Free radicals trigger the closure of open pores in lignin-derived hard carbons toward improved sodium-storage capacity

The chemical activation of various precursors is effective for creating additional closed pores in hard carbons for sodium storage.However,the formation mechanism of closed pores under the influence of pore-forming agents is not well understood.Herein,an effective chemical activation followed by a high-temperature self-healing strategy is employed to generate interconnected closed pores in lignin-derived hard carbon(HCs).By systematic experimental design combined with electron paramagnetic res-onance spectroscopy,it can be found that the content of free radicals in the carbon matrix influences the closure of open pores at high temperatures.Excessively high activation temperature(>700 C)leads to a low free radical concentration,making it difficult to achieve self-healing of open pores at high tempera-tures.By activation at 700°C,a balance between pore making and self-healing is achieved in the final hard carbon.A large number of free radicals triggers rapid growth and aggregation of carbon microcrys-tals,blocking pre-formed open micropores and creating additional interconnected closed pores in as-obtained hard carbons.As a result,the optimized carbon anode(LK-700-1300)delivers a high reversible capacity of 330.8 mA h g^(-1) at 0.03 A g^(-1),which is an increase of 86 mA h g^(-1) compared to the pristine lignin-derived carbon anode(L-700-1300),and exhibits a good rate performance(202.1 mA h g^(-1) at 1 A g^(-1)).This work provides a universal and effective guidance for tuning closed pores of hard carbons from otherprecursors.

Decontamination of Cr(Ⅵ) from water using sewage sludge-derived biochar: Role of environmentally persistent free radicals

Biochar is a well-known material for pollutant removal owing to its low cost and rich surface functionality. A kind of highly active substance, called environmentally persistent free radicals(EPFRs), can be produced in the preparation process of biochar, playing an important role in the removal of pollutants.In this study, sludge-derived biochars(SBC_(120) and SBC_(270)) were prepared by the hydrothermal carbonization under two temperatures(120℃ and 270℃) to investigate their removal abilities of Cr(Ⅵ). The maximum removal amounts of Cr(Ⅵ) by SBC_(120) and SBC_(270) were 16.58 and 22.93 mg·g^(-1), respectively. It was further revealed that the appearance of Cr(Ⅲ), as a result of EPFRs on sludge-derived biochar(SBC) transferred electrons to Cr(Ⅵ) in neutral solutions. That is to say, oxygen-centered(O-centered) EPFRs on SBC_(120) and carbon-centered(C-centered) EPFRs on SBC_(270) all could be used as electron donors to Cr(Ⅵ) to make it become Cr(Ⅲ). This study not only provides a theoretical basis for the mechanism of pollutants removal by sludge-derived biochar but also offers a new perspective on the direct effect of EPFRs on pollutants.

Sustainable Generation of Sulfate Radicals and Decontamination of Micropollutants via Sequential Electrochemistry

The removal of emerging micropollutants in the aquatic environment remains a global challenge.Conventional routes are often chemically,energetically,and operationally intensive,which decreases their sustainability during applications.Herein,we develop an advanced chemical-free strategy for micropollutants decontamination that is solely based on sequential electrochemistry involving ubiquitous sulfate anions in natural and engineered waters.This can be achieved via a chain reaction initiated by electrocatalytic anodic sulfate(SO_(4)^(2-))oxidation to produce persulfate(S_(2)O_(8)^(2-))and followed by a cathodic persulfate reduction to produce sulfate radicals(SO_(4)^(·-)).These SO_(4)^(·-)are powerful reactive species that enable the unselective degradation of micropollutants and yield SO_(4)^(2-)again in the treated water.The proposed flow-through electrochemical system achieves the efficient degradation(100.0%)and total organic carbon removal(65.0%)of aniline under optimized conditions with a single-pass mode.We also reveal the effectiveness of the proposed system for the degradation of a wide array of emerging micropollutants over a broad pH range and in complex matrices.This work provides the first proof-ofconcept demonstration using ubiquitous sulfate for micropollutants decontamination,making water purification more sustainable and more economical.

Abnormal Reactions of Free Radicals and Oxidative Damages in the Bodies of Patients With Chronic Glomerulonephritis

Objective To study the abnormal reactions of a series of free radicals and the oxidative damages induced by free radical abnormal reactions in the bodies of patients with chronic glomerulonephritis. Methods Eighty chronic glomerulonephritis patients (CGNP) and eighty healthy adult volunteers (HAV) were enrolled in a random control study, in which concentrations of nitric oxide (NO) in plasma, lipoperoxides (LPO) in plasma and in erythrocytes, and vitamin C (VC), vitamin E (VE) and beta-carotene (?CAR) in plasma as well as activities of superoxide dismutase (SOD), catalase (CAT) and glutathione peroxidase (GPX) in erythrocytes were determined with spectrophotometric assays. Results Compared with the average values of the above biochemical parameters in the HAV group, the average values of NO in plasma, and LPO in plasma and erythrocytes in the CGNP group were significantly increased (P = 0.0001), while those of VC, VE and -CAR in plasma as well as those of SOD, CAT and GPX in erythrocytes in the CGNP group were significantly decreased (P = 0.0001). Pearson product-moment correlation analysis showed that with increase of the concentration of blood creatinine as well as prolongation of the course of disease in the CGNP, the concentrations of NO in plasma, and LPO in plasma and erythrocytes in the CGNP increased gradually, while the concentrations of VC, VE and ?CAR in plasma as well as the activities of SOD, CAT and GPX in erythrocytes in the CGNP decreased gradually (P = 0.002454 0.000001). The relative risk ratio (RR) of the above biochemical parameters reflecting oxidative damages in the bodies of CGNP ranged from 6.061 to 72.429. The reliability coefficient (alpha) that the above biochemical parameters were used to reflect the oxidative damages of the CGNP was 0.8137, standardized item alpha = 0.9728, Hotelling抯 T-Squared = 1135680.191, F = 53274.6478, P = 0.000001. Conclusions The findings in this study show that in the bodies of CGNP a series of free radical chain reactions result in severe pathological aggravation and induce oxidative damages in their bodies. Therefore, suitable dose of antioxidants should be supplemented to them so as to alleviate oxidative damages in their bodies.

Component Analysis and Free Radicals Scavenging Activity of Physalis alkekengi L. Polysaccharide

A crude polysaccharide was extracted from Physalis alkekengi L. fruit. HPLC was used for the component analysis of the polysaccharide. The results indicate that Physalis alkekengi L. polysaccharide（PAP） was composed of rhamnose, xylose, arabinose, galactose, and glucose. Free radicals scavenging activity of PAP was studied through 3 free radicals scavenging tests. PAP exhibited high scavenging effects on OH and DPPH radicals, and both the scavenging rates were about 80%. The scavenging rate of O2^- radical was about 22%.

Changes of free radicals and digestive enzymes in saliva in cases with deficiency inspleen-yin syndrome

Objective：To explore the nature of deficiency in spleen-yin syndrome,which could provide scientific theoretical support and practical guidance for clinical Traditional Chinese Medicine（TCM）syndrome differentiation based on biology,and had a strong clinical significance.Methods：Serum Cu and Zn were detected by atomic absorption spectrophotometer,serum vitamin E by high performance liquid chromatography,serum vitamin C by 2,4-Dinitrophenylhydrazine Colorimetry,total superoxide dismutase（SOD）and Cu and Zn- SOD by the xanthine oxidase method,and malondialdehyde（MDA）by the 2-thiobarbituric acid method（TBA）.Total antioxidant capacity was detected by a colorimetry kit.Amylase Activity was detected by an automatic biochemical analyzer.Lysozyme was detected by lysozyme detection plate,the diameter of bacteriolysis circle was measured and the corresponding content of lysozyme was obtained from a table of standard curve values.Results： No significant difference in total SOD and Cu,Zn-SOD was found between deficiency in spleen-yin group and normal group.However,such factors in deficiency in kidney-yin group were significantly lower than the other groups（P〈0.05）.The MDA content in both deficiency in spleen-yin group and deficiency in kidney-yin group were significantly higher than that of normal group（P〈0.05）,while the total antioxidant capacity was significantly lower than normal group（P〈0.05）.The vitamin E content in deficiency in kidney-yin group was significantly lower than that in the other two groups（P〈0.05）.No significant difference in the contents of vitamin C,Cu and Zn were observed in these groups.The Zn/Cu level in deficiency in kidney-yin group and the vitamin E level in deficiency in spleen-yin group decreased,but with no significant difference.Amylase activity in unit time in cases with deficiency in spleen-yin was lower than and had significant differences with that in normal cases,and higher than that in cases with deficiency in kidney-yin.The sectional velocity of saliva and the ratio of lysozyme in normal case group were significantly higher than other two groups,while deficiency in the spleen-yin group was significantly higher than the deficiency in kidney-yin group.Conclusion：All the results indicated that the objective pathological mechanism between the deficiency in spleen-yin and deficiency in kidney-yin was different.

Non-Homogeneous Riemann Boundary Value Problem with Radicals

The solution of the non-homogeneous Riemann boundary value problem with radicals (1. 2) together with its condition of solvability is obtained for arbitrary positive integersp andq, which generalizes the results for the casep=q=2.

A Kinetic Evidence for the Nitroxyl Radicals Recycling Mechanism in the Photostabilizing Process of HALS

The photoinduced bulk polymerization of a reactive-hindered amine light stabilizers (r-HALS), 4-acryloyl-2, 2, 6,6-tetramethylpiperidinyl (ATMP), was performed at 80 C by using a DPC technique. An unique periodic exponential attenuation-type oscillating curve was found when the polymerization was carried out in air, but this phenomenon was not found in nitrogen. It is supposed that this unique kinetic performance may be attributed to nitroxyl radicals that are produced in situ from the oxidation of ATMP. ATMP polymer with narrow polydispersity (d = 1.03) can be obtained by photoinduced solution polymerization of ATMP. The signal detected in ESR may be assigned to the nitroxyl radicals in the matrix of ATMP polymer. Since this kind of recycling of nitroxyl radicals is well documented for the photostabilizing mechanism of HALS, the present results may serve as a kinetic evidence for this mechanism.

Photooxidation of hydrochlorofluocarbons and hydrofluorocarbons initiated by OH radicals

Under simulated atmospheric condition, photoomdation for HCFC-22 + H2O2, HCFC-22 + H2O2+O2, HFC-134A + H2O2 and HFC-134A + H2O2+ O2 systems were studied.H2O2 was irradiated by low pressure mercury lamp and produced OH radicals. The OH radicals can initiate photooxidation of HCFC-22 and 134A. The products of photooxidation were determined by a Fourier Transform infrared Spectroscopy with a 20ml long path cell. The products were COF2,CO2, HCI, H2O and HF for HCFC-22 + H2O2 system, HO, CO2, HCI and HF for HCFC-22 +H2O2 +O2 system, HCOF, CF3OOCF3,CO2, H2O and HF for HFC-134A +H2O2 system, HCOF, CO2, H2O, and HF for HFC-134A + H2O2+ O2 system. Based on those results, the mechanisms of photooxidation were suggested.

Free Radicals in Organic Matter for Thermal History Reconstruction of Carbonate Succession

Geothermometer is one of the most useful methods to reconstruct the thermal history of sedimentary basins. This paper introduces the application of free radicals concentration of organic matter as a thermal indicator in the thermal history reconstruction of carbonate succession, based on anhydrous thermal simulation results of type I and H1 kerogen. A series of free radicals data are obtained under thermal simulation of different heating temperatures and times, and quantitative modds between free radical concentration （Ng） of organic matter and time-temperature index （TTI） for types I and type H1 kerogen are also obtained. This Ng.TTI relation was used to model the Ordovician thermal gradients of Well TZ12 in the Tarim Basin. The modeling result is corresponding to the results obtained by apatite fission track data and published data. This new method of thermal history reconstruction will be benefit to the hydrocarbon generation and accumulation study and resource assessment of carbonate succession.

Degradation of Phenol by Hydroxyl Radicals on Different Coating Lead Dioxide Electrodes

Lead dioxide electrodes on Ti substrates were prepared by thermal-deposition or electro-deposition. The amount of hydroxyl radicals generated at the electrodes prepared by the above-mentioned two methods was compared with that at the electrodes mingled with Bi or La prepared by electro-deposition. The experimental results indicate that the highest concentration of hydroxyl radicals generated by thermal-deposition, electro-deposition mingled with nothing, electro-deposition mingled with Bi or La was 0.781, 1.048, 1.838 or 2.044 μmol/L, respectively. When phenol was electrolyzed on the four electrodes at a current density of 30 mA/cm2, the removal efficiency of phenol after electrolysis for 1.5 h was 87.30%, 93.55%, 97.95% or 98.70%, TOC removal efficiency after electrolysis for 5 h was 86.76%, 94.26%, 98.53% or 99.60%, respectively. Through the degradation experiments of phenol, the amount of hydroxyl radicals was responsible for the removal efficiency of phenol. The electro-catalytic characteristics were investigated by SEM, the generation amount of hydroxyl radicals, the degradation degree of phenol and the stability and conductivity of the electrodes were also investigated. The experimental results indicate that the four electrodes all show good electro-catalytic characteristics; the electro-catalytic characteristics of the electrode mingled with La were superior to those of the other three ones, and the electrochemical degradation of phenol followed one-step reaction dynamics.

Photo-Catalyzed Rare Earth Materials with Ability to Translate Free Radicals into Negative Ions

Materials with function of producing negative ions effection,containing valency-variable rare earth elements and semiconductor oxide,were fabricated.Free radicals produced by the materials were tested.The result shows that the materials can produce quite a few free radicals as·O^-_2 no matter whether they are under illumination of ultraviolet radiation or under visible light radiation,or under no light radiation, demonstrating semiconductor oxide can be catalysed under the visible light radiation.At the same time the result shows there is direct relation between the number of free radicals and of the negative ion produced by the materials,which meant that during photo-catalyzed and redox process of valency-variable rare earth elements free radicals translate into negative ions. A circular model is presented involving circulating change of valency-variable rare earth elements and water and oxygen absorbed on the surface of materials under the condition of photocatalysis.

Liver Nuclear Activation of Carbon Tetrachloride or Bromotrichloromethane to Trichloromethyl and Trichloromethylperoxyl Free Radicals.Their Reactions With Lipids and Proteins

The formation of·CCl3 radicals in liver nuclei was suggested by spin trapping of them with N-t-butyl-α-phenylnitrone followed by GC/MS detection of the resulting adduct. Comparison of its formation in microsomal biotransformation of CCl4 was made. In aerobic nuclear activation mixtures containing NADPH and CCl4, significant decrease in the arachidonic acid content of nuclear lipids was observed (27. 8%, compared to control), the intensity of this decrease was lower than that occurring in the corresponding microsomal incubation mixtures (29.1%). Significant decreases in arachidonic acid content of nuclear and endoplasmic reticulum lipids were also observed in animals at 6 hours of poisoning with the haloalkane. During aerobic nuclear metabolism of CCl4 or CBrCl3, cholesterol oxidation products were detected: a ketocholesterol, an epoxide like structure and 7-ketocholesterol. Nuclear protein carbonyl formation was not promoted during nuclear CCl4 biotransformation. NADPH by itself may lead to protein carbonyl formation during prolonged periods of incubation. CBrCl3 in contrast, led to decreased protein carbonyl formation. No increase in nuclear protein carbonyl formation was observed in CCl4 intoxicated animals during periods of time between 1 to 6 hours after treatment. The results indicate that during nuclear biotransformation of CCl4 or CBrCl3 reactive free radicals, PUFA degradation, reactive aldehydes and cholesterol oxidation products are formed, nearby DNA and regulatory proteins.

Optical Emission Spectroscopic Measurement of Hydroxyl Radicals in Air Discharge with Atomized Water

Effects of discharge mode, voltage applied, size of the nozzle discharge electrode and flow rate of water on the generation of hydroxyl radical were investigated in air discharge with atomized water, by using optical emission spectroscopy （OES）. Water was injected into the discharge region through the discharge nozzle electrode, and a large amount of fine water drops, formed and distributed in the discharge region, corona discharge was more effective to generate were observed. It was found that negative DC the hydroxyl radicals in comparison to positive DC corona discharge or negative pulsed discharge. A larger outer diameter of the nozzle electrode or a stronger electric field is beneficial for hydroxyl-radical generation. Moreover, there is a critical value in the flow rate of atomized water against the discharge voltage. Below this critical value, hydroxyl-radical generation increases with the increase in flow rate of the water, while above this value, it decreases. In addition, it is observed that OES from the discharge is mainly in the ultraviolet domain. The results are helpful in the study of the mechanism and application of plasma in pollution-control in either air or water.

Key Role of Some Specific Occupied Molecular Orbitals of Short Chain n-Alkanes in Their Surface Tension and Reaction Rate Constants with Hydroxyl Radicals: DFT Study

Basing on the DFT calculations we propose the new theoretical model which describes both the surface tension σ of the short chain n-alkanes at their normal boiling points and their reaction rate constants with hydroxyl radicals OH• (at 297 ± 2 K) on the basis of their molecular orbital electronic characteristics. It has been shown that intermolecular dispersion attraction within the surface liquid monolayer of these compounds, as well as their reaction rate constants k with OH• radicals are determined by the energies Eorb of the specific occupied molecular orbitals which are the same in the determination of both the above physico-chemical characteristics of the studied n-alkanes. The received regression equations confirm the theoretically found dependences between the quantities of σ and k and the module |Eorb|. For the compounds under study this fact indicates the key role of their electronic structure particularities in determination of both the physical (surface tension) and the chemical (reaction rate constants) properties.

Chemical composition and free radicals restraining activity of extracts from three Manglietia species leaves

The extracts from leaves of Manglietia insignis （Wall） Blume, Manglietia chingii Dandy and Manglietia yuyuanensis Law were prepared by organic solvent extraction and their components were analyzed by GC/MS and quantified. Meanwhile, the free radicals restraining activities were detected. The 21 compounds in M. insignis, 36 compounds in M. chigii and 20 compounds in M. yuyuanensis were identified. There were 11 common components in the extracts from three Manglietia species, and 12 components in two Manglietia species. The results of relative contents of every component in three extracts showed that the main constituents of M. insignis were terpenoids and alkene, amounting to 38.93%, followed by alkane （28.18%）, the nitrogen containing compounds （15.73%） and aromatic compounds （7.23 %）. The main constituents of leaf extract from M. chingii were the terpenoids and alkene, carboxylic acid, alkane and aromatic compounds, amounting to 30.22%, 14.17%, 13.87% and 13.29%, respectively, The main constituents of M. yuyuanensis were alcohol compounds, the terpenoids and alkene, and aromatic compounds, amounting to 28.00%, 25.38% and 18.00% respectively. The results showed that the three extracts had strong function of restraining oxygen free radicals. The ultra oxygen anions activity was restrained at the highest level, when the three extracts were diluted by hundred-fold, whereas the restraining capacity of hydroxyl free radicals reached maximum, when the three extracts were diluted by twenty-fold. The above results provide scientific evidences for further approaching the ecological healthy function of three MangUetia species

Oncogenes, Oncogenesis, and Oxygen Radicals

The role that free radicals in general and oxygen radicals in particular play in carcinogenesis has attracted considerable attention in recent years. The oxygen radicals are undesirable but inevitable products of aerobic metabolism in the normal living cell. The cellular antioxidant defense system maintains an appropriate balance between necessary oxidative events and those that are excessive. When this critical balance cannot be maintained because of the overloading of the cellularredox system, oxygen radicals can induce cell damage. They can influence carcinogenesis by inducing DN A damage from direct oxidation or indirectly from DNA-binding products of lipid peroxidation. Oxygen radicals can induce conformational changes in the plasma membrane by lipid peroxidation and protein degradation, thus influencing membrane-associated cellular activities. They are capable of affecting membrane-bound protein kinases, growth factors and their receptors, and, therefore, signal transduction and oncogene activation. Thus, the oxygen radicals can have a major influence on oncogenes and oncogenesis. (C)1990 Academic Press.Inc.

The investigation of OH radicals produced in a DC glow discharge by laser-induced fluorescence spectrometry

In this paper the OH radicals produced by a needle-plate negative DC discharge in water vapor,N_(2)+H_(2)O mixture gas and He+H_(2)O mixture gas are investigated by a laser-induced fluorescence(LIF)system.With a ballast resistor in the circuit,the discharge current is limited and the discharges remain in glow.The OH rotation temperature is obtained from fluorescence rotational branch fitting,and is about 350 K in pure water vapor.The effects of the discharge current and gas pressure on the production and quenching processes of OH radicals are investigated.The results show that in water vapor and He+H_(2)O mixture gas the fluorescence intensity of OH stays nearly constant with increasing discharge current,and in N_(2)+H_(2)O mixture gas the fluorescence intensity of OH increases with increasing discharge current.In water vapor and N_(2)+H_(2)O mixture gas the fluorescence intensity of OH decreases with increasing gas pressure in the studied pressure range,and in He+H_(2)O mixture gas the fluorescence intensity of OH shows a maximum value within the studied gas pressure range.The physicochemical reactions between electrons,radicals,ground and metastable molecules are discussed.The results in this work contribute to the optimization of plasma reactivity and the establishment of a molecule reaction dynamics model.

Effect of Nonenzymatic Antioxidants on Sperm Motility and Survival Relative to Free Radicals and Antioxidant Enzymes of Chilled-Stored Ram Semen

The effect of inclusion of three antioxidants (Vitamin E, cysteine and glutathione) in ram semen extender on the release of antioxidant enzymes and free radicals was studied. A 3 × 3 factorial experiment was conducted to test effects of supplementing ram semen extender with Vitamin E (1, 5 and 10 IU), cysteine (1, 5 and 10 mM) or glutathione (0.5, 1 and 2 mM) on the sperm survival and release of superoxide dismutase (SOD), glutathione peroxidase (GPX) and thiobarbituric acid reactive substances (TBARS). Eighty ejaculates of eight fertile Najdi rams were collected, assessed for the gross examination and the good ejaculates (≥90% motility) were pooled and sperm count was assessed. Therefore ten extenders;control (C) and 9 treated (C plus antioxidant) were tested. Extended semen was stored at 5°C for 96 h, examined for motility and survival and sperm cells were separated from plasma, sonicated, homogenized and exposed to the determinations of SOD, GPX and TBARS. The highest sperm survival was found in diluents containing 5 IU Vitamin E/ml, 1 and 2 mM glutathione (55.5% survival), while the lowest survival was found in 10 mM cysteine (11.1%). TBARS concentration was highest (P < 0.05) in control than other treatments, however, Vitamin E and glutathione exhibited low values. Contrariwise, activities of SOD and GPX increased (P < 0.05) within sperm cells and seminal plasma in diluents containing 5 IU E, 1 mM and 2 mM glutathione. The enzymatic activities were generally higher in seminal plasma than in sperm cells. It was concluded that supplementing ram semen extender during chilled storage with 5 IU Vitamin E per ml or 1 - 2 mM glutathione enhanced sperm survival and reduced free radicals.