Preparation of PrFe_(x)Co_(1-x)O_(3)/Mt catalyst and study on degradation of 2-hydroxybenzoic acid wastewater by catalytic wet peroxide oxidation

In this study,the perovskite nanocomposite PrFe_(x)Co_(1-x)O_(3)(Pr(S))was successfully synthesized by the sol-gel method;PrFe_(x)Co_(1-x)O_(3)/Al-pillared montmorillonite(Pr(S)/Mt)catalysts were prepared by impregnation(D)method and solid-melting(G)method,respectively,with Pr(S)as the active component and Al-pillared montmorillonite as the carrier.The catalysts were applied to treat the 2-hydroxybenzoic acid(2-HA)-simulated wastewater by catalytic wet peroxide oxidation(CWPO)technique,and the chemical oxygen demand(COD)removal rate and the 2-HA degradation rate were used as indicators to evaluate the catalytic performance.The results of the experiment indicated that the solid-melting method was more conducive to preparing the catalyst when the Co/Fe molar ratio of 7:3 and the optimal structural properties of the catalysts were achieved.The influence of operating parameters,including reaction temperature,catalyst dosage,H_(2)O_(2)dosage,pH,and initial 2-HA concentration,were optimized for the degradation of 2-HA by CWPO.The results showed that 97.64%of 2-HA degradation and 75.23%of COD removal rate were achieved under more suitable experimental conditions.In addition,after the catalyst was used five times,the degradation rate of 2-HA could still reach 76.93%,which implied the high stability and reusability of the catalyst.The high catalytic activity of the catalyst was due to the doping of Co into PrFeO_(3),which could promote the generation of HO·,and the high stability could be attributed to the loading of Pr(S)onto Al-Mt,which reduced the leaching of reactive metals.The study of reaction mechanism and kinetics showed that the whole degradation process conformed to the pseudo-firstorder kinetic equation,and the Langmuir-Hinshelwood method was applied to demonstrate that catalysis was dominant in the degradation process.

Sulfonated carbon catalyzed oxidation of aldehydes to carboxylic acids by hydrogen peroxide

Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.

Degradation of 2,4-dichlorophenoxyacetic acid in water by ozonehydrogen peroxide process

This study reports an investigation into the degradation of 2,4-dichlorophenoxyacetic acid in bubble contactor column by O2/H2O2 process, which is widely used as a principal advanced oxidation process. The degradation of 2,4-dichlorophenoxyacetic acid was studied under different H202/O3 molar ratio and pH value. Meanwhile, TOC removal was investigated both in distilled water and tap water. The influences of ozone transfer and consumed hydrogen peroxide were also discussed. The degradation products and oxidation intermediates were identified by GC-MS and LC-MS. A possible reaction mechanism was thus proposed.

Oxidative Desulfurization of Non-hydrotreated Kerosene Using Hydrogen Peroxide and Acetic Acid

The oxidative desulfurization of a real refinery feedstock (i.e.,non-hydrotreated kerosene with total sulfur mass content of 0.16%) with a mixture of hydrogen peroxide and acetic acid was studied.The influences of various operating parameters including reaction temperature (T),acid to sulfur molar ratio (nacid/nS),and oxidant to sulfur molar ratio (nO/nS) on the sulfur removal of kerosene were investigated.The results revealed that an increase in the reaction temperature (T) and nacid/nS enhances the sulfur removal.Moreover,there is an optimum nO/nS related to the reaction temperature and the best sulfur removal could be obtained at nO/nS=8 and 23 for the reaction temperatures of 25 and 60°C,respectively.The maximum observed sulfur removal in the present oxidative desulfurization system was 83.3%.

Endogenous nitric oxide and hydrogen peroxide detection in indole-3-butyric acid-induced adventitious root formation in Camellia sinensis

Nitric oxide（NO）and hydrogen peroxide（H2O2）are essential signaling molecules with key roles in auxin induced adventitious root formation in many plants.However,whether they are the sole determinants for adventitious root formation is worth further study.In this study,endogenous NO and H2O2 were monitored in tea cutting with or without indole-3-butyric acid（IBA）treatment by using the fluorescent probes diaminofluorescein diacetate（DAF-2DA）and 2＇,7＇-dichlorodihydrofluorescein diacetate（DCF-DA）,respectively.The overproduction of NO and H2O2 was detected in the rooting parts of tea cuttings treated with or without IBA.But little NO and H2O2 was detected before the initiation phase of tea cuttings even with IBA treatment indicating that they might be not directly induced by IBA.Further carbon and nitrogen analysis found that the overproduction of NO and H2O2 were coincident with the consumption of soluble sugars and the assimilation of nitrogen.These results suggest that rooting phases should be taken into consideration with the hypothesis that auxin induces adventitious root formation via NO-and H2O2-dependent pathways and sink establishment might be a prerequisite for NO and H2O2 mediated adventitious root formation.

A Study on Anti-oxidative Activity of Soybean Peptideswith Linoleic Acid Peroxidation Systems

Soybean bioactive peptides（SBPs） were prepared from the isolated soybean protein by proteolysis with an alkaline protease, alcalase, at 50℃ and pH = 8.0. The dependence of hydrolysis time on hydrolysis degree and molecular weight distribution were examined. The hydrolysate was fractionated on a Sephadex G-25 column and the anti-oxidative activities of the fractions were detected by the method of pyrogallol auto-oxidation. The average chain length of soybean peptides that have anti-oxidative activity was estimated to be about 7. The anti-oxidative properties of the soy- bean peptide were also studied by using linoleic acid peroxidation systems. The optimal condition of the peroxidation system was set up, Vc/Cu^2 ＋ as the inducer at pH = 7.4 and 25 ℃. In addition, soybean peptides show higher antioxidative activity compared with GSH.

Study on the Mechanisms for Baeyer-Villiger Oxidation of Cyclohexanone with Hydrogen Peroxide in Different Systems

The green and effective Baeyer-Villiger oxidation reaction of cyclohexanone for preparing ε-caprolactone is of particular importance in the synthesis of new polymer materials. We have discussed here several mechanism types of Baeyer-Villiger oxidation of cyclohexanone with H2O2 in different reaction systems. Five main types have been addressed, i. e.: (1) the non-catalyzed reaction type, where the C=O of ketones is activated by H+, which is electrolytically dissociated from H2O2 and H2O, to improve the capability of C=O group for accepting the electron pairs; (2) the thermally activated radical reaction type, where the Criegee intermediate is produced via two steps of radical reaction with ·OH attack, with much more hydroxyl radicals being excited in the presence of TS-1 zeolite; (3) the Brnsted acid catalysis reaction type, where both O-O moiety and C=O group could be activated by Brnsted acid; (4) the solid Lewis acid catalyzed C=O of the substrate activation reaction type through enhancing the donor-acceptor interaction between the antibonding π*C=O orbital of cyclohexanone and HOMO of Sn-containing zeolites; and (5) the solid Lewis acid catalyzed H2O2 to form Me-OOH oxidative species by converting the highest occupied molecular orbital (HOMO) of Ti-OOH into a singly occupied molecular orbital (SOMO), making the O-O group highly electrophilic to attack the C=O of cyclohexanone during the Baeyer-Villiger oxidation process. In the end, we have also compared the different mechanisms and put forward our opinions on the development direction of catalytic materials aiming at eco-friendly Baeyer-Villiger oxidation of cyclohexanone in the years to come.

Protection of Salvianolic Acid B for Human Endothelial Cells Against Hydrogen Peroxide-Induced Oxidative Damage

Salvianolic acid B(Sal B) is an active component of traditional Chinese medicine Salvia miltiorrhiza and is used to treat vascular diseases. To better understand its mechanism, the antioxidant capacities of Sal B was evaluated with human endothelial cells under oxidative stress. Human endothelial cells were pretreated with Sal B for 12 h followed by hydrogen peroxide for another 12 h. Production of reactive oxygen species (ROS), activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX), and concentration of glu-tathione were measured. Protective effect of Sal B on the endothelial cells from hydrogen peroxide-induced damage was observed, and ROS production in the cells was found significantly inhibited. Sal B remarkably enhanced the activities of antioxidant enzymes SOD, CAT and GPX. Furthermore, Sal B up-regulated the intracellular glu-tathione concentration. The results indicate that Sal B protected endothelial cells from oxidative stress by improving the redox status of the cells through enhancing the antioxidant enzyme activities and increasing the reductive glu-tathione concentration after the oxidative challenge.

Highly dispersed metal incorporated hexagonal mesoporous silicates for catalytic cyclohexanone oxidation to adipic acid

Adipic acid is a dicarboxylic acid of great industrial importance,mainly used in the production of nylon-6,6 and polyurethane.The use of nitric acid as an oxidant in the industrial production of adipic acid poses significant carbon footprint to the environment.Clean adipic acid synthesis methods using a heterogeneous catalyst with H2O2 as oxidant and water as solvent have potential advantages of low catalyst cost,easy synthesis and recovery,cleanness and environmental protection.In this work,hexagonal mesoporous silicate materials were synthesized by a sol–gel method and evaluated for cyclohexanol/cyclohexanone oxidation to adipic acid.The physical and chemical properties of Fe-HMS were characterized by XRD,HR-TEM,BET and UV–Vis.The experimental results showed that Fe-HMS materials show pore sizes ranging from 2–3 nm.W-and Mo-based polyoxometalates were also evaluated and compared to the Fe-based HMS catalysts.To improve the adipic acid yield,the influence of the transition metal as well as the effect of metal loading,reaction temperature and catalyst amount on the catalytic performances of Fe-HMS have been investigated in details.When Si/Fe atomic ratio=100,Fe-HMS catalyst shows the highest activity,with a cyclohexanone conversion of 92.3%and adipic acid selectivity of 29.4%.The reaction pathway of cyclohexanone oxidation was further proposed based on experimental data.

Preparation of Vitamin E Intermediate from an Inexpensive Substrate by Selective Oxidation of Pseudocumene in HCOOH–H_2O_2 System

In this paper, 2,3,5-trimethyl-1,4-benzoquinone(TMBQ) was synthesized through the direct oxidation of1,2,4-trimethylbenzene(pseudocumene, TMB) in the HCOOH–H_2O_2 system. The influence ofthree active species was studied, including performic acid(PFA) generated in formic acid, peracetic acid(PAA) generated in acetic acid, and trifluoroperacetic(TFPA) acid generated in trifluoroacetic acid. The effects ofsulfuric acid and sodium formate addition were investigated, the overoxidation ofTMB was discussed, and the main reason for the decreasing selectivity was revealed. The oxidation ofTMB can be controlled and improved through adjusting the reaction temperature, mole ratio ofoxidant to substrate, and reactant concentration. The TMBQ yield of28% was achieved with a TMB concentration of0.2 mol/L, H_2O_2/TMB mole ratio of6:1, and reaction temperature 37 °C. The selectivity of72% was obtained with a TMB concentration of0.2 mol/L, H_2O_2/TMB mole ratio of5:1, and reaction temperature of27 °C. The reaction mechanisms were proposed and discussed based on the gas chromatography–flame ionization detection(GC–FID) and gas chromatography–mass spectrometer(GC–MS) results.

Chlorogenic acid alleviates hypoxic-ischemic brain injury in neonatal mice

Recent studies have shown that chlorogenic acid(CGA),which is present in coffee,has protective effects on the nervous system.However,its role in neonatal hypoxic-ischemic brain injury remains unclear.In this study,we established a newborn mouse model of hypoxic-ischemic brain injury using a modified Rice-Vannucci method and performed intraperitoneal injection of CGA.We found that CGA intervention effectively reduced the volume of cerebral infarct,alleviated cerebral edema,restored brain tissue structure after injury,and promoted axon growth in injured brain tissue.Moreover,CGA pretreatment alleviated oxygen-glucose deprivation damage of primary neurons and promoted neuron survival.In addition,changes in ferroptosis-related proteins caused by hypoxic-ischemic brain injury were partially reversed by CGA.Furthermore,CGA intervention upregulated the expression of the key ferroptosis factor glutathione peroxidase 4 and its upstream glutamate/cystine antiporter related factors SLC7A11 and SLC3A2.In summary,our findings reveal that CGA alleviates hypoxic-ischemic brain injury in neonatal mice by reducing ferroptosis,providing new ideas for the treatment of neonatal hypoxic-ischemic brain injury.

五氟丙酰氟的制备及应用

综述了以六氟环氧丙烷及其低聚物、三氟甲基三氟乙烯基醚、全氟丙酸全氟丙酯及丙酸丙酯、丙酸酐为原料制备五氟丙酰氟的方法及其优缺点,概述了五氟丙酰氟下游含氟精细化学品的的应用前景,为五氟丙酰氟的制备及应用提供参考。

Antioxidative effect of folate-modified chitosan nanoparticles

Objective:To evaluate the potency of carboxymethyl chitosan-2,2' ethylenedioxy bisethylamine-folate(CMC-EDBE-FA) on tissue injury,antioxidant status and glutathione system in tissue mitochondria and serum against nicotine-induced oxidative stress in mice.Methods: CMC-EDBE-FA was prepared on basis of carboxymethyl chitosan tagged with folic acid by covalently linkage through 2,2' ethylenedioxy bis-ethylamine.Animals were divided into four groups,i.e.,control,nicotine(1 mg/kg bw/day),CMC-EDBE-FA(1 mg/kg bw/day) and nicotine(1 mg/kg bw/day) and CMC-EDBE-FA(1 mg/kg bw/day) for 7 days.Levels of lipid peroxidation, oxidized glutathione level,antioxidant enzyme status and DNA damage were observed and compared.Results:The significantly increase of lipid peroxidation,oxidized glutathione levels and DNA damage was observed in nicotine treated group as compared with control group;those were significantly reduced in CMC-EDBE-FA supplemented group.Moreover,significantly reduced antioxidant status in nicotine treated group was effectively ameliorated by the supplementation of CMC-EDBE-FA.Only CMC-EDBE-FA treated groups showed no significant change as compared with control group;rather than it repairs the tissue damage of nicotine treated group.Conclusions:These findings suggest that CMC-EDBE-FA is non-toxic and ameliorates nicotine-induced toxicity.

Biochemical changes in grape rootstocks resulted from humic acid treatments in relation to nematode infection

Objective:To investigate the effect of humic acid on nematode infected,resistant and susceptible grapes in relation to lipid peroxidation and antioxidant mechanisms on selected biochemical parameters known as proactive substances.Methods:The grape rootstocks,superior,superior/ freedom and freedom were reacted differently to Meloidogyne incognita and Rotylenchulus reniformis according to rootstock progenitor.Two weeks after inoculation,two commercial products of humic acid were applied at the rate of(2,4 mL or grams/plant) as soil drench.After 4 months,nematode soil populations were extracted and counted.A subsample of roots from each plant was stained and gall numbers,embedded stages per root were calculated,final population, nematode build up(Pf/Pi),average of eggs/eggmass were estimated.Subsamples of fresh root of each treatment were chemically analyzed.Results:Freedom reduced significantly the nematode criteria and build up.Humic acid granules appeared to be more suppressive to nematode build up on superior and the higher dose on superior/freedom than liquid treatments.On freedom,all treatments reduced significantly the nematode build up regardless to the material nature.The higher dose was more effective than the lower one.As a result of humic acid applications,the malondialdehyde(MDA) and H_2O_2 contents were significandy reduced after humic acid treatments while the antioxidant compounds glutathione(GSH),ascorbic acid(ASA) and total phenol contents were significandy increased when compared with check.Antioxidant defense enzymes ascorbate peroxidase(AFX),superoxide dismutase(SOD),catalase(CAT) and polyphenol oxidase(PPO) showed significant increase in their specific activities in treated plants compared with nematode treated check.Conclnsions:Humic acid treatments improve we yield of grape by increasing the contents of antioxidant compounds and the specific activities of antioxidant enzymes.

Enhanced degradation of trichloroethene by calcium peroxide activated with Fe（III） in the presence of citric acid

Trichloroethene （TCE） degradation by Fe（III）- activated calcium peroxide （CP） in the presence of citric acid （CA） in aqueous solution was investigated. The results demonstrated that the presence of CA enhanced TCE degradation significantly by increasing the concen- tration of soluble Fe（III） and promoting H202 generation. The generation of HO· and O2^-· in both the CP/Fe（III） and CP/Fe（III）/CA systems was confirmed with chemical probes. The results of radical scavenging tests showed that TCE degradation was due predominantly to direct oxidation by HO·, while O2^-· strengthened the generation of HO· by promoting Fe（III） transformation in the CP/Fe （III）/CA system. Acidic pH conditions were favorable for TCE degradation, and the TCE degradation rate decreased with increasing pH. The presence of Cl·-, HCO3·-, and humic acid （HA） inhibited TCE degradation to different extents for the CP/Fe（III）/CA system. Analysis of Cl·- production suggested that TCE degradation in the CP/Fe （III）/CA system occurred through a dechlorination process. In summary, this study provided detailed information for the application of CA-enhanced Fe（III）-activated calcium peroxide for treating TCE contaminated groundwater.

Low temperature catalytic conversion of methane to formic acid by simple vanadium compound with use of H_2O_2

Selective oxidation of methane with hydrogen peroxide was catalyzed by several simple vanadium compounds in CH3CN. The reaction could afford formic acid as the major product. Vanadyl oxysulfate （VOSO4） was found to be an efficient catalyst. Specifically, the selectivity to formic acid of 70% at a methane conversion of 6.5% could be achieved over the VOSO4 catalyst under the reaction conditions of methane pressure 3.0 MPa and temperature 333 K for 4 h. The UV-Vis spectroscopic measurements revealed that the formation of V5＋ species during the reaction might be vital for the methane activation. The reaction probably proceeded via radical mechanism.

A critical role of gastric mucosal ascorbic acid in the progression of acute gastric mucosal lesions induced by compound 48/80 in rats

AIM: To study the role of gastric mucosal ascorbic acid(AA) in the progression of acute gastric mucosal lesions induced by compound 48/80 (C48/80), a mast cell degranulator, in rats.METHODS: C48/80 (0.75 mg/kg) was intraperitoneally injected to fasted Wistar rats. Oral administration of AA (10, 50 or 100 mg/kg) was performed 0.5 h after C48/80treatment. Determinations for gastric mucosal lesion severity and blood flow, and assays for gastric mucosal total AA, reduced AA, oxidized AA, vitamin E, thiobarbituric acid reactive substances (TBARS), adherent mucus, nitrite/nitrate (NOx), non-protein SH (NPSH), and myeloperoxidase(MPO), and serum total AA, reduced AA, oxidized AA,and NOx were conducted 0.5 and 3 h after C48/80treatment.RESULTS: Gastric mucosal lesions occurred 0.5 h after C48/80 treatment and progressed at 3 h. Gastric mucosal blood flow decreased 0.5 h after C48/80 treatment but the decrease was recovered at 3 h. Gastric mucosal total AA, reduced AA, vitamin E, and adherent mucus concentrations decreased 3 h after C48/80 treatment.Gastric mucosal oxidized AA concentration remained unchanged after C48/80 treatment. Gastric mucosal NPSH concentration decreased 0.5 h after C48/80 treatment,but the decrease was recovered at 3 h. Gastric mucosal TBARS concentration and MPO activity increased 0.5 h after C48/80 treatment and further increased at 3 h.Serum total AA and reduced AA concentrations increased 0.5 h after C48/80 treatment and further increased at 3 h, while serum oxidized AA concentration increased at 0.5 h. Serum and gastric mucosal NOx concentrations increased 3 h after C48/80 treatment. AA administration to C48/80-treated rats at 0.5 h after the treatment prevented the gastric mucosal lesion progression and the changes in gastric mucosal total AA, reduced AA, vitamin E, adherent mucus, NOx, and TBARS concentrations and MPO activity and serum NOx concentration found at 3 h after the treatment dose-dependently. The AA administration to C48/80-treated rats caused further increases in serum total AA and reduced AA concentrations at 3 h after the treatment dose-dependently.CONCLUSION: Gastric mucosal AA plays a critical role in the progression of C48/80-induced acute gastric mucosal lesions in rats.

Protective effect of estradiol on hepatocytic oxidative damage

AIM: To examine the protective effect of estradiol on the cultured hepatocytes under oxidative stress.METHODS: Hepatocytes of rat were isolated by using perfusion method, and oxidative stress wes induced by a serum-free medium and FeNTA. MDA level was determined with TBA method. Cell damage was assessed by LDH assay. Apoptosis of hepatocytes was assessed with cytoflowmetric analysis. Expression of Bcl-xl in cultured hepatocytes was detected by Western blot.The radicalscavenging activity of estradiol was valued by its ability to scavenge the stable free radical of DDPH.RESULTS: Oxidative stress increased LDH (from 168 ± 25 x10-6 IU. cell 1 to 780 ± 62 x 10-6 IU. cell-1 ) and MDA(from 0.28 ±0.07 x 10-6 nmol. cell-1 to 1. 35 ± 0.12 × 10-6 nmol. cell-1 ) levelsin cultured hepatocyte, and estradiol inhibited both LDH andMDA production in a dose dependent manner. In thepresence of estradiol t0-6 mol. L-1, 107 mol. L-1 and 10-8 mol.L-1 ,the LDH levels are 410 ± 53 × 10-6 IU. cell-1 ( P ＜ 0.01 vsoxidative group), 530 ± 37 × 10-6 IU. cell-1 ( P ＜ 0. 01 vsoxidative group), 687 ± 42 x 10-6 IU. cell-1 ( P ＜ 0.05 vsoxidative group) respectively, and the MDA level are 0.71 ±0.12 x 10-6 nmol. cell-1 ( P ＜ 0.01 vs oxidative group), 0.97 ± 0.11 × 10-6 nmol. cell-1 ( P ＜ 0.01 vs oxidative group) and 1.27 ±0. 19 x 10-6 nmol. cell-1 respectively. Estradiol suppressedapoptosis of hepatocytes induced by oxidative stress,administration of estradiol (10-6 mol/ L)decreased theapoptotic rate of hepatocytes under oxidative stress from 18.6 ± 1.2% to 6.5 ± 2.5%, P ＜ 0.01. Bcl-xl expression wasrelated to the degree of liver cell damage due to oxidativestress, and estradiol showed a protective action.CONCLUSION: Estmdiol protects hepatocytes from oxidativedamage by means of its antioxidant activity.