A phosphrous-containing poly（aryl ether ketone） was synthesized derived from bisphenol-A and bis[4-（4- fluorobenzoyl）phenyl] phenyl phosphine oxide （FPPPO） by nucleophilic substitution reaction. The structure of...A phosphrous-containing poly（aryl ether ketone） was synthesized derived from bisphenol-A and bis[4-（4- fluorobenzoyl）phenyl] phenyl phosphine oxide （FPPPO） by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature （Tg） of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer＇s CH2Cl2 solution. The limiting oxygen index （LOI） of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.展开更多
Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)...Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)or ZnCl_(2)as the activating agent into the polyacrylonitrile(PAN)in dimethylformamide solution for electrospinning prior to pyrolysis.Bisphenol-A(BPA),an endocrine disruption pollutant,is widely applied in the production of polycarbonate plastics and epoxy resins.Accordingly,BPA is often used as a model contaminant commonly removed via adsorption.Batch adsorption studies were used to evaluate the kinetics and adsorption capacity of the ACNFs.Redlich-Peterson(R-P)and Langmuir models were found to fit the isotherm of BPA adsorption better than Freundlich model,showing the homogeneous nature of the PAN originated ACNFs.The adsorption kinetics was better described by the pseudo second-order model than that by the pseudo first-order model.The fitting by intraparticle diffusion model indicates the adsorption of BPA onto ACNFs is mainly controlled by pore diffusion.High pH value and ionic strength reduced BPA adsorption from aqueous solution.The breakthrough curves studied in two different fixed bed systems(cross flow bed system and packed flow bed system)confirmed the scalability of BPA removal by ACNFs in dynamic adsorption processes.The modified dose-response model predicted well the fixed-bed outlet concentration profiles.展开更多
Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild con...Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.展开更多
Bisphenol-A（BPA） has been considered as an endocrine disrupting chemical（EDC） because it can exert estrogenic properties.For bisphenol-S（BPS） and bisphenol-F（BPF） that are BPA analogs and substitutes,their ris...Bisphenol-A（BPA） has been considered as an endocrine disrupting chemical（EDC） because it can exert estrogenic properties.For bisphenol-S（BPS） and bisphenol-F（BPF） that are BPA analogs and substitutes,their risk to estrogendependent cancer has been reported rarely compared with the numerous cases of BPA.In this study,we examined whether BPA,BPS,and BPF can lead to the proliferation,migration,and epithelial mesenchymal transition（EMT） of MCF-7 clonal variant（MCF-7 CV） breast cancer cells expressing estrogen receptors（ERs）.In a cell viability assay,BPA,BPS,and BPF significantly increased proliferation of MCF-7 CV cells compared to control（DMSO） as did17β-estradiol（E2）.In Western blotting assay,BPA,BPS,and BPF enhanced the protein expression of cell cycle progression genes such as cyclin D1 and E1.In addition,MCF-7 CV cells lost cell to cell contacts and acquired fibroblast-like morphology by the treatment of BPA,BPS,or BPF for 24 hours.In cell migration assay,BPA,BPS,and BPF accelerated the migration capability of MCF-7 CV cells as did E2.In relation with the EMT process,BPA,BPS,and BPF increased the protein expression of N-cadherin,while they decreased the protein expression of Ecadherin.When BPA,BPS,and BPF were co-treated with ICI 182,780,an ER antagonist,proliferation effects were reversed,the expression of cyclin D1 and cyclin E1 was downregulated,and the altered cell migration and expression of N-cadherin and E-cadherin by BPA,BPS,and BPF were restored to the control level.Thus,these results imply that BPS and BPF also have the risk of breast cancer progression as much as BPA in the induction of proliferation and migration of MCF-7 CV cells by regulating the protein expression of cell cycle-related genes and EMT markers via the ER-dependent pathway.展开更多
An Ethos EZ Microwave Lab Station is employed in the development of a robust and efficient microwave extraction method for organic contaminants of anthropogenic origin in river sediments. The extraction method is desi...An Ethos EZ Microwave Lab Station is employed in the development of a robust and efficient microwave extraction method for organic contaminants of anthropogenic origin in river sediments. The extraction method is designed for a small, representative set of target compounds encompassing a range of physicochemical properties. Listed in order of gas chromatography elution they are para-cresol, indole, 4-tert-octylphenol, phenanthrene, triclosan, bisphenol-A, carbamazepine, and benzo [a] pyrene. The sediments samples are extracted wet, which reduces preparation time, and allows the ambient moisture of the sediments to aid in microwave energy absorption and the extraction process. The microwave can hold up to 12 samples that can be simultaneously extracted allowing for rapid sample preparation. Utilizing the pressurized vessels, microwave energy, and a unique mixture of three organic solvents allows for multiple samples to be extracted rapidly with minimal solvent consumption. The final extracts are quantified by gas chromatography/mass spectrometry. Recoveries of the 8 target compounds in sediment range from 49% to 113%, and method detection limits range between 14 and 114 μg kg–1, which are comparable with other more time consuming methods.展开更多
Research efforts on permanganate(Mn(VII))combined with redox-mediator(RM),have received increasing attention due to their significant performance for bisphenol-A(BPA)removal.However,the mechanisms underpinning BPA deg...Research efforts on permanganate(Mn(VII))combined with redox-mediator(RM),have received increasing attention due to their significant performance for bisphenol-A(BPA)removal.However,the mechanisms underpinning BPA degradation remain underexplored.Here we show the overlooked interactions between RM and BPA during permanganate oxidation by introducing an RMdN-hydroxyphthalimide(NHPI).We discovered that the concurrent generation of MnO_(2) and phthalimide-N-oxyl(PINO)radical significantly enhances BPA oxidation within the pH range of 5.0e6.0.The detection of radical cross-coupling products between PINO radicals and BPA or its derivatives corroborates the pivotal role of radical cross-coupling in BPA oxidation.Intriguingly,we observed the formation of an NHPI-BPA complex,which undergoes preferential oxidation by Mn(VII),marked by the emergence of an electronrich domain in NHPI.These findings unveil the underlying mechanisms in the Mn(VII)/RM system and bridge the knowledge gap concerning BPA transformation via complexation.This research paves the way for further exploration into optimizing complexation sites and RM dosage,significantly enhancing the system's efficiency in water treatment applications.展开更多
This study investigated the degradation of bisphenol-A （BPA） by ultrasonic irradiation in the presence of different additives （H2O2, air bubbles and humic acid） under various operating conditions, i.e., ultrasonic...This study investigated the degradation of bisphenol-A （BPA） by ultrasonic irradiation in the presence of different additives （H2O2, air bubbles and humic acid） under various operating conditions, i.e., ultrasonic frequency, power intensity and power density. The results demonstrated that the BPA degradation followed pseudo first-order kinetics under different experimental conditions. The optimum power intensities were 0.9, 1.8, and 3.0 W/cm2 at the frequencies of 400, 670, and 800 kHz, respectively. At the fixed frequency （800 kHz）, the degradation rate of BPA was shown proportional to the increase of power density applied. With this manner, the BPA sonolysis could be facilitated at H202 dosage being lower than 0.1 mmol/L; while BPA degradation was hindered at H202 concentration in excess of 1 mmol/L. Additionally, BPA removal was shown to be inhibited by the presence of aeration and humic acid during ultrasonic irradiation. The present study suggested that the degradation rate of BPA assisted by ultrasonic irradiation was influenced by a variety of factors, and high BPA removal rate could be achieved under appropriate conditions.展开更多
A Zn Cl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was prepared by the ion exchange method. Scanning electron microscope（SEM）, Fourier transform infrared spectrophotometer（FT-IR）, therm...A Zn Cl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was prepared by the ion exchange method. Scanning electron microscope（SEM）, Fourier transform infrared spectrophotometer（FT-IR）, thermo gravimetric analyzer（TGA） and pyridine adsorbed IR were employed to characterize the catalyst. As a result, the modified catalyst showed high acidity and good thermal stability. Zn2＋coordinated with a sulfonic acid group to form a stable active site, which effectively decreased the deactivation caused by the degradation of sulfonic acid. Thus the prepared catalyst exhibited excellent catalytic activity, selectivity and stability compared to the unmodified counterpart.展开更多
基金This work was supported by the National Natural Science Foundation of China(No.50203008).
文摘A phosphrous-containing poly（aryl ether ketone） was synthesized derived from bisphenol-A and bis[4-（4- fluorobenzoyl）phenyl] phenyl phosphine oxide （FPPPO） by nucleophilic substitution reaction. The structure of the polymer was characterized by FT-IR, ^1H-NMR and ^31p-NMR. The thermal property of the PAEK was measured by DSC and TGA. The glass transition temperature （Tg） of the polymer was 205℃, and the 5% weight loss temperature under nitrogen was 475℃. Good solubility of the polymer in organic solvents, such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide and chloroalkanes was observed, flexible film was obtained from the polymer＇s CH2Cl2 solution. The limiting oxygen index （LOI） of the PAEK was 40, which indicated that organic phosphorus moiety can offer good flame retardant property to the polymer.
基金financially supported by the National Science Foundation(1438518)。
文摘Activated carbon nanofibers(ACNFs)with small diameter can significantly increase the accessibility of intra pores and accelerate adsorption of molecules from water.In this study,ACNFs were made by blending K_(2)CO_(3)or ZnCl_(2)as the activating agent into the polyacrylonitrile(PAN)in dimethylformamide solution for electrospinning prior to pyrolysis.Bisphenol-A(BPA),an endocrine disruption pollutant,is widely applied in the production of polycarbonate plastics and epoxy resins.Accordingly,BPA is often used as a model contaminant commonly removed via adsorption.Batch adsorption studies were used to evaluate the kinetics and adsorption capacity of the ACNFs.Redlich-Peterson(R-P)and Langmuir models were found to fit the isotherm of BPA adsorption better than Freundlich model,showing the homogeneous nature of the PAN originated ACNFs.The adsorption kinetics was better described by the pseudo second-order model than that by the pseudo first-order model.The fitting by intraparticle diffusion model indicates the adsorption of BPA onto ACNFs is mainly controlled by pore diffusion.High pH value and ionic strength reduced BPA adsorption from aqueous solution.The breakthrough curves studied in two different fixed bed systems(cross flow bed system and packed flow bed system)confirmed the scalability of BPA removal by ACNFs in dynamic adsorption processes.The modified dose-response model predicted well the fixed-bed outlet concentration profiles.
文摘Four series of copolyesters were synthesized by direct polycondonsation reaction between aromatic dicarboxylic acids and bisphenols by using tosyi chloride and N, N-dimethylformamide ( DMF ) in pyridine under mild conditions. The electron-rich hydroxyl groups of bisphenols favoured the polycondensation reaction and the order of relative reactivities of bisphenols is as follow:bisphenoI-A> hydroquinone ～ bisphenol-S> chlorohydroquinone. The mesomorphic properties of copolyesters were examined by birefringence under polarizing microscope, melt transparency. DSC and X-ray diffraction. The minimum molar fraction of mesogenic units needed for the appearance of liquid crystallinity is not higher than 0. 1 despite of the different varieties and lengths of the spacers studied.
基金supported by a grant from the NextGeneration BioGreen 21 Program(no.PJ011355-2015)supported by Priority Research Centers Program through NRF funded by the Ministry of Education,Science and Technology (2015R1A6A1A04020885)
文摘Bisphenol-A（BPA） has been considered as an endocrine disrupting chemical（EDC） because it can exert estrogenic properties.For bisphenol-S（BPS） and bisphenol-F（BPF） that are BPA analogs and substitutes,their risk to estrogendependent cancer has been reported rarely compared with the numerous cases of BPA.In this study,we examined whether BPA,BPS,and BPF can lead to the proliferation,migration,and epithelial mesenchymal transition（EMT） of MCF-7 clonal variant（MCF-7 CV） breast cancer cells expressing estrogen receptors（ERs）.In a cell viability assay,BPA,BPS,and BPF significantly increased proliferation of MCF-7 CV cells compared to control（DMSO） as did17β-estradiol（E2）.In Western blotting assay,BPA,BPS,and BPF enhanced the protein expression of cell cycle progression genes such as cyclin D1 and E1.In addition,MCF-7 CV cells lost cell to cell contacts and acquired fibroblast-like morphology by the treatment of BPA,BPS,or BPF for 24 hours.In cell migration assay,BPA,BPS,and BPF accelerated the migration capability of MCF-7 CV cells as did E2.In relation with the EMT process,BPA,BPS,and BPF increased the protein expression of N-cadherin,while they decreased the protein expression of Ecadherin.When BPA,BPS,and BPF were co-treated with ICI 182,780,an ER antagonist,proliferation effects were reversed,the expression of cyclin D1 and cyclin E1 was downregulated,and the altered cell migration and expression of N-cadherin and E-cadherin by BPA,BPS,and BPF were restored to the control level.Thus,these results imply that BPS and BPF also have the risk of breast cancer progression as much as BPA in the induction of proliferation and migration of MCF-7 CV cells by regulating the protein expression of cell cycle-related genes and EMT markers via the ER-dependent pathway.
文摘An Ethos EZ Microwave Lab Station is employed in the development of a robust and efficient microwave extraction method for organic contaminants of anthropogenic origin in river sediments. The extraction method is designed for a small, representative set of target compounds encompassing a range of physicochemical properties. Listed in order of gas chromatography elution they are para-cresol, indole, 4-tert-octylphenol, phenanthrene, triclosan, bisphenol-A, carbamazepine, and benzo [a] pyrene. The sediments samples are extracted wet, which reduces preparation time, and allows the ambient moisture of the sediments to aid in microwave energy absorption and the extraction process. The microwave can hold up to 12 samples that can be simultaneously extracted allowing for rapid sample preparation. Utilizing the pressurized vessels, microwave energy, and a unique mixture of three organic solvents allows for multiple samples to be extracted rapidly with minimal solvent consumption. The final extracts are quantified by gas chromatography/mass spectrometry. Recoveries of the 8 target compounds in sediment range from 49% to 113%, and method detection limits range between 14 and 114 μg kg–1, which are comparable with other more time consuming methods.
基金supported by the National Natural Science Foundations of China(No.22076016).
文摘Research efforts on permanganate(Mn(VII))combined with redox-mediator(RM),have received increasing attention due to their significant performance for bisphenol-A(BPA)removal.However,the mechanisms underpinning BPA degradation remain underexplored.Here we show the overlooked interactions between RM and BPA during permanganate oxidation by introducing an RMdN-hydroxyphthalimide(NHPI).We discovered that the concurrent generation of MnO_(2) and phthalimide-N-oxyl(PINO)radical significantly enhances BPA oxidation within the pH range of 5.0e6.0.The detection of radical cross-coupling products between PINO radicals and BPA or its derivatives corroborates the pivotal role of radical cross-coupling in BPA oxidation.Intriguingly,we observed the formation of an NHPI-BPA complex,which undergoes preferential oxidation by Mn(VII),marked by the emergence of an electronrich domain in NHPI.These findings unveil the underlying mechanisms in the Mn(VII)/RM system and bridge the knowledge gap concerning BPA transformation via complexation.This research paves the way for further exploration into optimizing complexation sites and RM dosage,significantly enhancing the system's efficiency in water treatment applications.
基金supported by the National Natural Science Foundation of China (No.50878163,50708067)the National Major Project of Science & Technology Ministry of China (No.2008ZX07421-002)+1 种基金the National High Technology Research and Development Program (863) of China (No.2008AA06A412)the Research and Development Project of Ministry of Housing and Urban-Rural Development (No. 2009-K7-4)
文摘This study investigated the degradation of bisphenol-A （BPA） by ultrasonic irradiation in the presence of different additives （H2O2, air bubbles and humic acid） under various operating conditions, i.e., ultrasonic frequency, power intensity and power density. The results demonstrated that the BPA degradation followed pseudo first-order kinetics under different experimental conditions. The optimum power intensities were 0.9, 1.8, and 3.0 W/cm2 at the frequencies of 400, 670, and 800 kHz, respectively. At the fixed frequency （800 kHz）, the degradation rate of BPA was shown proportional to the increase of power density applied. With this manner, the BPA sonolysis could be facilitated at H202 dosage being lower than 0.1 mmol/L; while BPA degradation was hindered at H202 concentration in excess of 1 mmol/L. Additionally, BPA removal was shown to be inhibited by the presence of aeration and humic acid during ultrasonic irradiation. The present study suggested that the degradation rate of BPA assisted by ultrasonic irradiation was influenced by a variety of factors, and high BPA removal rate could be achieved under appropriate conditions.
文摘A Zn Cl2-modified ion exchange resin as the catalyst for bisphenol-A synthesis was prepared by the ion exchange method. Scanning electron microscope（SEM）, Fourier transform infrared spectrophotometer（FT-IR）, thermo gravimetric analyzer（TGA） and pyridine adsorbed IR were employed to characterize the catalyst. As a result, the modified catalyst showed high acidity and good thermal stability. Zn2＋coordinated with a sulfonic acid group to form a stable active site, which effectively decreased the deactivation caused by the degradation of sulfonic acid. Thus the prepared catalyst exhibited excellent catalytic activity, selectivity and stability compared to the unmodified counterpart.
