Physicochemical Characterization and Oxidative Potential of Iron-Containing Particles Emitted from Xuanwei Coal Combustion.

Respiratory diseases have been proven to be directly related to air pollutants. Xuanwei, located in South China, has been known to have the highest mortality rate for lung cancer in China because of the air pollutants emitted through local coal combustion. However, the mechanism of lung cancer induced by air pollutants is not clear. Based on the fact that a large number of iron-bearing mineral particles was found in Xuanwei coal combustion particles, the iron-containing particles were hypothesized to play important roles in the pathogenesis of the high incidence rate of lung cancer in this area. In this study, raw coal samples were collected from a coal mine in the Xuanwei area. Size-resolved particles emitted from the raw coal samples were collected using an Anderson high-volume sampler. Mineralogical characterization and an assessment of the oxidative potential of the iron-containing particles were conducted using cutting-edge technologies, and the biological activity of the particles were evaluated via DTT assay. Our data showed that the iron-containing minerals accounted for more than 10% of the measured particles emitted from Xuanwei coal combustion samples. The content analysis of ·OH generated from Xuanwei coal combustion particles showed that ·OH content was dependent on the size of particles in the surrogated lung fluid. The concentration of ·OH increased as the particle size decreased. The DTT assay data further demonstrated that when the mass concentration of dissolved irons increased, the oxidation potential of the particles increased. The highest proportion of divalent iron in the total dissolved iron was found in the submicron particles in low pH solution(pH = 1), which indicated that the oxidative potential induced by submicron particles was stronger than that induced by coarse particles and fine particles. Armed with the above data, the toxicological mechanism of the iron-containing mineral particles can be investigated further.

Effects of Calcium Ions on the Antimicrobial Activity of Gramicidin A.

Gramicidin A (gA) is a linear antimicrobial peptide that can form a channel and specifically conduct monovalent cations such as H+ across the lipid membrane. The antimicrobial activity of gA is associated with the formation of hydroxyl free radicals and the imbalance of NADH metabolism, possibly a consequence caused by the conductance of cations. The ion conductivity of gramicidin A can be blocked by Ca2+ ions. However, the effect of Ca2+ ions on the antimicrobial activity of gA is unclear. To unveil the role of Ca2+ ions, we examined the effect of Ca2+ ions on the antimicrobial activity of gramicidin A against Staphylococcus aureus (S. aureus). Results showed that the antimicrobial mechanism of gA and antimicrobial activity by Ca2+ ions are concentration-dependent. At the low gA concentration (≤1 µM), the antimicrobial mechanism of gA is mainly associated with the hydroxyl free radical formation and NADH metabolic imbalance. Under this mode, Ca2+ ions can significantly inhibit the hydroxyl free radical formation and NADH metabolic imbalance. On the other hand, at high gA concentration (≥5 µM), gramicidin A acts more likely as a detergent. Gramicidin A not only causes an increase in hydroxyl free radical levels and NAD+/NADH ratios but also induces the destruction of the lipid membrane composition. At this condition, Ca2+ ions can no longer reduce the gA antimicrobial activity but rather enhance the bacterial killing ability of gramicidin A.

Incorporation of Oxidized Phenylalanine Derivatives into Insulin Signaling Relevant Proteins May Link Oxidative Stress to Signaling Conditions Underlying Chronic Insulin Resistance.

A link between oxidative stress and insulin resistance has been suggested. Hydroxyl free radicals are known to be able to convert phenylalanine (Phe) into the non-physiological tyrosine isoforms ortho- and meta-tyrosine (o-Tyr, m-Tyr). The aim of our study was to examine the role of o-Tyr and m-Tyr in the development of insulin resistance. We found that insulin-induced uptake of glucose was blunted in cultures of 3T3-L1 grown on media containing o- or m-Tyr. We show that these modified amino acids are incorporated into cellular proteins. We focused on insulin receptor substrate 1 (IRS-1), which plays a role in insulin signaling. The activating phosphorylation of IRS-1 was increased by insulin, the effect of which was abolished in cells grown in m-Tyr or o-Tyr media. We found that phosphorylation of m- or o-Tyr containing IRS-1 segments by insulin receptor (IR) kinase was greatly reduced, PTP-1B phosphatase was incapable of dephosphorylating phosphorylated m- or o-Tyr IRS-1 peptides, and the SH2 domains of phosphoinositide 3-kinase (PI3K) bound the o-Tyr IRS-1 peptides with greatly reduced affinity. According to our data, m- or o-Tyr incorporation into IRS-1 modifies its protein-protein interactions with regulating enzymes and effectors, thus IRS-1 eventually loses its capacity to play its role in insulin signaling, leading to insulin resistance.

NOx attenuation in flue gas by •OH/SO4•--based advanced oxidation processes.

The combustion of fossil fuels has resulted in rapidly increasing emissions of nitrogen oxide (NOx), which has caused serious human health and environmental problems. NO capture has become a research focus in gas purification because NO accounts for more than 90% of NOx and is difficult to remove. Advanced oxidation processes (AOPs), features the little secondary pollution and the broad-spectrum strong oxidation of hydroxyl radicals (•OH), are effective and promising strategies for NO removal from coal-fired flue gas. This review provides the state of the art of NO removal by AOPs, highlighting several methods for producing •OH and SO4•-. According to the main radicals responsible for NO removal, these processes are classified into two categories: hydroxyl radical-based AOPs (HR-AOPs) and sulfate radical-based AOPs (SR-AOPs). This paper also reviews the mechanisms of NO capture by reactive oxygen species (ROS) and SO4•- in various AOPs. A HiGee (high-gravity) enhanced AOP process for improving NO removal, characterized by intensified gas-liquid mass transfer and efficient micro-mixing, is then proposed and discussed in brief. We believe that this review will be useful for workers in this field. Graphical abstract.

Effect of crystalline structure on terbuthylazine degradation by H2O2-assisted TiO2 photocatalysis under visible irradiation.

Various methods for shifting the optical response of TiO2 into the visible (Vis) range have been reported. Herein, we reported the application of a TiO2/H2O2/Vis process and the effects of TiO2 crystalline structure on the degradation of terbuthylazine. The results indicated that TiO2 crystalline structure and H2O2 addition had significant effects on terbuthylazine degradation: its degradation rate could be increased from 7% to 70% with H2O2 addition after 180 min of reaction, the synergistic degradation of terbuthylazine by TiO2-Fe3+ was substantially accelerated, with the degradation rate reaching up to 100% after 20 min of reaction, and rutile TiO2 showed better photocatalytic activity and a more obvious synergistic effect than anatase TiO2. The addition of free-radical scavengers (tert-butyl alcohol or methanol) inhibited the degradation efficiency of rutile TiO2, but had a relatively minor effect on anatase TiO2. Fluorescence spectrophotometry analysis indicated that hydroxyl free radicals could be continuously produced when using rutile TiO2 as the photocatalyst. Degradation of terbuthylazine catalyzed by rutile TiO2 occurred mainly in solution, but occurred on the particle surface of the photocatalyst when catalyzed by anatase TiO2. This study provides new insight into the role of TiO2 crystalline structure on the degradation of terbuthylazine and its photocatalytic degradation mechanism.

Simultaneous removal of NO and SO2 using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS).

Simultaneous removal process of SO2 and NO from flue gas using vacuum ultraviolet light (VUV)/heat/peroxymonosulfate (PMS) in a VUV spraying reactor was proposed. The key influencing factors, active species, reaction products and mechanism of SO2 and NO simultaneous removal were investigated. The results show that vacuum ultraviolet light (185 nm) achieves the highest NO removal efficiency and yield of and under the same test conditions. NO removal is enhanced at higher PMS concentration, light intensity and oxygen concentration, and is inhibited at higher NO concentration, SO2 concentration and solution pH. Solution temperature has a double impact on NO removal. CO2 concentration has no obvious effect on NO removal. and produced from VUV-activation of PMS play a leading role in NO removal. O3 and ·O produced from VUV-activation of O2 also play an important role in NO removal. SO2 achieves complete removal under all experimental conditions due to its very high solubility in water and good reactivity. The highest simultaneous removal efficiency of SO2 and NO reaches 100% and 91.3%, respectively.

The mechanism for cleavage of three typical glucosidic bonds induced by hydroxyl free radical.

A novel mechanism for cleavage of three typical α(1→2), α(1→4) and ß(1→4) glucosidic bonds induced by hydroxyl free radical was examined with DFT theory at B3LYP/6-31+G(d,p) level using PCM water solvent model. It was found that the hydrogen abstraction from the CH bonds outside the saccharide rings could induce the hydrogen transfer from the hydroxyl at the radical carbon to the oxygen atom of saccharide ring with the mediation of water, which led to the opening of saccharide ring and the breakage of glucosidic bonds. Alternatively, the hydrogen in COH outside the saccharide ring of maltose and sucrose could also transfer to the adjacent glucosidic oxygen atom with a water molecule mediation to make glucosidic bond break directly. Based on this study, it can be well explained the experimental results that the oxidation of some oligosaccharides with hydroxyl free radicals can produce molecules of glucose, fructose and other monosaccharides.

Radical scavenging propensity of Cu2+, Fe3+ complexes of flavonoids and in-vivo radical scavenging by Fe3+-primuletin.

Cu2+ and Fe3+ complexes of three flavonoids (morin or mo, quercetin or quer and primuletin or prim) were synthesized with the objective of improving antioxidant capacities of flavonoids. The radical scavenging activities of pure flavonoids and their metal complexes were assayed to monitor their tendencies towards sequestering of radicals at physiological conditions. The scavenger potencies of metal-flavonoid complexes were significantly higher than those of the parent flavonoids. Further, influence of the solvent polarity on the radical capturing by flavonoids and their metal complexes was in favor for the polar solvent. Fe3+-prim displayed its radical scavenging ability via up gradation of CAT and SOD activities in in-vivo antioxidant assays.

MnO2/CeO2 for catalytic ultrasonic decolorization of methyl orange: Process parameters and mechanisms.

MnO2/CeO2 catalyst was prepared and characterized by means of Brunauer-Emmet-Teller (BET) method, X-ray diffraction (XRD) and scanning electron microscope (SEM). The characterization showed that MnO2/CeO2 had big specific surface area and MnO2 was dispersed homogeneously on the surface of CeO2. Excellent degradation efficiency of methyl orange was achieved by MnO2/CeO2 catalytic ultrasonic process. Operating parameters were studied and optimized. The optimal conditions were 10 min of ultrasonic irradiation, 1.0 g/L of catalyst dose, 2.6 of pH value and 1.3 W/ml of ultrasonic density. Under the optimal conditions, nearly 90% of methyl orange was removed. The mechanism of methyl orange degradation was further studied. The decolorization mechanism in the ultrasound-MnO2/CeO2 system was quite different with that in the ultrasound-MnO2 system. Effects of manganese and cerium in catalytic ultrasonic process were clarified. Manganese ions in solution contributed to generating hydroxyl free radical. MnO2/CeO2 catalyst strengthened the oxidation ability of ultrasound and realized complete decolorization of methyl orange.