Green Efficient One-Pot Synthesis and Separation of Nitrones in Water Assisted by a Self-Assembled Nanoreactor.

This article reports an alternative method for preparing nitrones using a tetrahedral capsule as a nanoreactor in water. Using the hydrophobic cavity of the capsule allowed us to reduce the reaction times and easily separate the nitrones from the reaction mixture, obtaining reaction yields equal or comparable to those obtained with the methods already reported. Furthermore, at the basis of this methodology, there is an eco-friendly approach carried out that can certainly be extended to other synthesis methods for the preparation of other substrates by exploiting various types of macrocyclic hosts, suitably designed and widely used in supramolecular chemistry.

A DFT study on the effect of oxygen vacancies and H2O in Mn-MOF-74 on SCR reactions.

As one of the main air pollutants, nitrogen oxides (NOx) have serious effects on human health and the environment. In our previous study, we found that Mn-MOF-74 shows excellent catalytic performance for the selective catalytic reduction (SCR) reaction with NH3 being the reductant (NH3-SCR) at low temperature. To obtain a further understanding of the NH3-SCR mechanism in Mn-MOF-74, in this paper, we investigated two important parts of the NH3-SCR process in Mn-MOF-74 using the density functional theory (DFT) method. On the one hand, the structural characteristics of two types of oxygen vacancies of Mn-MOF-74, namely carboxyl oxygen vacancies and hydroxyl oxygen vacancies, and their adsorption properties to reaction species were calculated. It was found that the oxygen vacancies not only activate the reaction species, but also promote the desorption of NO2 molecules from metal sites for the subsequent rapid SCR reactions. On the other hand, we studied the effect of H2O on the structural stability and catalytic performance of Mn-MOF-74. It was found that the interaction of Mn-O bonds was weakened by H2O. Therefore, the influence of H2O should be considered for the future design of MOF-based catalysts for the SCR process.

Dihydroxy-Substituted Coumarins as Fluorescent Probes for Nanomolar-Level Detection of the 4-Amino-TEMPO Spin Label.

This paper reports on dihydroxycoumarins as fluorescent probes suitable for the detection and determination of the nitroxide radical, namely 4-amino-TEMPO. Since 4-amino-TEMPO is used as a spin label for the detection of various radicals and damage caused by these species, its determination under physiological conditions might help us to understand the mechanism of the oxidative stress. Among different coumarins studied, only dihydroxy-substituted derivatives show high sensitivity, specificity, and selectivity for the nitroxide radical. In this assay, dihydroxy-substituted coumarins under the action of 4-amino-TEMPO show a very fast and significant increase in fluorescence intensity and lifetime. Among them 6,7-dihydroxycoumarin (esculetin) exhibits the strongest fluorescence enhancement (up to 40 times), with an estimated limit of detection equal to 16.7 nM-a significantly lower value when compared with UV-Vis or electron paramagnetic resonance (EPR) spectroscopy. The method is characterized by an easy procedure of sample preparation and very short time of analysis. The mechanism of the interaction between 6,7-dihydroxycoumarin and 4-amino-TEMPO has been examined with the use of a series of complementary techniques, such as steady-state and time-resolved fluorescence spectroscopy, UV-Vis spectroscopy, electron paramagnetic resonance spectroscopy, potentiometric titration, and high-performance liquid chromatography. It has been proven that the only route of the reaction in the system studied is a proton transfer from the molecule of esculetin to the amino group of the nitroxide. Biological studies performed on prostate cancer cells, breast cancer cells, and normal skin fibroblasts revealed significant anticancer properties of 6,7-dihydroxycoumarin, which caused a considerable decrease in the viability and number of cancer cells, and affected their morphology, contrary to normal fibroblasts. Furthermore, the experiment performed on prostate cancer cells showed that fluorescence emission of esculetin is closely related to intracellular pH-the higher pH, the higher observed fluorescence intensity (in accordance with a chemical experiment). On the other hand, the studies performed in different pH levels revealed that when pH of the solution increases, the observed fluorescence intensity enhancement under the action of 4-amino-TEMPO decreases (better sensing properties of esculetin towards the nitroxide in lower pH).

Photo-assisted SCR removal of NO by upconversion CeO2/Pr3+/attapulgite nanocatalyst.

The emission of nitrogen oxides has caused severe harm to the ecosystem; thus, the development of low-cost and high-efficiency denitrification catalysts and new methods are of great significance. In this work, a co-precipitation method was employed to prepare Pr-doped CeO2/attapulgite (CeO2/Pr3+/ATP) nanocomposites. X-ray diffraction (XRD), photoluminance spectroscopy (PL), ultraviolet-visible diffuse reflectance (UV-Vis), Fourier transform infrared (FT-IR), and high-resolution transmission electron microscopy (HRTEM) were utilized to characterize the products. Results showed that the CeO2/Pr3+ nanoparticles were uniformly coated on the surface of ATP and demonstrated outstanding upconversion effect which converted the visible light to ultraviolet light. The upconversion luminescence of CeO2/Pr3+/ATP was strongest when the molar doping amount of Pr was 1 mol%, and the photo-SCR denitrification achieved the highest of 90% conversion and 95% selectivity when the loading amount of CeO2/Pr3+ was 40 wt%. The ATP and CeO2/Pr3+ constructed an indirect Z-type heterojunction structure mediated by oxygen vacancy which benefited the separation of charge carriers and enhanced the reduction-oxidation potentials, both are responsible for the remarkable denitrification performance.

Advanced treatment technique for swine wastewater using two agents: Thermally polymerized amorphous silica and hydrated lime for color and phosphorus removal and sulfur for nitrogen removal.

The efficacy of advanced treatment of swine wastewater using thermally polymerized, modified amorphous silica and hydrated lime (M-CSH-lime) for color and phosphorus removal and sulfur for nitrogen removal was examined with a demonstration-scale treatment plant. The color removal rate was approximately 78% at M-CSH-lime addition rates of > 0.055 wt/v%. The PO43--P removal rate exceeded 99.9% with > 0.023 wt/v%. pH of the effluent from the M-CSH-lime reactor increased with the addition rate till a maximum value of 12.7, which was effective in disinfection. The recovered M-CSH-lime would be suitable as a phosphorus fertilizer because the total P2 O5 content was approximately 10%. The nitrogen oxide (NOx-N) removal rate by sulfur denitrification increased to approximately 80% when the NOx-N loading rate was around 0.1 kg-N/ton-S/day. It was suggested that the combination of the two processes would be effective in the advanced treatment of swine wastewater.

Removal kinetics for gaseous NO and SO2 by an aqueous NaClO2 solution mist in a wet electrostatic precipitator.

Removal kinetics for NO and SO2 by NaClO2 solution mist were investigated in a wet electrostatic precipitator. By varying the molar concentrations of NO, SO2, and NaClO2, the removal rates of NO and SO2 confirmed to range from 34.8 to 72.9 mmol/m3 s and 36.6 to 84.7 mmol/m3 s, respectively, at a fixed gas residence time of 0.25 s. The rate coefficients of NO and SO2 were calculated to be 0.679 (mmol/m3)-0.33 s-1 and 1.401 (mmol/m3)-0.1 s-1 based on the rates of the individual removal of NO and SO2. Simultaneous removal of NO and SO2 investigated after the evaluation of removal rates for their individual treatment was performed. At a short gas residence time, SO2 gas removed more quickly by a mist of NaClO2 solution than NO gas in simultaneous removal experiments. This is because SO2 gas, which has a relatively high solubility in solution, was absorbed more rapidly at the gas-liquid interface than NO gas. NO and SO2 gases were absorbed as nitrite [Formula: see text] and sulfite [Formula: see text] ions, respectively, by the NaClO2 solution mist at the gas-liquid interface. Then, [Formula: see text] and [Formula: see text] were oxidized to nitrate [Formula: see text] and sulfate [Formula: see text], respectively, by reactions with [Formula: see text], ClO2, HClO, and ClO in the liquid phase.

In vivo evaluation of different alterations of redox status by studying pharmacokinetics of nitroxides using magnetic resonance techniques.

Free radicals, particularly reactive oxygen species (ROS), are involved in various pathologies, injuries related to radiation, ischemia-reperfusion or ageing. Unfortunately, it is virtually impossible to directly detect free radicals in vivo, but the redox status of the whole organism or particular organ can be studied in vivo by using magnetic resonance techniques (EPR and MRI) and paramagnetic stable free radicals - nitroxides. Here we review results obtained in vivo following the pharmacokinetics of nitroxides on experimental animals (and a few in humans) under various conditions. The focus was on conditions where the redox status has been altered by induced diseases or harmful agents, clearly demonstrating that various EPR/MRI/nitroxide combinations can reliably detect metabolically induced changes in the redox status of organs. These findings can improve our understanding of oxidative stress and provide a basis for studying the effectiveness of interventions aimed to modulate oxidative stress. Also, we anticipate that the in vivo EPR/MRI approach in studying the redox status can play a vital role in the clinical management of various pathologies in the years to come providing the development of adequate equipment and probes.

Pathway of FeEDTA transformation and its impact on performance of NOx removal in a chemical absorption-biological reduction integrated process.

A novel chemical absorption-biological reduction (CABR) integrated process, employing ferrous ethylenediaminetetraacetate (Fe(II)EDTA) as a solvent, is deemed as a potential option for NOx removal from the flue gas. Previous work showed that the Fe(II)EDTA concentration was critical for the NOx removal in the CABR process. In this work, the pathway of FeEDTA (Fe(III)/Fe(II)-EDTA) transformation was investigated to assess its impact on the NOx removal in a biofilter. Experimental results revealed that the FeEDTA transformation involved iron precipitation and EDTA degradation. X-ray photoelectron spectroscopy analysis confirmed the iron was precipitated in the form of Fe(OH)3. The iron mass balance analysis showed 44.2% of the added iron was precipitated. The EDTA degradation facilitated the iron precipitation. Besides chemical oxidation, EDTA biodegradation occurred in the biofilter. The addition of extra EDTA helped recover the iron from the precipitation. The transformation of FeEDTA did not retard the NO removal. In addition, EDTA rather than the iron concentration determined the NO removal efficiency.

Nanomaterials to Combat NO(x) Pollution.

The presence of NO9x) gases (NO+NO2) in the atmosphere is a major concern of society because of their associated adverse and harmful effects. In order to remove the NO(x) gases from the air, photocatalysis arises as an innovative and promising technique. Through the use of photochemical oxidation processes the NO and NO2 gases are oxidised to NO3- form and thus removed from the air. In recent years new nanomaterials are being developed by researchers with the aim to enhance their photocatalytic activity to combat the NO(x) pollution. The main focus is devoted to preparing new TiO2 based compounds with the highest specific surface area (SSA), different morphology and chemical modifications. In order to increase the SSA, different substrates were used to disperse the TiO2 nanoparticles: organic and carbon fibres, mesoporous materials, clays composites and nanoporous microparticles. In the other hand, high photocatalytic performances were obtained with nanotubes, self-orderer nano-tubular films and nanoparticles with the lowest size. Conversely, when TiO2 is doped with ions the oxide exhibited a better photocatalytic performance under visible light, which is related to the creation of intermediate energy states between the conduction band and the valence band. Alternatively, visible light photocatalysts different from titanium oxide have been studied, which exhibit a good De-NO(x) efficiency working under λ > 400 nm visible light irradiation.

Evaluation of Residence Time on Nitrogen Oxides Removal in Non-Thermal Plasma Reactor.

Non-thermal plasma (NTP) has been introduced over the last few years as a promising after- treatment system for nitrogen oxides and particulate matter removal from diesel exhaust. NTP technology has not been commercialised as yet, due to its high rate of energy consumption. Therefore, it is important to seek out new methods to improve NTP performance. Residence time is a crucial parameter in engine exhaust emissions treatment. In this paper, different electrode shapes are analysed and the corresponding residence time and NOx removal efficiency are studied. An axisymmetric laminar model is used for obtaining residence time distribution numerically using FLUENT software. If the mean residence time in a NTP plasma reactor increases, there will be a corresponding increase in the reaction time and consequently the pollutant removal efficiency increases. Three different screw thread electrodes and a rod electrode are examined. The results show the advantage of screw thread electrodes in comparison with the rod electrode. Furthermore, between the screw thread electrodes, the electrode with the thread width of 1 mm has the highest NOx removal due to higher residence time and a greater number of micro-discharges. The results show that the residence time of the screw thread electrode with a thread width of 1 mm is 21% more than for the rod electrode.

Simultaneous removal of PCDD/Fs and NOx from the flue gas of a municipal solid waste incinerator with a pilot plant.

The pilot-scale plant on the simultaneous removal of PCDD/Fs and NOx from the flue gas of a municipal solid waste incinerator is presented. In order to research the influence of temperature on the catalytic decomposition of PCDD/Fs and the selective catalytic reduction of NOx, the experiments were performed at 220 °C, 260 °C, and 300 °C, and the congener profiles of PCDD/Fs for the samples collected at the inlet and outlet were illustrated. Noteworthy, the detailed congener distributions of PCDD/Fs in the gas-phase and particle-phase of the inlet and 300-outlet (decomposition temperature = 300 °C) samples are presented, and the removal efficiencies η(g-I-TEQ) and η(p-I-TEQ) reached to 94.94% and 99.67%, respectively. The effect of the SCR process on the removal of PCDD/Fs was also studied at a relatively low temperature of 220 °C. Additionally, the NOx emissions and the SCR efficiencies were investigated.

Adsorption of SOx and NOx in activated viscose fibers.

SOx and NOx are emissions resulting from combustion processes and are the main agents that contribute to the formation of acid rain, which causes harm to humans and the environment. Several techniques for removing these pollutants are applied in i.e. oil refineries, thermoelectric that use petroleum oils and vehicular pollution. Among these, highlight the adsorption of contaminants by the usage of activated carbon fibers and activated carbon, which are characterized by high surface area and uniform distribution of pores, providing appropriate conditions for application in processes of removing environmental contaminants. In the present work, activated viscose fibers (AVF) were prepared and applied in adsorption experiments of NO and SO2. The materials produced showed high values of surface area, with a predominance of micro pores with diameters in the range of 1.0 nm. The AVF had satisfactory performance in the removal of contaminants and are compatible with other synthetic fibers. Thus, the formation of active sites of carbon provides contaminants adsorption, demonstrating that carbon fibers cloth can be applied for the removal of pollutants.

Evaluation of an oil-producing green alga Chlorella sp. C2 for biological DeNOx of industrial flue gases.

NOx, a significant portion of fossil fuel flue gases, are among the most serious environmental issues in the world and must be removed in an additional costly gas treatment step. This study evaluated the growth of the green alga Chlorella sp. C2 under a nitrite-simulated NOx environment and the removal rates of actual flue gas fixed salts (FGFSs) from Sinopec's Shijiazhuang refinery along with lipid production. The results showed that nitrite levels lower than 176.5 mM had no significant adverse effects on the cell growth and photosynthesis of Chlorella sp. C2, demonstrating that this green alga could utilize nitrite and NOx as a nitrogen source. High concentrations of nitrite (88.25-176.5 mM) also resulted in the accumulation of neutral lipids. A 60% nitrite removal efficiency was obtained together with the production of 33% algae lipids when cultured with FGFS. Notably, the presence of nitrate in the FGFS medium significantly enhanced the nitrite removal capability, biomass and lipid production. Thus, this study may provide a new insight into the economically viable application of microalgae in the synergistic combination of biological DeNOx of industrial flue gases and biodiesel production.

Biological NOx removal by denitrification process in a jet-loop bioreactor: system performance and model development.

Nitrogen monoxide (NO) and nitrogen dioxide referred as NOx are one of the most important air pollutants in the atmosphere. Biological NOx removal technologies have been developing to reach a cost-effective control method for upcoming stringent NOx emission standards. The BioDeNOx system was seen as a promising biological NOx control technology which is composed of two reactors, one for absorbing of NO in an aqueous Fe(II)EDTA2- solution and the other for subsequent reduction to N2 gas in a biological reactor by the denitrification process. In this study, instead of two discrete reactors, only one jet-loop bioreactor (JLBR) was utilized as both absorption and denitrification unit and no chelate-forming chemicals were added. In other words, the advantage of better mass transfer conditions of jet bioreactor was used instead of Fe(II)EDTA2-. The process was named as Jet-BioDeNOx. The JLBR was operated for the removal of NOx from air streams containing 500-3000 ppm NOx and the results showed that the removal efficiency was between 81% and 94%. The air to liquid flow ratio (Q(G)/Q(RAS)) varied in the range of 0.07-0.12. Mathematical modelling of the system demonstrated that the removal efficiency strongly depends on this ratio. The high mass transfer conditions prevailed in the reactor provided a competitive advantage on removing NO gas without any requirement of chelating chemicals.

Preparation of Mn-based selective catalytic reduction catalysts by three methods and optimization of process conditions.

Mn-based catalysts enable high NO x conversion in the selective catalytic reduction of NO x with NH3. Three catalyst-production methods, namely, co-precipitation, impregnation, and sol-gel, were used in this study to determine the optimum method and parameters. The maximum catalytic activity was found for the catalyst prepared by sol-gel with a 0.5 Mn/Ti ratio. The denitrification efficiency using this catalyst was >90%, which was higher than those of catalysts prepared by the two other methods. The critical temperature of catalytic activity was 353 K. The optimum manganese acetate concentration and weathering time were 0.10 mol and 24 h, respectively. The gas hourly space velocity and O2 concentration were determined to be 12000 h(-1) and 3%, respectively.

Spray absorption and electrochemical reduction of nitrogen oxides from flue gas.

This work developed an electrochemical reduction system which can effectively scrub NO× from flue gas by using aqueous solution of Fe(II)(EDTA) (ethylenediaminetetraacetate) as absorbent and electrolyte. This new system features (a) complete decomposition of NOX to harmless N2; and (b) fast regeneration of Fe(II)(EDTA) through electrochemical reaction. The Fe(II)(EDTA) solution was recycled and reused continuously during entire process, and no harmful waste was generated. The reaction mechanism was thoroughly investigated by using voltammetric, chromatographic and spectroscopic approaches. The operating conditions of the system were optimized based on NOX removal efficiency. Approximately 98% NO removal was obtained at the optimal condition. The interference of SO2 in flue gas and the system operating stability was also evaluated.

Combination of photocatalysis and HC/SCR for improved activity and durability of DeNOx catalysts.

A photocatalytic HC/SCR system has been developed and its high deNOx performance (54.0-98.6% NOx conversion) at low temperatures (150-250 °C) demonstrated by using a representative diesel fuel hydrocarbon (dodecane) as the reductant over a hybrid SCR system of a photocatalytic reactor (PCR) and a dual-bed HC/SCR reactor. The PCR generates highly active oxidants such as O3 and NO2 from O2 and NO in the feed stream, followed by the subsequent formation of highly efficient reductants such as oxygenated hydrocarbon (OHC), NH3, and organo-nitrogen compounds. These reductants are the key components for enhancing the low temperature deNOx performance of the dual-bed HC/SCR system containing Ag/Al2O3 and CuCoY in the front and rear bed of the reactor, respectively. The OHCs are particularly effective for both NOx reduction and NH3 formation over the Ag/Al2O3 catalyst, while NH3 and organo-nitrogen compounds are effective for NOx reduction over the CuCoY catalyst. The hybrid HC/SCR system assisted by photocatalysis has shown an overall deNOx performance comparable to that of the NH3/SCR, demonstrating its potential as a promising alternative to the current urea/SCR and LNT technologies. Superior durability of HC/SCR catalysts against coking by HCs has also been demonstrated by a PCR-assisted regeneration scheme for deactivating catalysts.

[Effects of gaseous compositions the on simultaneous removal of NO(x) and SO2 from simulated flue gas by ammonia absorption].

The effects of NO(x) oxidation ratio, O2 and SO2 concentrations in simulated flue gas as well as addition of S(IV) oxidation inhibitor NaS2O3 on the simultaneous removal of SO2 and NO(x) by ammonia absorption were investigated under the conditions of pH 5.9-6.1 and aqueous S(IV) concentration > or = 1.0 mol x L(-1). The research results showed that NO2 could be effectively absorbed by ammonium sulfite, but the NO absorption was negligible. Therefore, NO oxidation is the premise of NO(x) removal. Aqueous S(IV) concentration is a key factor affecting NO2 absorption removal, the higher the O2 concentration or the lower the SO2 concentration, the faster the aaqueous S(IV) concentration decreased, which resulted in a faster decrease of NO2 removal efficiency. S(IV) oxidation was inhibited to some extent by the addition of oxidation inhibitor S2O3(2-) into the absorption solution. As a result, the decrease of NO2 removal efficiency became slower.

Reduction of Fe(III)EDTA by Klebsiella sp. strain FD-3 in NOx scrubber solutions.

Biological reduction of Fe(III) to Fe(II) is a key step in nitrogen oxides (NOx) removal by the integrated chemical absorption-biological reduction method, which determines the concentration of Fe(II) in the scrubbing liquid. A new Fe(III)EDTA reduction strain, named as FD-3, was isolated from mixed cultures used in the integrated NOx removal process and identified as Klebsiella sp. by 16S rDNA sequence analysis. The reduction abilities of FD-3 and the influence of nitrogen-containing compounds (Fe(II)EDTA-NO, NO3(-) and NO2(-)) and sulfur-containing compounds (SO4(2-), SO3(2-)) on the Fe(III)EDTA reduction were investigated. The results indicated that strain FD-3 could reduce Fe(III)EDTA efficiently. NO3(-), NO2(-) and Fe(II)EDTA-NO inhibit the reduction of Fe(III)EDTA and could also serve as electron acceptor for strain FD-3. SO3(2-) inhibited Fe(III)EDTA reduction while SO4(2-) had no obviously effect on Fe(III)EDTA reduction. The relationship between cell growth and Fe(III)EDTA reduction could be described by the models based on Logistic equation.