Decabromodiphenyl ethane(DBDPE)is widely used as an additive flame retardant and has led to global pollution.Its has a large molecular mass and is prone to debromination and degradation under photothermal conditions,r...Decabromodiphenyl ethane(DBDPE)is widely used as an additive flame retardant and has led to global pollution.Its has a large molecular mass and is prone to debromination and degradation under photothermal conditions,resulting in smaller homologous compounds.Due to the lack of standard substances for debromination products,the in-depth study of DBDPE environmental geochemical behavior through debromination conversion has been hindered.Therefore,based on DBDPE photodegradation experiment,this study first analyzed and identified the brominated products of DBDPE using high-performance liquid chromatography-atmospheric pressure photoionization-time of flight mass spectrometry(HPLC-APPI-TOF/MS).Four debromination products-nonabromodiphenyl ethane(nonaBDPE),octabromodiphenyl ethane(octa-BDPE),heptabromodiphenyl ethane(hepta-BDPE)and hexabromodiphenyl ethane(hexa-BDPE)are identified based on the characteristic ion peak of[M-Br+O]^(-) in negative ion mode.Subsequently,using methanol as the mobile phase,four debromination products of DBDPE were separated and purified with a semi-preparative high-performance liquid chromatography(SP-HPLC)system equipped with an Agilent Zorbax Eclipse PAH column(4.6 mm×250 mm,5μm).The first-time acquisition of hexa-BDPE(60.00μg),octa-BDPE(19.40μg),hepta-BDPE(31.20μg)and octa-BDPE(isomer,45.20μg)with purity exceeding 90%has been achieved.Among them,the purity of one hepta-BDPE monomer is as high as 98.91%.This study indicates that based on photodegradation experiments,the combination of HPLC-APPI-TOF/MS and SP-HPLC techniques can rapidly identify and prepare DBDPE debrominated products.This approach meets the requirements for preliminary research on the pollution characteristics of DBDPE debrominated compounds and offers a feasible solution for the preparation of standard reference materials for emerging pollutants.展开更多
Uptake, translocation and debromination of three polybrominated diphenyl ethers （PBDEs）, BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solution...Uptake, translocation and debromination of three polybrominated diphenyl ethers （PBDEs）, BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability. PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants. Furthermore, PBDE concentrations decreased from roots to stems and then to leaves, and a very clear decreasing gradient was found in segments upwards along the stem. These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize. More highly brominated PBDEs were translocated with more difficulty. Radial translocation of PBDEs from nodes to sheath inside maize was also observed. Both acropetal and radial translocations were enhanced at higher transpiration rates, suggesting that PBDE transport was probably driven by the transpiration stream. Debromination of PBDEs occurred in all parts of the maize, and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences. This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants, elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.展开更多
Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we s...Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol（4-BP） by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH（6.1–10） and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.展开更多
Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides wi...Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides with metallic zinc powder in aqueous media has been developed, which generates E-alkenes with excellent yields. The reactivity of vic-dibromides decreases in the order of 1,2-dibromo-1,2-diphenylethane>1,2-dibromo-1-phenylethane>1,2-dibromo-1,2-dialkylethane.展开更多
Polybrominated diphenyl ethers(PBDEs)are widely used as brominated flame retardants,which had attracted amounts of attention due to their harmful characteristics of high toxicity,environmental persistence and potentia...Polybrominated diphenyl ethers(PBDEs)are widely used as brominated flame retardants,which had attracted amounts of attention due to their harmful characteristics of high toxicity,environmental persistence and potential bioaccumulation.Many chemical reductive debromination technologies have been developed for the debromination of PBDEs,including photolysis,photocatalysis,electrocatalysis,zero-valent metal reduction,chemically catalytic reduction and mechanochemical method.This review aims to provide information about the degradation thermodynamics and kinetics of PBDEs and summarize the degradation mechanisms in various systems.According to the comparative analysis,the rapid debromination to generate bromine-free products in an electron-transfer process,of which photocatalysis is a representative one,is found to be relatively difficult,because the degradation rate of PBDEs depended on the Br-rich phenyl ring with the lowest unoccupied molecular orbital(LUMO)localization.On the contrary,the complete debromination occurs easily in other systems with active hydrogen atoms as the main reactive species,such as chemically catalytic reduction systems.The review provides the knowledge on the chemical reductive technique of PBDEs,which would greatly help not only clarify the degradation mechanism but also design the more efficient system for the rapid and deep debromination of PBDEs in the future.展开更多
The ? ?vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.
The debromination of diphenyl bromomethane (Ph_2CHBr) using polymers with viologen structure as electron--transfer catalyst (ETC) afforded tetraphenylethane in good yields under het- erophase conditions.
The active intermediate'carbon radical' was detected by the spin—trapping reagent (POBN) during the debromination of Ph_2CHBr in the presence of viologen derivatives as electron—transfer catalysts(ETC).
In the presence of equimolar triethylamine,vicinal dibromides were found to be easily debrominated by dibutyl telluride,forming the co- rresponding olefins.
研究了改性蒙脱石负载纳米铁材料(NZVI-CMT)在甲醇-水体系中对四溴双酚A(TBBPA)的去除作用,并确定了反应温度、TBBPA初始浓度以及材料投加量等因素对去除效果的影响.结果表明,在25℃条件下,0.02 g NZVI-CMT对初始浓度为10 mg·L-1TB...研究了改性蒙脱石负载纳米铁材料(NZVI-CMT)在甲醇-水体系中对四溴双酚A(TBBPA)的去除作用,并确定了反应温度、TBBPA初始浓度以及材料投加量等因素对去除效果的影响.结果表明,在25℃条件下,0.02 g NZVI-CMT对初始浓度为10 mg·L-1TBBPA溶液的去除率可达97.5%,而且NZVI-CMT对TBBPA的去除率明显高于两种单一材料即纳米零价铁(NZVI)及有机蒙脱石(CMT)的去除率(18.3%、67.3%),同时也大于两者之和(85.6%).利用NZVI-CMT对TBBPA进行重复去除实验时,前3次的去除率均可达到90%以上.通过检测降解产物并分析材料对TBBPA去除过程的特性,发现NZVI-CMT对TBBPA的去除以吸附为主,并伴有少量还原脱溴反应发生,而且较高的反应温度对降解反应有利.展开更多
基金supported by the National Natural Science Foundation of China(Nos.42107284 and 22078177)the Postdoctoral Fellowship Program of CPSF(No.GZB20240410)。
文摘Decabromodiphenyl ethane(DBDPE)is widely used as an additive flame retardant and has led to global pollution.Its has a large molecular mass and is prone to debromination and degradation under photothermal conditions,resulting in smaller homologous compounds.Due to the lack of standard substances for debromination products,the in-depth study of DBDPE environmental geochemical behavior through debromination conversion has been hindered.Therefore,based on DBDPE photodegradation experiment,this study first analyzed and identified the brominated products of DBDPE using high-performance liquid chromatography-atmospheric pressure photoionization-time of flight mass spectrometry(HPLC-APPI-TOF/MS).Four debromination products-nonabromodiphenyl ethane(nonaBDPE),octabromodiphenyl ethane(octa-BDPE),heptabromodiphenyl ethane(hepta-BDPE)and hexabromodiphenyl ethane(hexa-BDPE)are identified based on the characteristic ion peak of[M-Br+O]^(-) in negative ion mode.Subsequently,using methanol as the mobile phase,four debromination products of DBDPE were separated and purified with a semi-preparative high-performance liquid chromatography(SP-HPLC)system equipped with an Agilent Zorbax Eclipse PAH column(4.6 mm×250 mm,5μm).The first-time acquisition of hexa-BDPE(60.00μg),octa-BDPE(19.40μg),hepta-BDPE(31.20μg)and octa-BDPE(isomer,45.20μg)with purity exceeding 90%has been achieved.Among them,the purity of one hepta-BDPE monomer is as high as 98.91%.This study indicates that based on photodegradation experiments,the combination of HPLC-APPI-TOF/MS and SP-HPLC techniques can rapidly identify and prepare DBDPE debrominated products.This approach meets the requirements for preliminary research on the pollution characteristics of DBDPE debrominated compounds and offers a feasible solution for the preparation of standard reference materials for emerging pollutants.
基金supported by the National Basic Research Program (973) of China (No. 2009CB421603)the National Natural Science Foundation of China (No.40730740, 20921063, 20807048)
文摘Uptake, translocation and debromination of three polybrominated diphenyl ethers （PBDEs）, BDE-28, -47 and -99, in maize were studied in a hydroponic experiment. Roots took up most of the PBDEs in the culture solutions and more highly brominated PBDEs had a stronger uptake capability. PBDEs were detected in the stems and leaves of maize after exposure but rarely detected in the blank control plants. Furthermore, PBDE concentrations decreased from roots to stems and then to leaves, and a very clear decreasing gradient was found in segments upwards along the stem. These altogether provide substantiating evidence for the acropetal translocation of PBDEs in maize. More highly brominated PBDEs were translocated with more difficulty. Radial translocation of PBDEs from nodes to sheath inside maize was also observed. Both acropetal and radial translocations were enhanced at higher transpiration rates, suggesting that PBDE transport was probably driven by the transpiration stream. Debromination of PBDEs occurred in all parts of the maize, and debromination patterns of different parent PBDEs and in different parts of a plant were similar but with some differences. This study for the first time provides direct evidence for the acropetal translocation of PBDEs within plants, elucidates the process of PBDE transport and clarifies the debromination products of PBDEs in maize.
基金supported by the National Natural Science Foundation of China(No.21307057)the Natural Science Foundation of Jiangsu Province(No.BK20130577)+1 种基金the Specialized Research Fund for the Doctoral Program of Higher Education of China(SRFDP,No.20130091120014)the Fundamental Research Funds for the Central Universities(No.20620140128)
文摘Halogenated aromatic compounds have attracted increasing concerns due to their toxicity and persistency in the environment, and dehalogenation is one of the promising treatment and detoxification methods. Herein, we systematically studied the debromination efficiency and mechanism of para-bromophenol（4-BP） by a recently developed UV/sulfite process. 4-BP underwent rapid degradation with the kinetics accelerated with the increasing sulfite concentration, pH（6.1–10） and temperature, whereas inhibited by dissolved oxygen and organic solvents. The apparent activation energy was estimated to be 27.8 kJ/mol. The degradation mechanism and pathways of 4-BP were explored by employing N2O and nitrate as the electron scavengers and liquid chromatography/mass spectrometry to identify the intermediates. 4-BP degradation proceeded via at least two pathways including direct photolysis and hydrated electron-induced debromination. The contributions of both pathways were distinguished by quantifying the quantum yields of 4-BP via direct photolysis and hydrated electron production in the system. 4-BP could be readily completely debrominated with all the substituted Br released as Br-, and the degradation pathways were also proposed. This study would shed new light on the efficient dehalogenation of brominated aromatics by using the UV/sulfite process.
基金Supported by the National Natural Science Foundation of China(No.2 0 372 0 2 4 2 0 172 0 18) +2 种基金the Excellent ScientistFoundation of Anhui ProvinceChina(No.2 0 0 10 4 0 ) the Natural Science Foundation of the Educational Departm entof AnhuiProvince
文摘Carbon-carbon double bond functional groups are often protected through a popular bromination/debromination method because of their reactivity. An ultrasonic-enhanced stereoselective debromination of vic-dibromides with metallic zinc powder in aqueous media has been developed, which generates E-alkenes with excellent yields. The reactivity of vic-dibromides decreases in the order of 1,2-dibromo-1,2-diphenylethane>1,2-dibromo-1-phenylethane>1,2-dibromo-1,2-dialkylethane.
基金supported by the National Natural Science Foundation of China(Nos.21707170,21777194 and 22076052)the Natural Science Foundation of Hubei Province(No.2021CFB535)the Fundamental Research Funds for the Central Universities of South-Central MinZu University(No.CZT20019).
文摘Polybrominated diphenyl ethers(PBDEs)are widely used as brominated flame retardants,which had attracted amounts of attention due to their harmful characteristics of high toxicity,environmental persistence and potential bioaccumulation.Many chemical reductive debromination technologies have been developed for the debromination of PBDEs,including photolysis,photocatalysis,electrocatalysis,zero-valent metal reduction,chemically catalytic reduction and mechanochemical method.This review aims to provide information about the degradation thermodynamics and kinetics of PBDEs and summarize the degradation mechanisms in various systems.According to the comparative analysis,the rapid debromination to generate bromine-free products in an electron-transfer process,of which photocatalysis is a representative one,is found to be relatively difficult,because the degradation rate of PBDEs depended on the Br-rich phenyl ring with the lowest unoccupied molecular orbital(LUMO)localization.On the contrary,the complete debromination occurs easily in other systems with active hydrogen atoms as the main reactive species,such as chemically catalytic reduction systems.The review provides the knowledge on the chemical reductive technique of PBDEs,which would greatly help not only clarify the degradation mechanism but also design the more efficient system for the rapid and deep debromination of PBDEs in the future.
基金Project supported by the National Natural Science Foundation of China(No.29872010)the Natural Science Foundation of Zhejiang Province(No.298067)
文摘The ? ?vicinal dibromo carboxylic acid and its derivatives were debrominated with Sm/HOAc system to afford the corresponding cinnamic acid and its derivatives in good yields under mild conditions.
文摘The debromination of diphenyl bromomethane (Ph_2CHBr) using polymers with viologen structure as electron--transfer catalyst (ETC) afforded tetraphenylethane in good yields under het- erophase conditions.
文摘The active intermediate'carbon radical' was detected by the spin—trapping reagent (POBN) during the debromination of Ph_2CHBr in the presence of viologen derivatives as electron—transfer catalysts(ETC).
文摘In the presence of equimolar triethylamine,vicinal dibromides were found to be easily debrominated by dibutyl telluride,forming the co- rresponding olefins.
文摘研究了改性蒙脱石负载纳米铁材料(NZVI-CMT)在甲醇-水体系中对四溴双酚A(TBBPA)的去除作用,并确定了反应温度、TBBPA初始浓度以及材料投加量等因素对去除效果的影响.结果表明,在25℃条件下,0.02 g NZVI-CMT对初始浓度为10 mg·L-1TBBPA溶液的去除率可达97.5%,而且NZVI-CMT对TBBPA的去除率明显高于两种单一材料即纳米零价铁(NZVI)及有机蒙脱石(CMT)的去除率(18.3%、67.3%),同时也大于两者之和(85.6%).利用NZVI-CMT对TBBPA进行重复去除实验时,前3次的去除率均可达到90%以上.通过检测降解产物并分析材料对TBBPA去除过程的特性,发现NZVI-CMT对TBBPA的去除以吸附为主,并伴有少量还原脱溴反应发生,而且较高的反应温度对降解反应有利.
