Detection of Oxidants Such as Hydroxyl Radicals and Chlorine Electrogenerated on a BDD Electrode by Simple Methods

The aim of this work is to detect electrogenerated hydroxyl radicals and chlorine by simple and less expensive methods. Preparative electrolyses of perchloric acid (HClO4) and sodium chloride (NaCl) were performed on a boron-doped diamond (BDD) electrode. The hydroxyl radicals were quantified indirectly by assaying the samples from the HClO4 (0.1 M) electrolysis with a 10−4 M potassium permanganate solution. The investigations showed that the amount of hydroxyl radicals depends on the concentration of HClO4 and the current density. As for chlorine, a qualitative determination was carried out. A mixture of the electrolyte solution of HClO4 (0.1 M) + NaI (0.2 M) + 2 mL of hexane, taken in this order, leads to a purplish-pink coloration attesting to the presence of Cl2. The same test was carried out with NaBr and NaI giving pale and very pale pink colourations, respectively, showing that the intensity of the colouration depends on the strength of the oxidant present. In addition, oxidants were detected during the electrooxidation of metronidazole (MNZ). The results showed the participation of electrogenerated hydroxyl radicals. The generation of chlorine has also been proven. Furthermore, the degradation leads to a chemical oxygen demand (COD) removal rate of 83.48% and the process is diffusion-controlled.

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.

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.

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.

Rate constants for the reaction of hydroxyl radicals with HFC-134a

Rate constants for the reaction of hydroxyl radicals with HFC 134a (CH 2FCF 3) have been measured by the discharge flow resonance fluorescence (DF RF) technique over the temperature range 288—370 K. The derived Arrhenius equation is: k″ =(1.27±0.16)×10 -12 exp(-(1662±41)/ T )cm 3/(mol·s). The tropospheric lifetime of HFC 134a is estimated to be 10.5 years, which is in excellent agreement with the most recent results.

Kinetics for the reaction of hydroxyl radicals with CH_3Br and its implications in the atmosphere

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Singlet oxygen synergistic surface-adsorbed hydroxyl radicals for phenol degradation in CoP catalytic photo-Fenton

In recent years,there have been numerous studies on Fenton or Fenton-like reactions mediated by nonfree radicals such as singlet oxygen(1O_(2));however,there are few studies on the synergistic effect of 1O_(2) and free radicals on the degradation of organic molecules,such as phenol in Fenton reaction.In this study,a cocatalyst,CoP,commonly used in photocatalysis was synthesized using a simple two-step method,and a CoP/Fe^(2+)/AM1.5 system was constructed by introducing Fe^(2+)and simulated sunlight(AM1.5)irradiation.The newly constructed CoP/Fe^(2+)/AM1.5 system could effectively degrade various organic pollutants,including dyes,phenols,and antibiotics.Radical quenching experiments and electron paramagnetic resonance detection confirmed that there were three reactive oxygen species(ROS)in the CoP/Fe^(2+)/AM1.5 system,including·OH_(ads),·O_(2)^(-),and 1O_(2).Further,combined with the liquid chromatogram of phenol,its intermediate products,and the fluorescence diagram of o-hydroxybenzoic acid,it can be concluded that a synergistic effect exists between 1O_(2) and the surface-adsorbed·OH_(ads) in the CoP/Fe^(2+)/AM1.5 system.The controllable formation of surface 1O_(2) and·OH_(ads) was achieved through the oxidation(Co^(3+))and reduction(Pδ−)centers exposed on the CoP surface,and the synergistic effect between them results in phenol’s hydroxylation,ring-opening,and degradation.The study of this new mechanism provides a new perspective for revealing the surface interface reaction between ROS and organic pollutants.

Hydroxyl radicals-mediated oxidative cleavage of the glycosidic bond in cellobiose by copper catalysts and its application to low-temperature depolymerization of cellulose

As the most abundant source of biomass in nature for sustainable production of fuels and chemicals,efficient depolymerization of cellulose under mild conditions,due to the difficulty in selective cleavage of itsβ-1,4-glycosidic bonds,still remains challenging.Here,we report a novel method for oxidative cleavage of the glycosidic bonds by free radicals.Probed by the cellobiose reaction,it was found that·OH radicals,generated from the decomposition of H2O2 catalyzed by CuSO4 or CuO/SiO2,were efficient for selective conversion of cellobiose to glucose and gluconic acid at a low temperature of 333 K,and their selectivities reached 30.0%and 34.6%,respectively,at 23.4%cellobiose conversion.Other radicals,such as·SO4?,also exhibited high efficacy in the cellobiose reaction.Mechanistic studies suggest that the oxidative cleavage of theβ-1,4-glycosidic bond by the free radicals involve formation of the carbon radical intermediate via abstraction of the H atom dominantly at the C1 position.Following this oxidative mechanism,treatment of microcrystalline cellulose with·OH by impregnation with H2O2 and CuSO4 catalyst at 343 K led to significant enhancement in its hydrolysis efficiency.These results demonstrate the effectiveness of this new method in the oxidative cleavage of glycosidic bonds,and its viability for the efficient depolymerization of cellulose at low temperatures,which can be further improved,for example,by exploring new free radicals and optimizing their reactivity and selectivity.

Effects of Hydroxyl Radicals on Introduced Organisms of Ship's Ballast Water Based Micro-Gap Discharge

With the physical method of micro-gap gas discharge, OH. radicals were produced by the ionization of O2 in air and H2O in the gaseous state, in order to explore more effective method totreat the ship＇s ballast water. The surface morphology of Al2O3 dielectric layer was analysed using Atomic Force Microscopy （AFM）, where the size of Al2O3 particles was in the range of 2 μm to 5 μm. At the same time, the biochemical effect of hydroxyl radicals on the introduced organisms and the quality of ship＇s ballast water were studied. The results indicate that the main reasons of cell death are lipid peroxide and damage of the antioxidant enzyme system in Catalase （CAT）, Peroxidase （POD） and Superoxide dismutase （SOD）. In addition, the quality of the ballast water was greatly improved.

Determination of hydroxyl radicals with salicylic acid in aqueous nitrate and nitrite solutions

The qualitative and quantitative analyses of reactive oxygen species are essential to determine their steady-state concentration and related reaction mechanisms in environmental aquatic systems. In this study, salicylic acid was employed as an innovative molecular probe of hydroxyl radical(OH) generated in aqueous nitrate and nitrite solutions through photochemical reactions. Kinetic studies showed that the steady-state concentrations of OH in aqueous NO- 3(10 mmol/L, pH=5) and NO- 2(10 mmol/L, pH=5) solutions under ultraviolet irradiation were at a same magnitude, 10 -15 mol/L. Apparent quantum yields of OH at 313 nm were measured as 0.011 and 0.07 for NO- 3 and NO- 2 respectively, all comparable to the results of previous studies.

Determination of hydroxyl radicals in TiO2/Ti photoelectrocatalytic oxidation system using Fe（phen）3^2＋ spectrophotometry

A new method of determining the cumulate concentration of hydroxyl radicals in the TiO2/Ti photoelectrocatalytic（PEC） oxidation system was established by o-phenanthroline-Fe（Ⅱ）（Fe（phen）3^2＋） spectrophotometry and using anion exchange membrane. Fe （phen）3^2＋ can be oxidized to o-phenanthroline-Fe（Ⅲ）（Fe（phen）3^3＋） by strong oxidization of hydroxyl radicals（·OH）. Then the cumulate concentration of hydroxyl radicals can be calculated through determining the change of the Fe（phen）3^3＋ absorbency at 509 nm. In addition, the research results showed the production rate of hydroxyl radicals was affected obviously by pH of solution, the cumulate concentration of hydroxyl radicals was the largest at nearby the initial pH 6.3 （isoelectric point）, and the change direction of pH after illumination tended to nearby isoelectric point.

Production and contribution of hydroxyl radicals between the DSA anode and water interface

Hydroxyl radicals play the key role during electrochemical oxidation and photoelectrochemical oxidation. The production and effect of hydroxyl radicals on the interface between DSA anode and water was investigated by examining the quenching effect of iso-propanol on Orange II decolorization. We observed that with an increase in electrode potential from 4 to 12 V across electrodes at pH 7.0, the contribution percentage of hydroxyl radicals increased dramatically. More OH radicals were produced in acidic and alkaline conditions than at neutral conditions. At electrode potential of 4 V, the contribution percentage of hydroxyl radicals was obviously higher at near neutral pH conditions, while removal efficiency of Orange/I achieved was the lowest concurrently. Finally, for photocatalytic oxidation, electrochemical oxidation, and photoelectrochemical oxidation using the same DSA electrode, the effect of hydroxyl radicals proved to be dominant in photocatalytic oxidation but the contribution of hydroxyl radicals was not dominant in electrochemical oxidation, which implies the necessity of UV irradiation for electrochemical oxidation during water treatment.

Kinetics and mechanism of nitrobenzene degradation by hydroxyl radicals-based ozonation process enhanced by high gravity technology

This study investigated the indirect oxidation of nitrobenzene(NB)by hydroxyl radicals(·OH)in a rotating packed bed(RPB)using competitive kinetics method with p-nitrochlorobenzene as a reference compound.The rate constants of NB with·OH are calculated to be between(1.465±0.113)×10^(9)L/(mol·s)and(2.497±0.192)×10^(9)L/(mol·s).The experimental data are fitted by the modified Arrhenius equation,where the activation energy is 4877.74 J/mol,the order of NB concentration,rotation speed,and initial pH is 0.2425,0.1400 and 0.0167,respectively.The ozonation process of NB could be enhanced by RPB,which is especially effective for highly concentrated NB-containing waste-water under alkaline conditions.The high gravity technology can accelerate ozone mass transfer and self-decomposition of ozone to produce more·OH,resulting in an increase in the indirect oxidation rate of NB by·OH and consequently effective degradation of NB in wastewater.

Electron Spin Resonance Analyse on the Production of Hydroxyl Radicals by Ozone Photolysis

In order to explore the production of hydroxyl radical （.OH） in a confined space, a novel ozone-light irradiation system is constructed in this study, and the .OH radical is measured by spin-trapping electron spin resonance （ESR） method in which 5,5-dimethyl-l-pyrroline-N-oxide （DMPO） is selected as the spin-trap. Several influence factors including the light intensity, the irradiation time and DMPO mass concentration are discussed. The results show that in this experimental system, with DMPO mass concentration of lg/L and the irradiation time of 30 rain, the -OH radical can be best captured. Besides, both wavelength and intensity of the irradiation light could effect the generation of .OH radical. These results are of great importance to further study the sterilization effect of .OH radical in confined space.

A highly selective and sensitive upconversion nanoprobe for monitoring hydroxyl radicals in living cells and the liver

Excessive reactive oxygen species(ROS)would attack living cells and cause a series of oxidative stress related diseases,such as liver damage.Hydroxyl radicals(·OH)are currently known as one of the most toxic and harmful free radicals to organisms.Therefore,studies involving hydroxyl radicals have become important research topics in the fields of biology,biochemistry,and biomedicine.In addition,imaging of analytes using upconversion nanoparticles(UCNPs)possesses significant advantages over that using general fluorescent dyes or nanoparticles due to its high spatial resolution,reduced photodamage,and deep tissue penetration properties.Herein,we designed a highly selective and sensitive hydroxyl radical nanoprobe based on the luminescence resonance energy transfer between upconversion nanoparticles and methylene blue(MB).The concentration of·OH could be determined by the fluorescence recovery of the UCNPs due to the oxidative damage of MB.Using this nanoprobe,the·OH in living cells or in liver tissues could be monitored with high sensitivity and selectivity.

Dual roles of hydroxyl radicals and effects of competition on ozonation kinetics of two phenazone-type pollutants

Ozonation has been proved to be a promising approach for eliminating emerging pollutants in wastewater.In previous studies,emerging pollutants including diverse pharmaceuticals were found to exhibit significantly different ozonation reactivity.However,how the structural differences of emerging pollutants determine ozonation reactivity and mechanisms are still ambiguous.In this work,ozonation of dimethylaminophenazone(DMP)and acetylaminophenazone(AAA)with the same parent structure of phenazone but different substitution groups was investigated,in order to probe influencing mechanisms of structural differences on ozonation reactivity.Results show that DMP reacts with ozone and HO
almost 2 and 1 order of magnitude faster than AAA,respectively.At pH 8,HO· accelerates ozonation of DMP,but decreases ozonation of AAA.Competition simultaneously decreases degradation rate of the two phenazones,but effects on AAA are more significant than that on DMP.According to theoretical calculation results,differences in ozonation reactivity and mechanisms of the two phenazones can be mainly attributed to different substitution groups.The dimethylamino group in the structure of DMP increases the ozonation reactivity of phenazone by increasing reaction orbital energies and altering reaction sites,while the acetylamino group in the structure of AAA decreases the reaction orbital energy and therefore lowers the reactivity.

Flow Cytometric Evidence for Hydroxyl Radical-induced Apoptosis in Tobacco Protoplasts

Protoplasts prepared from tobacco (Nicotiana tabacum L., cultivar BY-2) suspension cells have similar morphological characteristics to those in animal cells. The hallmarks of apoptosis such as condensation and peripheral distribution of nuclei, TUNEL positive reaction, and DNA ladders were observed when tobacco protoplasts were treated with the hydroxyl radical generating system (1.0 mmol/L FeSO4/0.5 mmol/L H2O2). In animals, the loss of transmembrane potential (DeltaPsi(m)) and the exposure of phospholipid phosphatidylserine (PS) are believed to be the main apoptosis events. To test whether these significant processes take place in plants, flow cytometry was used to detect annexin V binding and changes in DeltaPsi(m). Results showed that the PS turned out from inner membrane and DeltaPsi(m) gradually decreased during the apoptosis. All these apoptotic characteristics proved that hydroxyl radicals can cause typical programmed cell death (PCD) in tobacco protoplasts and this design can be served as an effective experiment system to explore the mechanism of plant apoptosis.

Microwave-assisted hydroxylation of benzene to phenol with H_2O_2 over FeSO_4/SiO_2

Hydroxyl radicals HO are generated under Fenton-like (Fe2++H2O2→HO?+OH?+Fe3+) catalytic conditions upon microwave irradiation. Liquid-phase direct catalytic oxidation of benzene to phenol was obtained using FeSO4 supported on silica gel as a solid catalyst and hydrogen peroxide as the oxidant. The effects of various parameters, such as the different solvents, the amount of solvent used, the amount of catalyst used, the reaction time, the reaction temperature and the amount of hydrogen peroxide used on the yield of phenol were studied to identify optimum reaction conditions. Conventionally heated reaction gives a phenol yield of 0.6%. A higher phenol yield of 13.9% with a selectivity of 100% is obtained when the reaction mixture was irradiated with micro-wave energy. It is concluded that microwave irradiation offers more effective control of energy input for hydroxyl radical generation that is appropriate for various synthetic reactions.

Glow Discharge Induced Hydroxyl Radical Degradation of 2-Naphthylamine

In an aqueous solution, normal electrolysis at high voltages switches over spontaneously to glow discharge electrolysis and gives rise to hydroxyl radical, hydrogen peroxide, and aqueous electron, as well as several other active species. Hydroxyl radical directly attacks organic contaminants to make them oxidized. In the present paper, 2-naphthylamine is eventually degraded into hydrogen carbonate and carbon dioxide. The degradation process is analyzed by using an Ultraviolet (UV) absorption spectrum, high-performance liquid chromatography (HPLC) and chemical oxygen demand (COD). It is demonstrated that 2-naphthylamine (co =30 mg·1-1) is completely converted within 2h at 30℃ and 600 V by glow discharge electrolysis, and the degradation is strongly dependent upon the presence of ferrous ions. COD is ascended in the absence of ferrous ions and descended in the presence of them.

Study on Solid Fermentation and Antioxidant Function of Natto

[Objectives]To study the optimum conditions of solid fermentation of natto with antioxidant function as an index.[Methods]Single factor experiment and orthogonal experiment were designed to study the effects of temperature,time,initial pH and inoculum amount on the antioxidant activity of natto solid fermentation.The optimum conditions of natto solid fermentation were determined and the antioxidant ac-tivity of natto extract was compared.[Results]The optimal fermentation conditions were as follows:temperature 32℃,initial pH 7.0,inocu-lation amount 8%,fermentation time 32 h.The hydroxyl radical scavenging rate of natto solid fermentation crude extract was the highest,which was 82.7%.The optimized nato fermentation extract showed stronger scavenging ability for-OH and O,:,and showed obvious dose-effect relationship.ICso was 3.63 and 4.24 mg/mL,respectively,and the scavenging efficiency was 1.3 and 1.9 times higher than that of the unoptimized fermentation extract,respectively.[Conclusions]Natto is rich in nattokinase and other functional factors,and its antioxidant ac-tivity can be improved by optimizing fermentation technology,so that natto products can be widely used,including cosmetic raw materials,nat-to skin care soap,health food and medicine,etc.,and have a broader development prospect.