Oxygen vacancy boosting Fenton reaction in bone scaffold towards fighting bacterial infection

Bacterial infection is a major issue after artificial bone transplantation due to the absence of antibacterial function of bone scaffold,which seriously causes the transplant failure and even amputation in severe cases.In this study,oxygen vacancy(OV)defects Fe-doped Ti O2(OV-FeTiO2)nanoparticles were synthesized by nano TiO2and Fe3O4via high-energy ball milling,which was then incorporated into polycaprolactone/polyglycolic acid(PCLGA)biodegradable polymer matrix to construct composite bone scaffold with good antibacterial activities by selective laser sintering.The results indicated that OV defects were introduced into the core/shell-structured OV-FeTiO2nanoparticles through multiple welding and breaking during the high-energy ball milling,which facilitated the adsorption of hydrogen peroxide(H2O2)in the bacterial infection microenvironment at the bone transplant site.The accumulated H2O2could amplify the Fenton reaction efficiency to induce more hydroxyl radicals(·OH),thereby resulting in more bacterial deaths through·OH-mediated oxidative damage.This antibacterial strategy had more effective broad-spectrum antibacterial properties against Gram-negative Escherichia coli(E.coli)and Gram-positive Staphylococcus aureus(S.aureus).In addition,the PCLGA/OV-FeTiO2scaffold possessed mechanical properties that match those of human cancellous bone and good biocompatibility including cell attachment,proliferation and osteogenic differentiation.

Magnetic field assisted Fenton reactions for the enhanced degradation of methyl blue

Magnetic field was tentatively introduced into Fenton reactions system for the degradation and discoloration of methyl blue as the represent of organic chemical dye, which was a bio-refractory organic pollutant in industry wastewater. It was found that under optimal Fenton reaction conditions, with the assistant of magnetic field in Fenton reactions, the degradation rate of methyl blue, the decomposition rate of H2O2 and the conversion rate of Fe^2＋ were accelerated, the extent of them would be improved by the increase of magnetic field intensity. Meanwhile, the mineralization of methyl blue （CODer） was improved by over 10% with magnetic field.

Different Heterogeneous Fenton Reaction Based on Foam Carrier Loaded with Photocatalysts

The effect of heterogeneous Fenton reaction was studied on methylene blue（MB） and Nitrosomonas europaea（N. europaea） cells. Four Fenton systems were prepared and compared with each other, including Nickel Foam（NF）/TiO2, NF/Bi2WO6, Ceramic foam（CM）/TiO2, and CM/Bi2WO6. The order of effect of fenton reaction ranked as NF/TiO2〉CM/TiO2〉NF/Bi2WO6〉CM/Bi2WO6. In acid or alkaline solution, the removal efficiency also decreased compared with neutral solution. With lower p H values, the nanoparticles were easier to break off from NF skeleton. Thus the synergetic effect of photocatalysis and fenton reaction can not take action. As for CM skeleton, the bond –Si-O-can bind with TiO2 or Bi2WO6. The membrane fluidity was used as an indicating parameter. After being treated by Fenton reaction, N. europaea surface was rougher than the native bacterium and the bulges on cell surface became irregular, which is attributed to change of lipopolysaccharide patches. Polarization of N. europaea cell membrane in acid medium increased more obvious than alkaline medium.

A Novel and Convenient Assay for the Determination of OH Produced by Fenton Reaction

A novel, simple and convenient method for the determination of hydroxyl radicals isestablished. Hydroxyl radicals produced by Fenton reaction is trapped by spin trap reagent phenyl-t-butyl nitrone (PBN), and the free radical adduct of PBN can be detected by single sweeposcillopolarography, with its second order derivative cathodic wave at -0.52V vs SCE. Theoptimum experimental conditions for the detemination is discussed, and the scavenging effects ofsome compounds on OH was also studied.

Mechanism of chemiluminescence in Fenton reaction

A scheme of the processes in Fenton solution with various substances is offered, and the channels of light formation registered by the luminometer are analyzed. Under the proposed scheme we discuss the possibilities of studying the properties of antioxidants and prooxidants. Oxidation of alanine, albumin and sodium oxalate have been taken as an example. The properties of ascorbic acid and the mechanism of display of its oxidant and prooxidant properties are analyzed herewith. Methodical questions of the chemiluminescence research in Fenton solution such as the selection of reagents concentration, water preparation and the effect of the background radiation have been considered in this study as well.

Efficient Fe（Ⅲ）/Fe（Ⅱ） cycling triggered by MoO2 in Fenton reaction for the degradation of dye molecules and the reduction of Cr（Ⅵ）

There is a relatively low efficiency of Fe(Ⅲ)/Fe(Ⅱ) conversion cycle and H2 O2 decomposition(<30%) in conventional Fenton process,which further results in a low production efficiency of ·OH and seriously restricts the application of Fenton.Herein,we report that the commercial MoO2 can be used as the cocatalyst in Fenton process to dramatically accelerate the oxidation of Lissamine rhodamine B(L-RhB),where the efficiency of Fe(Ⅲ)/Fe(Ⅱ) cycling is greatly enhanced in the Fenton reaction meanwhile.And the L-RhB solution could be degraded nearly 100% in 1 min in the MoO2 cocatalytic Fenton system under the optimal reaction condition,which is apparently better than that of the conventional Fenton system(~50%).Different from the conventional Fenton reaction where the ’OH plays an important role in the oxidation process,it shows that 1 O2 contributes most in the MoO2 cocatalytic Fenton reaction.However,it is found that the exposed Mo^4+ active sites on the surface of MoO2 powders can greatly promote the rate-limiting step of Fe^3+/Fe^2+ cycle conversion,thus minimizing the dosage of H2 O2(0.400 mmol/L) and Fe^2+(0.105 mmol/L).Interestingly,the MoO2 cocatalytic Fenton system also exhibits a good ability for reducing Cr(Ⅵ) ions,where the reduction ability for Cr(Ⅵ) reaches almost 100% within 2 h.In short,this work shows a new discovery for M002 cocatalytic advanced oxidation processes(AOPs),which devotes a lot to the practical water remediation application.

Catalytic degradation of methylene blue by Fenton like system: model to the environmental reaction

To develop more efficient chemical methods for the demineralization of organic pollutants from water bodies, which one was also mimic to the nature, a degradation of methylene blue by Fe(Ⅲ) and H 2O 2 in the absence of light instead of Fe(Ⅱ) and H 2O 2 was studied. Results showed that use of Fe (Ⅲ) is more promising than Fe(Ⅱ). The present study reflects that Fenton reaction is more efficient, in the presence of a small amount of salicylic acid is added which is a one of the priority pollutant.

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials： A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals（·OH）from reactions between recyclable solid catalysts and H2O2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions（HO2./O2^-.）and high-valent iron are the three main types of reactive oxygen species（ROS）,with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.

Fenton reactions drive nucleotide and ATP syntheses in cancer

We present a computational study of tissue transcriptomic data of 14 cancer types to address： what may drive cancer cell division？ Our analyses point to that persistent disruption of the intraceUular pH by Fenton reactions may be at the root of cancer development. Specifically, we have statistically demonstrated that Fenton reactions take place in cancer cytosoi and mitochondria across all the 14 cancer types, based on cancer tissue gene-expression data integrated via the Michaelis-Menten equation. In addition, we have shown that （i） Fenton reactions in cytosol of the disease cells will continuously increase their pH, to which the cells respond by generating net protons to keep the pH stable through a combination of synthesizing glycolytic ATPs and consuming them by nucleotide syntheses, which may drive cell division to rid of the continuously synthesized nucleotides; and （ii） Fenton reactions in mitochondria give rise to novel ways for ATP synthesis with electrons ultimately coming from H2O2, largely originated from immune cells. A model is developed to link these to cancer development, where some mutations may be selected to facilitate cell division at rates dictated by Fenton reactions.

Self-powered electrochemical system by combining Fenton reaction and active chlorine geheration for organic contaminant treatment

Environmental deterioration,especially water pollution,is widely dispersed and could affect the quality of people's life at large.Though the sewage treatment plants are constructed to meet the demands of cities,distributed treatment units are still in request for the supplementary of centralized purification beyond the range of plants.Electrochemical degradation can reduce organic pollution to some degree,but it has to be powered.Triboelectric nanogenerator(TENG)is a newly-invented technology for low-frequency mechanical energy harvesting.Here,by integrating a rotary TENG(R-TENG)as electric power source with an electrochemical cell containing a modified graphite felt cathode for hydrogen peroxide(H2O2)along with hydroxyl radical(·OH)generation by Fenton reaction and a platinum sheet anode for active chlorine generation,a self-powered electrochemical system(SPECS)was constructed.Under the driven of mechanical energy or wind flow,such SPECS can efficiently degrade dyes after power management in neutral condition without any O2 aeration.This work not only provides a guideline for optimizing self-powered electrochemical reaction,but also displays a strategy based on the conversion from distributed mechanical energy to chemical energy for environmental remediation.

Reinventing MoS2 Co-catalytic Fenton reaction:Oxygen-incorporation mediating surface superoxide radical generation

To better understand the mechanisms of hydrogen peroxide(H_(2)O_(2))’s decomposition and reactive oxygen species(ROS)’s formation on the catalyst’s surface is always a critical issue for the environmental application of Fenton/Fenton-like reaction.We here report a new approach to activate H_(2)O_(2) in a co-catalytic Fenton system with oxygen incorporated MoS2,namely MoS_(2−x) O_(x) nanosheets.The MoS_(2−x) O_(x) nanosheets assisted co-catalytic Fenton system exhibited superior degradation activity of emerging antibiotic contaminants(e.g.,sulfamethoxazole).Combining density functional theory(DFT)calculation and experimental investigation,we demonstrated that oxygen incorporation could improve the intrinsic conductivity of MoS_(2−x) O_(x) nanosheets and accelerate surface/interfacial charge transfer,which further leads to the efficacious activation of H_(2)O_(2).Moreover,by tuning the oxygen proportion in MoS_(2−x) O_(x) nanosheets,we are able to modulate the generation of ROS and further direct the oriented-conversion of H_(2)O_(2) to surface-bounded superoxide radical(·O_(2−surface)).It sheds light on the generation and transformation of ROS in the engineered system(e.g.,Fenton,Fenton-like reaction)for efficient degradation of persistent pollutants.

H_(2)O_(2) actuated molybdenum oxide nanodots:Multi-enzyme-like activities,leverage of Fenton reaction,and dual-mode sensitive detection of alendronate sodium

Unexpected benefits to the catalytic performance of materials often originate from the presence of surface defects.Here,novel Dpenicillamine modified molybdenum oxide nanodots,with abundant oxygen vacancy defects,were fabrication by a mild,simple,and cost-effective method.Ultraviolet–visible(UV–Vis)absorption spectra analysis showed that the nanodots had peroxidaselike and catalase-like activities.The reactive oxygen species were probed by electronic paramagnetic resonance technique and spectroscopic methods,demonstrating that the nanodots also had oxidase-like activity.Interestingly,the peroxidase-like activity of nanodots was synergistically enhanced in the presence of ferrous ions or ferric ions.Remarkably,less than nanomolar levels of ferrous ions were required to display this phenomenon,meaning Fenton reagent acted as leverage.Based on this,a sensitive colorimetric and fluorescent dual-mode sensor for alendronate sodium was developed.The linear ranges for colorimetric and fluorescence analysis were 0.2–2.5 and 0.2–2.0μM,with detection limits of 31.21 and 71.84 nM,correspondingly.The method has a simple large-scale material preparation process with higher sensitivity and shorter reaction time,which can inspire and enlighten the design of nanozyme sensors.

Simultaneous photoinduced generation of Fe^(2+) and H_2O_2 in rivers:An indicator for photo-Fenton reaction

The photo-Fenton reaction is a key source of the highly reactive hydroxyl radical（HOU） that is produced by the reaction of simultaneous photo-induced generation of Fe^（2＋）-dissolved organic matter（DOM） with H_2O_2 in sunlit surface waters as well as in the treatment of organic pollutants in the advanced oxidation processes（AOPs）.Concentrations of both H_2O_2 and Fe^（2＋）-DOM were dependent on time and total solar intensity flux,and their levels were highest in the diurnal samples collected at noon compared with the samples collected during the period before sunrise and after sunset.H_2O_2 and Fe^（2＋）-DOM concentrations during monthly readings were also found higher in comparison with the diurnal samples,shortly before sunrise or after sunset.A π-electron bonding system is formed between Fe and the functional groups in DOM（Fe-DOM）,through electron donation from the functional groups of DOM to an empty d-orbital of Fe.The π-electron is loosely bound and is highly susceptible to a rapid excitation upon light exposure that will provide better understanding of the formation of aqueous electrons,superoxide radical anions,H_2O_2 and finally,photo-Fenton reactions,too.Our results imply that simultaneous generation of H_2O_2 and Fe^（2＋）-DOM upon sunlight exposure during the daytime is most likely to be the key photo-Fenton reaction pathway,taking place in surface waters.

Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide-driven recycled visible-photocatalytic Fenton reactions to mineralize organic pollutants in a wide pH range

Photocatalytic Fenton reactions combined the advantages from both photocatalysis and Fenton reaction in mineralizing organic pollutants. The key problems are the efficiency and recycling stability. Herein, we reported a novel Fe_(2)O_(3)/TiO_(2)/reduced graphene oxide(FTG) nanocomposite synthesized by a facile solvothermal method. The TiO_(2)in FTG degraded organic pollutants and mineralized intermediates via photocatalysis under visible light irradiation, which could also promote Fenton reaction by accelerating Fe^(3+)-Fe^(2+)recycle. Meanwhile, the Fe_(2)O_(3)rapidly degraded organic pollutants via Fenton reactions, which also promoted photocatalysis by enhancing visible light absorbance and diminishing photoelectronhole recombination. The high distribution of TiO_(2)and Fe_(2)O_(3)on rGO, together with their strong interaction resulted in enhanced synergetic cooperation between photocatalysis and Fenton reactions, leading to the high mineralization efficiency of organic pollutants. More importantly, it could also inhibit the leaching of Fe species, leading to the long lifetime of FTG during photocatalytic Fenton reactions in a wide pH range from 3.4 to 9.2.

非贵金属催化电极Ni/C@CF的制备及绿色类Fenton性能

传统芬顿(Fenton)法利用Fe2+催化H_(2)O_(2)产生具有强氧化性的羟基自由基(•OH),可以高效氧化降解水中有机污染物,但其操作pH范围窄(pH≈3)和易产生铁絮凝沉淀的缺点限制了其应用发展.原子氢H*作为一种单电子供体,可以将电子快速转移到H_(2)O_(2)中,生成•OH,适用于广泛的pH值,没有铁污泥产生,是一种新型高效绿色芬顿法.然而,原子H*更易相互结合形成H_(2),极不稳定,因此,探索合适的电催化剂对H*绿色Fenton的应用起着至关重要的作用.本文以炭黑作为载体,通过液相还原法制备了具有催化活性高、性能稳定的Ni/C@碳毡(Ni/C@CF)非贵金属电催化材料,制备的Ni纳米粒子均匀分散在炭黑上.以此电极材料为阴极,构建绿色Fenton催化体系,能够催化H_(2)O和H+生成H*,进而催化H_(2)O_(2)产生•OH,高效降解去除水中抗生素污染物.通过调节制备方法、电压、溶液pH值及外加氧化剂量,确定了该体系下的最佳反应条件.

First principles study of Fenton reaction catalyzed by FeOCl:reaction mechanism and location of active site

Fe-based solid catalysts in promoting Fenton reaction to generate ·OH radical has drawn much attention,and interestingly,FeOCl was reported to have superior activity compared with the traditional Fe2 O3 catalysts.However,the mechanism of Fenton reaction on FeOCl and the origin of high activity remain unclear.Herein,by virtue of DFT+ U calculations,the H2 O2 decomposition and conversion mechanism on FeOCl(100)surface were systematically investigated.It is found that on clean FeOCl(100)surface,the exposed[Fe^3+-Fe^3+]sites can hardly break O-O bond of H2 O2 into OH groups,but instead H2 O2 tends to dehydrogenate by the surface lattice O,resulting in a series of side reactions and final conversion into O2,while the left H atoms gradually saturate the surface lattice O and reduce Fe^3+ into Fe^2+.On fully H-covered FeOCl(100),H2O2 can efficiently dissociate at[Fe^2+-Fe^2+]sites into two OH,but OH binds with Fe^2+ so strongly that it cannot desorb as OH radical as easily as that on Fe^3+.Interestingly,FeOCl(100)tends to be partially protonated in the real acid solution,which,along with H2 O2 dehydrogenation,results in the formation of active unit [Fe^2+-Fe^3+].On[Fe^2+-Fe^3+]unit,H2 O2 can easily break its O-O bond and OH at Fe3+ can desorb as OH radical,while the other OH at Fe^2+ couples with the surface H into H2O and finish the catalytic cycle.By comparison,Fe2 O3(012)cannot provide enough [Fe^2+-Fe^3+] active units due to the relative difficulty in H2 O2 dehydrogenation,which accounts for its inferior catalytic efficiency for Fenton reaction.

Effects of iron(hydr)oxides on the degradation of diethyl phthalate ester in heterogeneous(photo)-Fenton reactions

This work studied the structural effects of hematite(α-Fe2 O3), 2-line ferrihydrite(HFO) and goethite(α-FeOOH) on diethyl phthalate ester(DEP) degradation. The results showed that the degradation of DEP was faster under 365 nm light irradiation than in the dark in the presence of iron(hydr)oxides. The apparent kinetic rates of DEP degradation followed the order HFO > goethite ≈ hematite in the dark and HFO > hematite > goethite under 365 nm light irradiation. Two pathways governed H2 O2 decomposition efficiency on iron(hydr)oxide surfaces:(1) forming UOH on inherent surface hydroxyl groups(Fe-OH) and(2) producing O2 and H2 O on the surface oxygen vacancies. X-ray photoelectron spectroscopy(XPS) analyses indicated that HFO not only has high Fe-OH content but also has high Vo content, resulting in its low H2 O2 utilization efficiency(η). DEP was degraded through hydrogen abstraction and deesterification, and the major products were(OH)2-DEP, mono-ethyl phthalate(MEP), OH-MEP,and phthalate acid(PA). The study is important in understanding the transformation of phthalate esters in top surface soils and surface waters under ultraviolet light.

凹凸棒负载碳-铁复合材料的制备及非均相Fenton反应降解水中亚甲基蓝的研究

以凹凸棒为载体,采用共沉淀法和热解法制备了新型凹凸棒负载碳-铁复合材料。通过X射线衍射仪、傅里叶变换红外光谱仪、冷场发射扫描电子显微镜、X射线光电子能谱仪、热重分析仪对复合材料进行表征,用亚甲基蓝水溶液模拟有机染料废水,考察复合材料在光暗体系下非均相Fenton催化降解亚甲基蓝的性能。结果表明,光照和暗环境下,最佳pH分别为4.0、3.5,反应120min时脱色率分别可达99.6%和96.3%。复合材料在光照环境下具有更好的催化活性,循环5次后,亚甲基蓝的脱色率仍可达99%,总有机碳去除率为42.2%,表现出良好的重复使用性。

蒙脱土在光助非均相Fenton 反应中的应用研究进展

蒙脱土因具有良好的阳离子交换能力和吸附能力被广泛用作非均相Fenton催化剂的载体。介绍了蒙脱土负载铁氧化物、蒙脱土负载改性铁氧化物和蒙脱土负载半导体/铁氧化物三类催化剂在非均相光-Fenton反应处理水中污染物的应用,就三类催化剂对污染物的降解机理和蒙脱土的作用进行分析,并对蒙脱土基非均相Fenton催化剂未来的研究方向进行探讨。

缺陷诱导电子-金属载体相互作用加速固液界面Fenton反应

水体污染物的深度氧化去除是环境领域的研究热点.芬顿反应作为典型的高级氧化技术(AOPs)被广泛用于水中有机污染物的去除.对于非均相芬顿反应,催化剂表面Fe^(3+)/Fe^(2+)的循环是决定其活性的主要因素.Fe^(3+)还原的关键在于接受额外电子,因此电子是提升芬顿反应效率的关键.传统非均相催化剂由于表面“惰性”,限制了固液界面电子的传递,导致Fe^(3+)/Fe^(2+)的循环效率处于较低的水平.因此设计一种具有高效界面电子传递性能的催化剂对提高芬顿反应效率至关重要.本文通过简易的酸处理法,成功合成了富含缺陷的NH_(2)-UiO-66(d-NU)材料,并将其用于水中有机污染物的去除.核磁共振氢谱(1H NMR)、热重分析(TG)、傅里叶红外光谱(FTIR)和X射线吸收精细结构(EXAFS)等多种表征证明了酸处理诱导NH_(2)-UiO-66上缺陷结构的形成.光电流、电化学阻抗和时间分辨瞬态荧光光谱结果表明,缺陷结构的形成可有效促进光生电子-空穴的分离.与不含缺陷的NH_(2)-UiO-66(NU)相比,d-NU在光芬顿氧化过程中表现出更优的4-CP去除效率,其降解动力学速率常数是NU的11倍,极大地加速了4-CP的去除进程.实验及理论计算结果表明缺陷的形成破坏了Zr配位结构的几何对称性,导致Zr位点电荷密度的不对称分布.该不对称结构有利于Fe^(3+)富集到Zr-O簇上,并通过电子-金属-载体相互作用(EMSI)形成Zr‒O‒Fe桥键,促进催化剂固液界面电子的传输,提高催化剂界面Fe^(3+)/Fe^(2+)的循环效率.实际应用实验结果表明,在d-NU/Fe^(3+)/H_(2)O_(2)光芬顿体系中,环境水体中常见无机离子对4-CP的降解影响很小.同时,d-NU/Fe^(3+)/H_(2)O_(2)光芬顿体系能够对多种有机污染物保持较高的去除效率,且催化活性在经过10次循环后没有明显的衰减,说明d-NU具有较好的抗离子干扰性、降解多种污染物的普适性和结构稳定性.通过液相色谱-质谱监测确定了4-CP的降解途径,并通过毒理学模拟4-CP及其降解生成中间体的生物毒性,结果表明,4-CP降解过程中形成的中间体的综合毒性低于4-CP.综上,本研究揭示了MOF基芬顿催化剂中金属氧簇的配位关系对芬顿反应的作用机制,提出了富含缺陷的MOFs与Fe^(3+)之间电子转移的作用机制,为进一步开发高效芬顿催化剂提供了新思路.