained by varying the carrier alloy, these being Si3N4 powder with graphite, with average particle size of 1.5 and 5 μm, respectively. As a metallic Si graphite with average particle size of 12.5 and 5 μm, respectively. The reference material used was nickel carbonyl sintered without adding carriers. Microstructural characterization of the alloys was made by optical microscopy and scanning electron microscopy with semi-quantitative chemical analysis. We determined the densities of the samples and measurement of microhardness. We studied the dissociation of carriers alloy after sintering at 1200 ° C for 60 minutes. Was evaluated also in the same sintering conditions, the influence of the variation of average particle size of the SiC carrier to the proportion of 3% by mass. Finally, we studied the influence of variation of the temperatures of sintering at 950, 1080 and 1200 ° C without landing and also with heights of 30, 60, 120 and 240 minutes for sintering where the temperature was 950 °C. Dilatometry curves showed that the SiC sintered Ni favors more effectively than other carriers alloy analyzed. SiC with average particle size of 15 μm active sintering the alloy more effectively than other SiC used. However, with the chemical and morphological analyzes for all leagues, it was observed that there was dissociation of SiC and Si3N4, as well as diffusion of Si in Ni matrix and carbon cluster and dispersed in the matrix, which also occurred for the alloys with Si carriers and metallic graphite. So the league that was presented better results containing Si Ni with graphite metallic alloy as carriers, since this had dispersed graphite best in the league, reaching the microstructural model proposed, which is necessary for material characteristic of solid lubricant, so how we got the best results when the density and hardness of the alloy

UV and visible photoconductivity of undoped diamond films: morphology and related electrical transport phenomena

UV and visible photoconductivity and electrical features of undoped diamond thin films grown by microwave plasma-assisted chemical vapour deposition (MP-CVD) on silicon and copper substrates are studied. The results are correlated with morphology properties analysed by atomic force microscopy (AFM) and micro-Raman. The photoconductivity presents several bands from 1.8 to 3.8 eV that are dependent on the substrate used to grow the samples in spite of some common bands observed. The J-V curve tin DC) in samples grown on Si has a rectifier behaviour (Schottky emission) in opposition to the samples grown on Cu that have no rectification (SCLC conduction). With these results we can conclude that diamond based optoelectronic devices behaviour is controlled by two kinds of structural defects localized in microcrystal and in its boundaries. A general structure model for the optoelectronic behaviour is discussed. (C) 2000 Elsevier Science S.A. All rights reserved.

Estudo da molhabilidade de ligas de adição à base de prata sobre insertos cerâmicos para aplicação em brocas perfuração de poços de petróleo

Metal-ceramic interfaces are present in tricone drill bits with hard ceramic inserts for oil well drilling operations. The combination of actions of cutting, crushing and breaking up of rocks results in the degradation of tricone drill bits by wear, total or partial rupture of the drill bit body or the ceramic inserts, thermal shock and corrosion. Also the improper pressfitting of the ceramic inserts on the bit body may cause its total detachment, and promote serious damages to the drill bit. The improvement on the production process of metal-ceramic interfaces can eliminate or minimize some of above-mentioned failures presented in tricone drill bits, optimizing their lifetime and so reducing drilling metric cost. Brazing is a widely established technique to join metal-ceramic materials, and may be an excellent alternative to the common mechanical press fitting process of hard ceramic inserts on the steel bit body for tricone drill bit. Wetting phenomena plays an essential role in the production of metal/ceramic interfaces when a liquid phase is present in the process. In this work, 72Silver-28Copper eutectic based brazing alloys were melted onto zirconia, silicon nitride and tungsten carbide/Co substrates under high vacuum. Contact angle evolution was measured and graphically plotted, and the interfaces produced were analysed by SEM-EDX. The AgCu eutectic alloy did not wet any ceramic substrates, showing high contact angles, and so without chemical interaction between the materials. Better results were found for the systemns containing 3%wt of titanium in the AgCu alloy. The presence os titanium as a solute in the alloy produces wettable cand termodinamically stable compounds, increasing the ceramics wetting beahviour