Photocatalytic oxidation of nitric oxide with immobilized titanium dioxide films synthesized by hydrothermal method

Gas-phase photocatalytic oxidation (PCO) of nitric oxide (NO) with immobilized TiO2 films was studied in this paper. The immobilized TiO2 films were synthesized by hydrothermal method. The characterization for the physicochemical properties of catalysts prepared under different hydrothermal conditions were carried out by X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), high resolution-transmission electron microscopy (HR-TEM), Brunauer-Emmett-Teller measurements (BET) and scanning electron micrograph (SEM). It was found that the PCO efficiency of the catalyst was mainly depended on the hydrothermal conditions. The optimal values of hydrothermal temperature and hydrothermal time were 200 degrees C and 24 h, respectively. Furthermore, it was also known that the photocatalytic efficiency would decrease remarkably when the calcination temperature was over than 450 degrees C. Under the optimal conditions (hydrothermal condition: 200 degrees C for 24 h; calcination temperature: 450 degrees C), the photocatalytic efficiency of catalyst could reach 60% higher than that of Degussa P25.     

Detection of nitric oxide and nitrogen dioxide with photoluminescent porous silicon

The visible photoluminescence of porous Si is quenched by nitric oxide and nitrogen dioxide to detection limits of 1.4 × 10(-)(3) and 5.3 × 10(-)(5) Torr, respectively (corresponding to 2 ppm and 70 ppb). At analyte partial pressures in the low milliTorr range, the photoluminescence quenching is partially reversible; recovery from nitrogen oxide exposure occurs on a time scale of minutes. For both NO and NO(2), the reversible photoluminescence quenching response fits a Stern-Volmer kinetic model. At higher partial pressures, quenching deviates from Stern-Volmer kinetics and some permanent loss of photoluminescence intensity occurs due to oxidation of the porous Si surface. Photoluminescence from porous Si is not quenched by nitrous oxide or carbon dioxide and only slightly quenched by carbon monoxide and oxygen.     

Apatite deposition on polyamide films containing carboxyl group in a biomimetic solution

The development of organic–inorganic hybrids composed of hydroxyapatite and organic polymers is attractive because of their novelty in being materials that show a bone-bonding ability, i.e. bioactivity, and because they have mechanical properties similar to those of natural bone. The biomimetic process has received much attention for fabricating such a hybrid, where bone-like apatite is deposited under ambient conditions on polymer substrates in a simulated body fluid (SBF) having ion concentrations nearly equal to those of human extracellular fluid or related solutions. It has been shown that the carboxyl group is effective for inducing heterogeneous nucleation of apatite in the body. In the present study, apatite deposition on polyamide films containing various numbers of carboxyl groups was investigated in 1.5 SBF, which had ion concentrations 1.5 times those of a normal SBF. The effect of incorporation of calcium chloride on the formation of apatite was examined. Polyamide films containing 33 mol % CaCl₂ did not form apatite, even after soaking in 1.5 SBF for 7 days, and even when the polymer film contained 50 mol % carboxyl group. On the other hand, those modified with 40 mass % CaCl₂ formed apatite on their surfaces in 1.5 SBF. The ability of the modified film to form an apatite layer increased, and the adhesion of the apatite layer bonded to the film improved, with increasing carboxyl group content. It is concluded that novel apatite–polyamide hybrids can be prepared by a biomimetic process.     

Measurement of nitric oxide with an antimonide diode laser

An antimonide diode laser operating near 2.65 mum was used to measure absorption lines of NO gas in the first overtone band. A blended line pair of NO that is sufficiently free of interference from H(2) O to permit the selective detection of NO under reduced pressure conditions was identified. With wavelength-modulation spectroscopy, a rms noise level equivalent to an absorbance of 3.2 x 10(-5) was achieved at a measurement integration time (for a single spectral data point) of 0.1 s. The corresponding detection sensitivity (signal-to-noise ratio of 2) for NO in air at reduced pressure was ~15 ppm m (ppm is parts in 10(6)). Antimonide diode lasers show substantial promise for gas-sensing applications because they can gain access to relatively strong absorption lines of several gases of environmental interest at operating wavelengths at which cryogenic cooling is not required.     

Dosimetric and spectrometric neutron measurements around an annular vessel containing a plutonium nitrate fissile solution

The new ICPR60 recommendations and the consideration of the ALARA principle have led the operators of nuclear facilities to evaluate with a higher care, the doses received by workers. The aim of this paper is to present a recent study concerning mixed field characterisation at a workplace located in a reprocessing laboratory.As a first step, neutron spectrum determination was achieved by two ways: simulation using MCNP code and experimental measurements with Bonner spheres and recoil proton counters. Neutron spectrum allowed the evaluation of dosimetric quantities. Measurements were then performed with different devices routinely used in radioprotection. The authors describe the measurement techniques, present the results obtained, and finally compare and discuss them.     

Cyclic pressure test of a filament-wound vessel containing liquid nitrogen

This paper describes a test programme whereby a filament wound vessel was filled with liquid nitrogen and subjected to 2000 pressure cycles to 2068 N cm⁻² (3000 psi) without degradation of the structural capability of the vessel. This programme was initiated and organized by the Boulder Division of Beech Aircraft as a joint effort with the Brunswick Corporation which supplied the composite vessel and design expertise.     

Correlative analyses of nitric oxide generation rates and nitric oxide synthase levels in individual cells using a modular cell-retaining device

Nitric oxide (NO) is recognized as one of the major immune system agents involved in the pathogenesis and control of various diseases that may benefit from novel drug development, by exploiting NO signaling pathways and targets. This calls for detection of both intracellular levels of NO and expression of its synthesizing enzymes (NOS) in individual, intact, living cells. Such measurements are challenging, however, due to short half-life, low and fluctuating concentrations of NO, cellular heterogeneity, and inability to trace the same cells over time. The current study presents a device and methodology for correlative analysis of NO generation rates and NOS levels in the same individual cells, utilizing fluorescent imaging followed by immunohistochemistry (IHC). U937 promonocyte cell populations demonstrated significant heterogeneity in their baseline levels, in NO-generation kinetics, and in their response rates to stimuli. Individual cell analysis exposed cell subgroups which showed enhanced NO production upon stimulation, concomitantly with significant up-regulation of inducible NOS (iNOS) levels. Exogenous NO modulated the expression of iNOS in nondifferentiated cells within 1 h, in a dose-dependent manner, while treatment with lysophosphatidylcholine (LPC) enhanced the expression of iNOS, demonstrating a nondependence on NO production.     

Detection of nitric oxide release from single neurons in the pond snail, Lymnaea stagnalis

Multiple film-coated nitric oxide sensors have been fabricated using Nafion and electropolymerized polyeugenol or o-phenylenediamine on 30-microm carbon fiber disk electrodes. This is a rare study that utilizes disk electrodes rather than the widely used protruding tip microelectrodes in order to measure from a biological environment. These electrodes have been used to evaluate the differences in nitric oxide release between two different identified neurons in the pond snail, Lymnaea stagnalis. These results show the first direct measurements of nitric oxide release from individual neurons. The electrodes are very sensitive to nitric oxide with a detection limit of 2.8 nM and a sensitivity of 9.46 nA microM-1. The sensor was very selective against a variety of neurochemical interferences such as ascorbic acid, uric acid, and catecholamines and secondary oxidation products such as nitrite. Nitric oxide release was measured from the cell bodies of two neurons, the cerebral giant cell (CGC) and the B2 buccal motor neuron, in the intact but isolated CNS. A high-Ca2+/high-K+ stimulus was capable of evoking reproducible release. For a given stimulus, the B2 neuron released more nitric oxide than the CGC neuron; however, both cells were equally suppressed by the NOS inhibitor l-NAME.     

Two-photon nitric oxide laser-induced fluorescence measurements in a diesel engine

A two-photon nitric oxide (NO) laser-induced fluorescence (LIF) technique was developed and applied to study in-cylinder diesel combustion. The technique prevents many problems associated with in-cylinder, single-photon NO planar-laser-induced fluorescence measurements, including fluorescence interference from the Schumann-Runge bands of hot O2, absorption of a UV excitation beam by in-cylinder gases, and difficulty in rejecting scattered laser light while simultaneously attempting to maximize fluorescence signal collection. Verification that the signal resulted from NO was provided by tuning of the laser to a vibrational off-resonance wavelength that showed near-zero signal levels, which resulted from either fluorescence or interference at in-cylinder pressures of as much as 20 bar. The two-photon NO LIF signal showed good qualitative agreement with NO exhaust-gas measurements obtained over a wide range of engine loads.     

Combustion exhaust measurements of nitric oxide with an ultraviolet diode-laser-based absorption sensor

A diode-laser-based sensor has been developed for ultraviolet absorption measurements of the nitric oxide (NO) molecule. The sensor is based on the sum-frequency mixing (SFM) of the output of a tunable, 395-nm external-cavity diode laser and a 532-nm diode-pumped, frequency-doubled Nd:YAG laser in a beta-barium borate crystal. The SFM process generates 325 +/- 75 nW of ultraviolet radiation at 226.8 nm, corresponding to the (v' = 0, v" = 0) band of the A2Sigma+-chi2II electronic transition of NO. Results from initial laboratory experiments in a gas cell are briefly discussed, followed by results from field demonstrations of the sensor for measurements in the exhaust streams of a gas turbine engine and a well-stirred reactor. It is demonstrated that the sensor is capable of fully resolving the absorption spectrum and accurately measuring the NO concentration in actual combustion environments. Absorption is clearly visible in the gas turbine exhaust even for the lowest concentrations of 9 parts per million (ppm) for idle conditions and for a path length of 0.51 m. The sensitivity of the current system is estimated at 0.23%, which corresponds to a detection limit of 0.8 ppm in 1 m for 1000 K gas. The estimated uncertainty in the absolute concentrations that we obtained using the sensor is 10%.     

Direct detection of S-nitrosothiols using planar amperometric nitric oxide sensor modified with polymeric films containing catalytic copper species

The direct amperometric detection of S-nitrosothiol species (RSNOs) is realized by modifying a previously reported amperometric nitric oxide gas sensor with thin hydrophilic polyurethane films containing catalytic Cu(II)/(I) sites. Catalytic Cu(II)/(I)-mediated decomposition of S-nitrosothiols generates NO(g) in the thin polymeric film at the distal tip of the NO sensor. Three different species are examined to create the catalytic layer: (1) a lipophilic Cu(II)-ligand complex; (2) Cu(II)-phosphate salt; and (3) small (3-microm) metallic Cu(0) particles. All three catalytic layers yield reversible amperometric response in proportion to the concentration of S-nitrosothiols (e.g., nitrosocysteine, nitrosoglutathione, S-nitroso-N-acetylcysteine, S-nitrosoalbumin) present in the aqueous test solution. Sensitivity toward the different RSNO species is dependent on the respective catalytic rates of decomposition of the RSNO species by reactive Cu(I), accessibility of the species into the polyurethane layer containing the catalyst, the level of reducing agents (ascorbate) used in solution to help generate reactive Cu(I) species, and the concentration of metal ion complexing agents present in the test solution (e.g., EDTA). Under optimized conditions, all RSNO species can be detected at < or =1 microM levels, with sensor lifetimes of at least 10 days for the sensors based on Cu(II)-phosphate and Cu0 particles. It is further shown that the new RSNO sensors can be used to assess the "NO-generating" ability of fresh blood samples by effectively detecting the total level of reactive RSNO species present in such samples.     

Fracture phenomenology of a sintered silicon nitride containing oxide additives

Crack propagation mechanisms in a sintered silicon nitride containing various oxide additives (ceria, magnesia, zirconia and strontium oxide) were studied as a function of initial flaw size, temperature, applied stress and time. Surface cracks of controlled size were introduced using the microhardness indentation-induced-flaw technique. At 20° C, the fracture stress was found to depend on initial crack size according to the Griffith relationship and extrapolation of the data indicated that processing flaws of 20 to 35 were strength-controlling. The flexural strength was found to be independent of temperature from 20 to 800° C and the mode of crack propagation was primarily transgranular. At temperatures above 800° C the flexural strength decreased significantly, due to viscous flow of the glassy phase present in the material and resulting in sub-critical crack growth (SCG). The mode of crack propagation during SCG was essentially intergranular. Flexural stress-rupture evaluation in the temperature range 800 to 1000° C has identified the stress levels for time-dependent and time-independent failures.     

Oxidation of nitric oxide in a two-stage chemical scrubber using dc corona discharge

The dc corona was studied as an alternative for NO oxidation in a two-stage chemical scrubber. The dc corona plasma reactor completely oxidized 150 ppm of NO to NO₂ in an air stream. The NO₂ was further oxidized at a higher voltage. For some cases, the NO₂ in the effluents of the plasma reactor was absorbed quantitatively by a caustic sodium sulfite aqueous solution in a 2 l bubble column gas absorber. The outlet concentrations of both NO and NO₂ from the plasma-scrubber combination system (corona-induced chemical scrubber) were below the detection limit of the chemiluminescent NO_x analyzer.     

Reduction and functionalization of graphene oxide sheets using biomimetic dopamine derivatives in one step

An easy and environmentally friendly chemical method for the simultaneous reduction and noncovalent functionalization of graphene oxide (GO) using dopamine derivatives is described. The reaction takes place at room temperature under ultrasonication of an aqueous suspension of GO and a dopamine derivative. X-ray photoelectron spectroscopy, FT-IR spectroscopy, and cyclic voltammetry characterizations revealed that the resulting material consists of graphene functionalized with the dopamine derivative. This one-step protocol is applied for simultaneous reduction and functionalization of graphene oxide with a dopamine derivative bearing an azide function. The chemical reactivity of the azide function was demonstrated by a postfunctionalization with ethynylferrocene using the Cu(I) catalyzed 1,3-dipolar cyloaddition.     

Detection of toxic gases by a tin oxide multisensor

A tin oxide multisensor with eight sensor elements has been utilized to detect different gases that are emitted from the chemical industry. The different sensors have been prepared using the RF reactive sputtering technique. Some components of this multisensor were doped with Pt and Cr by sputtering. Each sensor has been characterized by electrical measurements for detection of atmospheric pollution (nitrogen dioxide, carbon monoxide, toluene, and propanal). The detected gases are toxic and their extreme concentrations recommended in air oscillate from 1 ppm to hundreds of ppm. Detections were carried out with a single gas or a gas mixture (two gases) in dry air at 250/spl deg/C. The sensitivity and selectivity to these gases were studied. Backpropagation neural networks and their classification results were discussed.     

Cavity ringdown spectroscopic detection of nitric oxide with a continuous-wave quantum-cascade laser

A spectroscopic gas sensor for nitric oxide (NO) detection based on a cavity ringdown technique was designed and evaluated. A cw quantum-cascade distributed-feedback laser operating at 5.2 mum was used as a tunable single-frequency light source. Both laser-frequency tuning and abrupt interruptions of the laser radiation were performed through manipulation of the laser current. A single ringdown event sensitivity to absorption of 2.2 x 10(-8) cm(-1) was achieved. Measurements of parts per billion (ppb) NO concentrations in N(2) with a 0.7-ppb standard error for a data collection time of 8 s have been performed. Future improvements are discussed that would allow quantification of NO in human breath.     

A study of the behaviour of a protected vessel containing LPG during pool fire engulfment

Theoretical and experimental investigations of various methods for protection against fires of vessels containing liquefied petroleum gases (LPG) (safety relief valves, intumescent fire retardant coatings, thermal isolation) have been carried out. A simple mathematical model has been proposed, which describes dependences of various parameters on time. These parameters are temperature, pressure and mass of LPG, temperatures of the vessel's walls and thermal protection layer. The case of total fire engulfment of the vessel with LPG was considered. Experiments have been executed, which were aimed on the investigation of the behaviour of vessels with LPG (50 l), equipped with protective devices during total fire engulfment. It was found out that the safety valve prevented an explosion of the vessels without any other protective measures. The presence of the intumescent fire retardant coating caused a significant delay in operation of the safety valve. A rather good agreement between the theoretical and experimental data was obtained. It has been revealed that the considered methods for protection of LPG vessels are promising in regard to prevention of explosions in these vessels at the fire engulfment.     

In vivo electrochemical detection of nitric oxide in tumor-bearing mice

Interest in elucidating the mechanisms of action of various classes of anticancer agents and exploring the pathways of the induced-nitric oxide (NO) release provides an impetus to conceive a better designed approach to locally detect NO in tumors, in vivo. We report here on the first use of an electrochemical sensor that allows the in vivo detection of NO in tumor-bearing mice. In a first step, we performed the electrochemical characterization of a stable electroactive probe, K4Fe(CN)6, directly injected into the liquid microenvironment especially created around the electrode in the tumor. Second, the ability of the inserted electrode system to detect the presence of NO itself in the tumoral tissue was achieved by using the chemically modified Pt/Ir electrode as NO sensor and two NO donor molecules: diethylammonium (Z)-1-(N,N-diethylamino)diazen-1-ium 1,2-diolate (DEA-NONOate) and (Z)-1-[N-(2-aminopropyl)-N-(2-ammonio propyl)amino]diazen-1-ium 1,2-diolate (PAPA-NONOate). These two NO donor molecules allowed proving the electrochemical detection of (i) directly injected exogenous NO phosphate buffer solution into the tumor (decomposed DEA-NONOate) and (ii) biomimetically induced endogeneous release of NO in the tumoral tissue, upon injection of PAPA-NONOate into the tumor. This approach could be applied to the in vivo study of candidate anticancer drugs acting on the NO pathways.