Academic literature on the topic 'Oxide - Nitrogen'

Thesis (M.S.); Submitted to the University of California, Berkeley, 210 Hearst Mining Memorial Bldg., Berkeley, CA 94720 (US); 15 Dec 2003.<br>Published through the Information Bridge: DOE Scientific and Technical Information. "LBNL--54116" Li, Sonny X. USDOE Director. Office of Science. Basic Energy Sciences (US) 12/15/2003. Report is also available in paper and microfiche from NTIS.

Thesis (Ph. D.)--Massachusetts Institute of Technology, Dept. of Chemical Engineering, 2012.<br>This electronic version was submitted by the student author. The certified thesis is available in the Institute Archives and Special Collections.<br>Cataloged from student-submitted PDF version of thesis.<br>Includes bibliographical references (p. 345-363).<br>Elevated levels of nitric oxide (NO) in vivo are associated with a variety of cellular modifications thought to be mutagenic or carcinogenic. These processes are likely mediated by reactive nitrogen species (RNS) such as nitrogen dioxide (NO2) and peroxynitrite formed from the respective reactions of NO with oxygen and superoxide anion. Controlled delivery of these RNS at levels expected to occur in vivo is desirable in studying these processes and their role in the etiology of various diseases. Two delivery systems were developed that provide novel capabilities for steady, quantitative exposure of biological targets to RNS over periods from hours to days. Quantitative models are presented that accurately describe the behavior of both systems. The first system achieves NO concentrations of 0.6-3.0 [mu]M in a stirred, liquid-filled vessel by diffusion from a gas stream through a porous poly(tetrafluoroethylene) membrane. Oxygen, consumed by reaction with NO or by other processes, is supplied by diffusion from a separate gas stream through a loop of poly(dimethylsiloxane) tubing. The adventitious chemistry observed in a prior device for NO delivery [Wang C. Ann Biomed Eng (2003) 31:65-79] is eliminated in the present design, as evidenced by the close match to model predictions of the accumulation rate of nitrite, the stable end product of NO oxidation. The second system delivers NO2 by direct contacting of a stirred liquid with an NO2- containing gas mixture. Accumulation rates of products in the presence and absence of the NO2-reactive substrate 2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) matched model predictions within 15% for all conditions studied. The predicted steady NO2 concentration in the liquid is on the order of 400 pM, similar to what is expected to be present in extracellular fluids in the presence of 1 [mu]M NO. This system appears to be the first reported with the capability for sustained, quantitative NO2 delivery to suspended cell cultures. Results from initial efforts to test a novel mixing model for bolus delivery of peroxynitrite to agitated solutions imply that the proposed model might accurately describe mixing in bolus delivery experiments with agitation by vortex mixing, but further work is required to validate the model.<br>by Brian Thomas Skinn.<br>Ph.D.

Reburning is examined as a means of NOₓ destruction in a 17 kW down-fired pulverized coal combustor. In reburning, a secondary fuel is introduced downstream of the primary flame to produce a reducing zone, favorable to NO destruction, and air is introduced further downstream to complete the combustion. Emphasis is on natural gas reburning and a bituminous coal primary flame. A parametric examination of reburning employing a statistical experimental design, is conducted, complemented by detailed experiments. Mechanisms governing the inter-conversion of nitrogenous species in the fuel rich reburn zone are explored. The effect of reburning on N₂O emissions, the effect of primary flame mode (premixed and diffusion) and the effect of distributing the reburning fuel, are also investigated. The parametric study allowed the effects of significant reburning variables to be identified and examined, but these effects could not be quantified. Detailed experiments identified optimum reburn zone stoichiometry between 0.8 and 0.9, depending on mixing in the reburn zone. Overall NO reductions, as high as 80%, were possible and depended mainly on reburn zone variables, namely, temperature, residence time and stoichiometry. Exhaust N₂O emissions increased after air addition in the final stage of reburning, but were less than 10 ppm. Lower reductions in NO emissions were obtained when the primary flame was of the diffusion type, rather than of the premixed type, but final NO emissions below 250 ppm (dry, 0% O₂) were still possible. Reburning fuel introduction in multiple streams did not enhance NO destruction, relative to single stream injections. Within the reburn zone, reburning mechanisms occurred in two regimes. One regime was in the vicinity of the reburning fuel flame and was distinguished by fast reactions between NO and hydrocarbons that were limited by mixing. The other regime covered the remainder of the reburn zone and was distinguished by slower reactions, without mixing complications. For the latter regime, a simplified model based on detailed gas phase chemical kinetic mechanisms and known rate coefficients was able to predict temporal profiles of NO, HCN and NH₃. Reactions involving hydrocarbons played important roles in both regimes and N₂ fixation by hydrocarbons limited reburning effectiveness at low primary NO values. Appropriate corrections for mixing effects in early time scales of the reburn zone allowed the prediction of nitrogenous species profiles from primary NO values, as well as overall reburning effectiveness.

Nitric oxide (NO) has been shown to both suppress and promote tumor growth, depending in part on concentration. Exogenous delivery of NO may lead to tumor suppression. Recent studies have proposed ruthenium nitrosyl complexes as catalytic donors of NO in reductive environments. Catalytic donation can provide a long-term, elevated NO flux compared to single use donors. Site-specific delivery is desirable to reduce systemic side effects, such as lowering of blood pressure. Three new ruthenium nitrosyl complexes were synthesized to impart site-specificity through amide coupling to polymers, silica nanoparticles, iron oxide nanoparticles and antibodies. The catalytic activity of new and existing compounds was then assessed. However, upon one-electron reduction of ruthenium nitrosyl complexes, insignificant amounts of NO were detected, suggesting an alternative mechanism than that proposed in prior reports. The mechanism of [Ru(EDTA)NO]²⁻ decay was more thoroughly analyzed. Spectrophotometric decay of [Ru(EDTA)NO]²⁻ indicates that one or multiple nitrogen oxide species are released. Previous studies have suggested a disproportionation mechanism leading to the generation of more highly reduced species such as N₂ and NH₄⁺. Experiments were designed to analyze possible decomposition products such as [Ru(EDTA)NO]⁻ and [Ru(EDTA)H₂O]²⁻. A disproportionation mechanism was determined likely. Decomposition of [Ru(EDTA)NO]²⁻ was also observable following reductive nitrosylation of [Ru(EDTA)H₂O]⁻ in the presence of HNO. The decomposition product, [Ru(EDTA)H₂O]²⁻, was observed through the binding of pyrazine (pz) or dipyridine (bipy) and formation of [Ru(EDTA)pz]²⁻ or [Ru(EDTA)bipy]³⁻. Formation of [Ru(EDTA)bipy]³⁻ or [Ru(EDTA)pz]²⁻ via reductive nitrosylation of [Ru(EDTA)H₂O]⁻ also provides an indirect method of HNO detection that is selective from NO.