A Tumor-Targeting Dual-Modal imaging probe for nitroreductase in vivo.

Nitroreductase (NTR) overexpression often occurs in tumors, highlighting the significance of effective NTR detection. Despite the utilization of various optical methods for this purpose, the absence of an efficient tumor-targeting optical probe for NTR detection remains a challenge. In this research, a novel tumor-targeting probe (Cy-Bio-NO2) is developed to perform dual-modal NTR detection using near-infrared fluorescence and photoacoustic techniques. This probe exhibits exceptional sensitivity and selectivity to NTR. Upon the reaction with NTR, Cy-Bio-NO2 demonstrates a distinct fluorescence "off-on" response at 800 nm, with an impressive detection limit of 12 ng/mL. Furthermore, the probe shows on-off photoacoustic signal with NTR. Cy-Bio-NO2 has been successfully employed for dual-modal NTR detection in living cells, specifically targeting biotin receptor-positive cancer cells for imaging purposes. Notably, this probe effectively detects tumor hypoxia through dual-modal imaging in tumor-bearing mice. The strategy of biotin incorporation markedly enhances the probe's tumor-targeting capability, facilitating its engagement in dual-modal imaging at tumor sites. This imaging capacity holds substantial promise as an accurate tool for cancer diagnosis.

Significant HONO formation by the photolysis of nitrates in the presence of humic acids.

The generation of HONO and NO2 by the photolysis of nitrates in the presence of humic acids (HA) was measured under various conditions. The photolysis experiments of HA, KNO3 and KNO3/HA under simulated sunlight was carried out by a flow tube reactor at ambient temperature and pressure. HONO and NO2 were major products by the photolysis of KNO3. By contrast, the photolysis of HA and KNO3/HA mainly generated HONO. HA significantly enhanced the formation of HONO during the photolysis process of KNO3. With increasing the KNO3 mass, the HONO formation rate (RHONO) on KNO3/HA increased while the photolysis rate normalized by the KNO3 mass exhibited an opposite trend. RHONO on KNO3/HA linearly increased with irradiation intensity (88-262 W/m2) and relative humidity (7-70%), whereas it linearly decreased with the pH (pH = 2-12). In addition, the reaction paths of the HONO formation by the photolysis of nitrates in the presence of HA were proposed according to experimental results. Finally, atmospheric implications of the enhanced HONO formation by the photolysis of nitrates in the presence of HA were discussed.

Reactive Oxygen and Nitrogen Species at Phospholipid Bilayers: Peroxynitrous Acid and Its Homolysis Products.

Peroxynitrite is a powerful and long-lived oxidant generated in vivo. Peroxynitrous acid (ONOOH), its protonated form, may penetrate into phospholipid bilayers and undergo homolytic cleavage to nitrogen dioxide (·NO2) and hydroxyl radicals (·OH), causing severe nitro-oxidative damage. The membrane environment is thought to influence ONOOH reactions, but the mechanisms remain speculative. Most experimental techniques lack the level of resolution required to keep track of the motion of very reactive species and their interactions with the membrane. Here, we performed molecular dynamics simulations of the permeation, interactions, and dynamics of ONOOH and its homolysis products in the phospholipid membrane environment. We started by developing an ONOOH model that successfully accounted for its conformational equilibria and solvation energies. Membrane permeation of ONOOH was accompanied by conformational changes. ONOOH exhibited a strong tendency to bind to and accumulate at the membrane headgroup region. There, ONOOH homolysis led to ·NO2 radicals, which in turn partitioned to the membrane interior. About one-third of the ·OH radicals readily escaped to the aqueous phase within 1 ns. However, a significant number of ·OH radicals became trapped at the lipid headgroup region for a longer period. The possible implications for membrane-based nitration and oxidation processes were discussed.

A bridged di-iron porphyrin hyponitrite complex as a model for biological N2O production from hyponitrite.

Heme-hyponitrites are intermediates that form at the bimetallic active sites of bacterial nitric oxide reductases. To probe a possible effect of the Fe-Fe distance on hyponitrite stability, we prepared a bridged bis-porphyrin Fe-hyponitrite compound, namely [(OEP-CH2)Fe]2(µ2,η(1),η(1)-ONNO). Its υNO of 992 cm(-1) (υ15NO of 976 cm(-1)) is close to the υNO of 983 cm(-1) reported previously by us for the crystallographically characterized [(OEP)Fe]2(µ2,η(1),η(1)-ONNO) compound. The bridged bis-porphyrin Fe-hyponitrite complex is unstable with respect to N2O production, supporting the role of the bis-Fe porphyrin system in hyponitrite conversion to N2O. The preparation and crystallographic determination of the bridging sulfato derivative is also reported.

Photooxidation of ammonia on TiO2 as a source of NO and NO2 under atmospheric conditions.

Ammonia is the most abundant reduced nitrogen species in the atmosphere and an important precursor in the industrial-scale production of nitric acid. A coated-wall flow tube coupled to a chemiluminescence NOx analyzer was used to study the kinetics of NH3 uptake and NOx formation from photochemistry initiated on irradiated (λ > 290 nm) TiO2 surfaces under atmospherically relevant conditions. The speciation of NH3 on TiO2 surfaces in the presence of surface-adsorbed water was determined using diffuse reflection infrared Fourier transform spectroscopy. The uptake kinetics exhibit an inverse dependence on NH3 concentration as expected for reactions proceeding via a Langmuir-Hinshelwood mechanism. The mechanism of NOx formation is shown to be humidity dependent: Water-catalyzed reactions promote NOx formation up to a relative humidity of 50%. Less NOx is formed above 50%, where increasing amounts of adsorbed water may hinder access to reactive sites, promote formation of unreactive NH4(+), and reduce oxidant levels due to higher OH radical recombination rates. A theoretical study of the reaction between the NH2 photoproduct and O2 in the presence of H2O supports the experimental conclusion that NOx formation is catalyzed by water. Calculations at the MP2 and CCSD(T) level on the bare NH2 + O2 reaction and the reaction of NH2 + O2 in small water clusters were carried out. Solvation of NH2OO and NHOOH intermediates likely facilitates isomerization via proton transfer along water wires, such that the steps leading ultimately to NO are exothermic. These results show that photooxidation of low levels of NH3 on TiO2 surfaces represents a source of atmospheric NOx, which is a precursor to ozone. The proposed mechanism may be broadly applicable to dissociative chemisorption of NH3 on other metal oxide surfaces encountered in rural and urban environments and employed in pollution control applications (selective catalytic oxidation/reduction) and during some industrial processes.

A nitrogen dioxide delivery system for biological media.

Nitrogen dioxide is formed endogenously via the oxidation of NO by O(2) or O(2)(-) and from NO(2)(-) via peroxidases, among other pathways. This radical has many potential biological targets and its concentration, like that of NO and other reactive nitrogen species, is thought to be elevated at sites of inflammation. To investigate the specific cytotoxic or mutagenic effects of NO(2), it is desirable to be able to maintain its concentration at constant, predictable, and physiological levels in cell cultures, in the absence of NO. To do this, a delivery system was constructed in which NO(2)-containing gas mixtures contact a liquid within a small (110 ml) stirred reactor. In such gas mixtures NO(2) is present in equilibrium with its dimer, N(2)O(4). The uptake of NO(2) and N(2)O(4) was characterized by measuring the accumulation rates of NO(2)(-) and NO(3)(-), the stable products of N(2)O(4) hydrolysis, in buffered aqueous solutions. In some experiments NO(2)-reactive 2,2'-azino-bis(3-ethyl-benzothiazoline-6-sulfonate) (ABTS) was included and formation of the stable ABTS radical was measured. A reaction-diffusion model was developed that predicts the accumulation rates of all three products to within 15% for gas-phase concentrations of NO(2) spanning 3 orders of magnitude. The model also provides estimates for the NO(2) concentration in the liquid. This system should be useful for exposing cells to NO(2) concentrations similar to those in vivo.

Synthesis, spectroscopic characterization and biological activities of N4O2 Schiff base ligand and its metal complexes of Co(II), Ni(II), Cu(II) and Zn(II).

The Schiff base ligand, bis(indoline-2-one)triethylenetetramine (L) obtained from condensation of triethylenetetramine and isatin was used to synthesize the complexes of type, [ML]Cl(2) [M=Co(II), Ni(II), Cu(II) and Zn(II)]. L was characterized on the basis of the results of elemental analysis, FT-IR, (1)H and (13)C NMR, mass spectroscopic studies. The stoichiometry, bonding and stereochemistries of complexes were ascertained on the basis of results of elemental analysis, magnetic susceptibility values, molar conductance and various spectroscopic studies. EPR, UV-vis and magnetic moments revealed an octahedral geometry for complexes. L and its Cu(II) and Zn(II) complexes were screened for their antibacterial activity. Analgesic activity of Cu(II) and Zn(II) complexes was also tested in rats by tail flick method. Both complexes were found to possess good antibacterial and moderate analgesic activity.

Enhancement by anthraquinone-2-sulphonate of the photonitration of phenol by nitrite: implication for the photoproduction of nitrogen dioxide by coloured dissolved organic matter in surface waters.

Anthraquinone-2-sulphonate (AQ2S) under UVA irradiation is able to oxidise nitrite to (·)NO(2) and to induce the nitration of phenol. The process involves the very fast reactions of the excited triplet state (3)AQ2S(*) and its 520-nm absorbing exciplex with water, at different time scales (ns and µs, respectively). Quinones are ubiquitous components of coloured dissolved organic matter (CDOM) in surface waters and AQ2S was adopted here as a proxy of CDOM. Using a recently developed model of surface-water photochemistry, we found that the oxidation of nitrite to (·)NO(2) by (3)CDOM(*) could be an important (·)NO(2) source in water bodies with high [NO(2)(-)] to [NO(3)(-)] ratio, for elevated values of column depth and NPOC.

MnO(x)/TiO(2) composite nanoxides synthesized by deposition-precipitation method as a superior catalyst for NO oxidation.

A series of MnO(x)/TiO(2) composite nanoxides were prepared by deposition-precipitation (DP) method, and the sample with the Mn/Ti ratio of 0.3 showed a superior activity for NO catalytic oxidation to NO(2). The maximum NO conversion over MnO(x)(0.3)/TiO(2)(DP) could reach 89% at 250°C with a GHSV of 25,000h(-1), which was much higher than that over the catalyst prepared by conventional wet-impregnation (WI) method (69% at 330°C). Characterization results including XRD, HRTEM, FTIR, XPS, H(2)-TPR, NO-TPD and Nitrogen adsorption-desorption implied that the higher activity of MnO(x)(0.3)/TiO(2)(DP) could be attributed to the enrichment of well-dispersed MnO(x) on the surface and the abundance of Mn(3+) species. Furthermore, DRIFT investigations and long-time running test indicated that NO(2) came from the decomposition of adsorbed nitrogen-containing species.

Oxidation of NO with O2 on Pt(111) and Pt(321) large single crystals.

The kinetics of the oxidation of NO by O(2) was studied on 1 cm diameter single crystals, Pt(111) and Pt(321), at atmospheric pressure. The surface of the (321) crystal is composed of 20% kink, 20% step, and 60% terrace atoms and simulates small 1-3 nm size Pt particles on supported catalysts, while the (111) surface simulates the most stable plane found on large, >5 nm, particles. The turnover rates (TORs), that is, rate normalized by the exposed platinum, on the two single crystals differ by less than a factor of 2 over the range of conditions studied and are also similar to the TOR on a supported catalyst with an average particle size of 9 nm. Both surfaces show a dynamic kinetic behavior as evidenced by a change in the apparent activation energy and reaction orders as a function of reaction conditions. The oxygen coverage after initial rate experiments on Pt(111) was 0.6 monolayer (ML) on average which is similar to that measured previously by in situ X-ray photoelectron spectroscopy (XPS) under similar conditions. This oxygen overlayer, which is likely controlled by the relative presence of NO and NO(2), inhibits O(2) dissociation but lowers the binding energy of reactants enough to allow the catalysis. Long-term stability studies on Pt(111) correlate catalyst deactivation with irreversibly bound oxygen on the surface at coverages over 1 ML, as measured after reaction. Ex situ Auger electron spectroscopy (AES) and XPS results suggest that the surface defect sites on Pt(321) begin to oxidize relative to atoms on the (111) plane at lower NO(2) to NO ratios.

Metabolismos microbianos involucrados en procesos avanzados para la remoción de nitrógeno, una revisión prospectiva / Microbial metabolisms over advanced processes for nitrogen removal, a prospective review

Los procesos avanzados para la remoción de nitrógeno están íntimamente relacionados con los metabolismos de las comunidades microbianas que intervienen en las transformaciones del mismo. Para el diseño, la optimización o el mejoramiento de los sistemas de tratamiento de aguas residuales domésticas, el ingeniero y el microbiólogo en forma conjunta, han logrado configurar reactores terciarios adecuados para el desenvolvimiento de estas comunidades, obteniendo altas eficiencias de remoción de los nutrientes. Este artículo presenta una revisión sobre la actividad bacteriana y su aplicación en los sistemas de tratamiento, inicia conceptualizando la influencia de los microorganismos y de la actividad humana en el ciclo global del nitrógeno, para después hacer un análisis de los procesos particulares en los cuales los microorganismos intervienen. Se clasifican e incluyen nuevas evidencias de metabolismos relacionados, y se describen como ejemplos algunos de los procesos de tratamiento terciario para aguas residuales desarrollados con éxito en las últimas décadas.

Advanced processes for nitrogen removal are intimately related to the microbial community metabolisms that take part in the transformations. For the design, optimization or improvement of domestic waste water treatment systems, engineers and microbiologists working together, have managed to implemented suitable tertiary reactors for the development of these communities, improving the efficiency of nutrient removal. This article presents a revision of the bacterial activity and its application in treatment systems. The article begins by giving an explanation about the influence of microorganism and human activity on the global nitrogen cycle. Then, it analyzes the particular processes in which the microorganisms take part. New evidence of related metabolisms are classified and included. Some of the processes of wastewater tertiary treatment, successfully developed over the last decades, are described as examples.

Nitrogen dioxide formation in the gliding arc discharge-assisted decomposition of volatile organic compounds.

To apply gliding arc discharge (GAD) plasma processing to volatile organic compounds (VOCs) emission control, the formation of NO(2) as an undesired byproduct needs to be addressed. Comparative results of effluent temperature and product concentrations between experiment and thermodynamic equilibrium calculation show that the NO(2) formation in dry air GAD is totally out of thermodynamic equilibrium. Meanwhile, obvious NO (A(2)Sigma+)) and N(2)(+) (B(2)Sigma(u)(+)) are detected as the major reactive species in the dry air GAD plasma region. These results suggest that the thermal (or Zeldovich) NO(x) formation mechanism is not significant in GAD system, while the energy level and the density of electrons in the plasma region will severely influence the NO(2) formation. The presence of 500 ppm VOCs in the feed gases shows a limiting influence on the NO(2) formation, which is in the order of aromatic hydrocarbon (C(6)H(6) and C(7)H(8))>straight-chain hydrocarbon (C(4)H(10) and C(6)H(14))>halogenated hydrocarbon (CCl(4)). The influences of VOCs chemical structure, supply voltage, feed gas humidity, and reactor geometry on NO(2) formation are investigated, and the results correspond to above mechanism analysis. Based on the above, the possible pathways of the inhibition of NO(2) formation in GAD-assisted VOCs decomposition process are discussed.

Enhanced surface photochemistry in chloride-nitrate ion mixtures.

Heterogeneous reactions of sea salt aerosol with various oxides of nitrogen lead to replacement of chloride ion by nitrate ion. Studies of the photochemistry of a model system were carried out using deliquesced mixtures of NaCl and NaNO3 on a Teflon substrate. Varying molar ratios of NaCl to NaNO3 (1 : 9 Cl- : NO3-, 1 : 1 Cl- : NO3-, 3 : 1 Cl- : NO3-, 9 : 1 Cl- : NO3-) and NaNO3 at the same total concentration were irradiated in air at 299 +/- 3 K and at a relative humidity of 75 +/- 8% using broadband UVB light (270-380 nm). Gaseous NO2 production was measured as a function of time using a chemiluminescence NO(y) detector. Surprisingly, an enhanced yield of NO2 was observed as the chloride to nitrate ratio increased. Molecular dynamics (MD) simulations show that as the Cl- : NO3- ratio increases, the nitrate ions are drawn closer to the interface due to the existence of a double layer of interfacial Cl- and subsurface Na+. This leads to a decreased solvent cage effect when the nitrate ion photodissociates to NO2+O*-, increasing the effective quantum yield and hence the production of gaseous NO2. The implications of enhanced NO2 and likely OH production as sea salt aerosols become processed in the atmosphere are discussed.

Spin trapping of nitrogen dioxide and of radicals generated from nitrous acid.

Spin trapping of nitrogen dioxide radical by several nitrones has been studied. The reaction results in the formation of persistent acyl nitroxides, after the oxidation of the intermediate spin adducts having an -ONO group on C-2 atom. The intermediate is effectively detected when DEPMPO is used as the spin trap. The reaction between PBN or 5,7-di-tert-butyl-3,3-dimethyl indoline N-oxide with nitrous acid gives the corresponding acyl nitroxide only when oxygen is present in the reaction milieu. On the other hand, nitroso spin traps do not trap *NO2 confirming that the unpaired electron of nitrogen dioxide is localized on the oxygen atom.

Generation of nitrogen dioxide during nitric oxide therapy and mechanical ventilation of children with a Servo 900C ventilator.

OBJECTIVE: To determine the combinations of nitric oxide (NO), oxygen (O2), minute ventilation (MV) and total gas flow (TGF) which generate toxic concentrations of nitrogen dioxide (NO2) during mechanical ventilation with a Servo 900C ventilator. DESIGN: The measurement of NO2 generated with NO (20, 40, 60, 80, 100 ppm) and O2 [fractional inspired oxygen (FIO2) 0.21, 0.4, 0.6, 0.9] during mechanical ventilation with MVs of 2.5, 5.0 and 7.5 l/min and TGFs from 2 to 14 l/min. SETTING: Laboratory of intensive care unit in paediatric tertiary hospital. RESULTS: Toxic concentrations of NO2 (> 5 ppm) were generated in the ventilator circuit when NO was 80 ppm or 100 ppm in FIO2 of 0.6 or 0.9 with MVs of 2.5, 5.0 and 7.5 l/ min; and with 80 ppm NO in FIO2 of 0.6 at all TGFs from 2.0 to 13.6 l/min and MVs of 2.5, 5.0 and 7.5 l/min (TGF/MV 0.3-5.4). NO2 1.5-2.6 ppm was generated with 40 ppm NO in FIO2 of 0.6, TGFs 2.1-13.7 l/ min, and MVs 2.5, 5.0 and 7.5 l/min (TGF/MV 0.3-5.5). NO2 0.9-0.6 ppm was generated with 20 ppm NO in FIO2 of 0.6, TGFs 2.5-13.8 and MVs 2.5, 5.0 and 7.5 (TGF/MV 0.3-5.5). NO2 generation was not affected significantly by the TGF/MV ratio. CONCLUSIONS: The generation of NO2 in the ventilator circuit is directly proportional to concentration of NO and O2 and inversely proportional to the TGF and MV but uninfluenced by the TGF/MV ratio. NO 80 ppm, but neither 20 nor 40 ppm in FIO2 of 0.6, generates toxic NO2 irrespective of TGF, MV or the TGF/MV ratio.

[Nitric oxide delivery through ventilator and its toxic oxidative product nitrogen dioxide].

OBJECTIVE: To observe nitric oxide(NO) delivery through mechanically ventilator. NO is rapidly converted to nitrogen dioxide(NO2)in oxygen(O2) environments. METHODS: NO(800 ppm)was blended with compressed air, delivered to the high-pressure air inlet of a Siemens Servo 900C or VIP BIRD ventilator, and used to ventilator as a test lung. The ventilator settings were varied, minute ventilation (VE)from 2 to 6 L/min, inspired O2 fraction(FiO2)from 0.25 to 0.65, and NO concentration from 10 to 80 ppm. The inspiratory gas mixture was sampled just at the outlet port of ventilator. NO and NO2 were measured both by hemiluminescence and electro-chemical fuel cell technique. RESULTS: No NO was detected during any trial with VE 5 or 6 L/min., with FiO2 0.35 or 0.25, with NO 20 or 10 ppm. Low VE and low NO, NO2 values were greater with Servo 900C ventilator than with VIP BIRD ventilator at similar settings High VE and low NO or low VE and high NO, NO2 values were similar with both ventilators. High VE and high NO, NO2 values were greater with VIP BIRD ventilator than with Servo 900C ventilator. At same VE, NO2 values increased with increased FiO2 and NO. (NO2) = 0.0607 (NO)- 0.6604 VE + 7.004 FiO2, R2 = 0.7649 with Servo 900C ventilator,(NO2) = 0.0929(NO)- 0.1296 VE + 7.9360 FiO2, R2 = 0.8687 with VIP BIRD ventilator. CONCLUSIONS: NO(800 ppm) was blended with compressed air, delivered to the high-pressure air inlet of a Siemens Servo 900C or VIP BIRD ventilator is a portable, accurate, and adaptable system to deliver NO. During NO inhalation, VIP BIRD ventilator is more adaptable while low VE. Servo 900C ventilator is more adaptable while high VE.