The amidoximated polyacrylonitrile （PAN） fiber Fe complexeswere prepared and used as the heterogeneous Fenton catalysts for thedegradation of28 anionicwater soluble azodyes inwater under visible irradiation. The mul...The amidoximated polyacrylonitrile （PAN） fiber Fe complexeswere prepared and used as the heterogeneous Fenton catalysts for thedegradation of28 anionicwater soluble azodyes inwater under visible irradiation. The multiple linear regression （MLR） methodwas employed todevelop the quantitative structure property relationship （QSPR） model equations for thedecoloration and mineralization of azodyes. Moreover, the predictive ability of the QSPR model equationswas assessed using Leave-one-out （LOO） and cross-validation （CV） methods. Additionally, the effect of Fe content of catalyst and the sodium chloride inwater on QSPR model equationswere also investigated. The results indicated that the heterogeneous photo-Fentondegradation of the azodyeswithdifferent structureswas conducted in the presence of the amidoximated PAN fiber Fe complex. The QSPR model equations for thedyedecoloration and mineralizationwere successfullydeveloped using MLR technique. MW/S （molecularweightdivided by the number of sulphonate groups） and N N=N （the number of azo linkage） are considered as the most importantdetermining factor for thedyedegradation and mineralization, and there is a significant negative correlation between MW/S or N N=N anddegradation percentage or total organic carbon （TOC） removal. Moreover, LOO and CV analysis suggested that the obtained QSPR model equations have the better prediction ability. The variation in Fe content of catalyst and the addition of sodium chloridedid not alter the nature of the QSPR model equations.展开更多
Tumor cell resistance is one of the big hurdles limiting the therapeutic efficacy of tumor necrosis factorrelated apoptosis-inducing ligand(TRAIL)-based cancer treatment.Therefore,the development of a sa fe and effect...Tumor cell resistance is one of the big hurdles limiting the therapeutic efficacy of tumor necrosis factorrelated apoptosis-inducing ligand(TRAIL)-based cancer treatment.Therefore,the development of a sa fe and effective sensitizer agent is greatly desired for optimizing TRAIL therapy.Herein,we successfully developed a Se/Fe complex with low toxicity to highly effectively inhibit tumor cells proliferation and migration capabilities through down-regulating ER stress related selenoproteins.Furthermore,it could more efficiently damage tumor spheroids with good penetration capability.More importantly,it could synergize with TRAIL treatment to induce the robust generation of reactive oxygen species(ROS),downregulating ER stress related selenoproteins for triggering tumor cells apoptosis in extrinsic and intrinsic signaling pathways.Taken together,this study provides a potential chemo-drug and sensitizer agent to improve the therapeutic efficacy of TRAIL-based cancer treatment.展开更多
A Fe-complexed dye containing crosslinkable polyamine groups was synthesized through diazotization and coupling reaction, chlorination, amination and metallization. The structure of the Fe-complexed crosslinking dye w...A Fe-complexed dye containing crosslinkable polyamine groups was synthesized through diazotization and coupling reaction, chlorination, amination and metallization. The structure of the Fe-complexed crosslinking dye was characterized by FT-IR and Atomic Absorption Spectroscopic techniques. The dyeing and light fastness properties of the Fe-complex on silk and wool were tested, and the results showed that the novel Fe-complex exhibited both high fixation and good light fastness.展开更多
Two azo dyes,C.I.Reactive Red 195(RR195)and C.I.Acid Black 234(AB234)were degraded by photocatalysis of Fe(Ⅲ)-oxalate complexes/H2O2 in aqueous non-ionic surfactant,Triton X-100(TX-100)solution.Some factors affecting...Two azo dyes,C.I.Reactive Red 195(RR195)and C.I.Acid Black 234(AB234)were degraded by photocatalysis of Fe(Ⅲ)-oxalate complexes/H2O2 in aqueous non-ionic surfactant,Triton X-100(TX-100)solution.Some factors affecting the dye degradation such as TX-100 concentration,irradiation intensity,and sodium chloride were investigated.The interaction and competition between dye and TX-100 during the degradation were also examined using spectrophotometry and maximum bubble pressure method,respectively.The results indicated that TX-100 showed a significant reduction effect on degradation of two azo dyes,but which was largely confined to TX-100 concentration below the Critical Micellar Concentration(CMC).And the reduction was considerably decreased above the CMC,especially in the case of AB234.Moreover,the reducing effect of TX-100 on dye degradation almost did not vary with irradiation intensity.And the impact of sodium chloride on dye degradation was limited by the addition of TX-100.展开更多
Fe(Ⅱ) complex Fe[HB(pz)_3]_2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)_3]_2(compound 2) have been obtained by the reaction of MCI_2(M=Fe and Ni) with NaHB(pz)_3 in MeOH. The two complexes(compounds 1 and ...Fe(Ⅱ) complex Fe[HB(pz)_3]_2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)_3]_2(compound 2) have been obtained by the reaction of MCI_2(M=Fe and Ni) with NaHB(pz)_3 in MeOH. The two complexes(compounds 1 and 2) were characterized by IR, NMR, elemental analysis and X-ray diffraction. Compound 1 crystallizes in space group P2_1/c with a=1.224(3) nm, b=1.161(2) nm, c=1.648(3) nm, β=107.62(15)°, V=2.233(8) nm3, Z=2. Compound 2 crystallizes in space group P2_1/c with a=0.97926(18) nm, b= 1.7423(3) nm, c=1.3156(2) nm, β=97.055(16)°, V=2.2277(7) nm3, Z=4. The results of X-ray structural analyses show that both compounds 1 and 2 are monomeric neutral, possessing a similar coordination mode and a similar structure around the metal centers. The related spectral characterizations, steric effects and binding properties are discussed.展开更多
The aqueous photodegradation of bisphenol A （BPA） in the presence of Fe（Ⅲ）-oxalate complexes （Fe（Ⅲ）-Ox）, which are common compositions of natural water, was investigated in this study. BPA underwent rapid in...The aqueous photodegradation of bisphenol A （BPA） in the presence of Fe（Ⅲ）-oxalate complexes （Fe（Ⅲ）-Ox）, which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe（Ⅲ）-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial BPA level and increasing Fe（Ⅲ）/oxalate concentration ratio. Hydroxyl radicals （·OH）, which were generated from the photochemical processes of Fe（Ⅲ）-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance （ESR） methods with the steady-state concentration of 2.56 × 10^-14 mol/L. Superoxide anion radical （O2^·-） was considered as the precursor of. OH and qualitatively determined by adding nitro blue tetrazolium as well as ESR experiments. Based on the structural analysis of the intermediate photoproducts of BPA in Fe（Ⅲ）-Ox complexes solution, the possible degradation pathways of BPA were proposed, involving ·OH addition, alkyl scission and alky oxidation. The results indicate that the photochemical reactivity of Fe（Ⅲ） may affect the environmental fate of BPA in natural water significantly.展开更多
The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and t...The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..展开更多
Concentrations of dissolved organic matter (DOM), dissolved humic substances (DHS), and DOM-complexed Fe (DOM-Fe) in Yamakuni and Oita Rivers, Japan, of which headstream is near in location, flow pass length is simila...Concentrations of dissolved organic matter (DOM), dissolved humic substances (DHS), and DOM-complexed Fe (DOM-Fe) in Yamakuni and Oita Rivers, Japan, of which headstream is near in location, flow pass length is similar, but watershed soil type differs, were investigated. Soil organic matter level was higher in black Andosols distributing 67% of the watershed area of the Oita River than in Cambisols covering 90% of the watershed area of Yamakuni River. However, the DOM concentration in the Yamakuni River (0.44 - 1.62 mg·C·L-1) tended to be higher than that in the Oita River (0.13 - 1.37 mg·C·L-1). DHS accounted for 49% - 80% of DOM in both rivers. Fe and DOM-Fe concentrations showed a trend to increase toward downstream but decrease at the estuary in both rivers. DOM-Fe accounted for 26% - 90% and 55% - 93% of dissolved Fe in the Yamakuni and Oita Rivers, respectively. Correlation analysis suggested that the DOM-Fe concentration in the river water was controlled by the capacity for supplying Fe ions rather than that for supplying DOM. Although the ability to form a complex with Fe was suggested to be greater in the DOM in the Oita River than that in the Yamakuni River, the DOM-Fe concentration at the estuary was similar in the two rivers. Thus, the effect of soil organic matter level in the watershed area on the supply of Fe or DOM-Fe to the estuarine ecosystem was not significant.展开更多
Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all...Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.展开更多
基金supported by the Research Program of Application Foundation and Advanced Technology from the Tianjin Municipal Science and Technology Committee(No.11JCZDJ24600)the Natural Science Foundationof China(No.20773093)
文摘The amidoximated polyacrylonitrile （PAN） fiber Fe complexeswere prepared and used as the heterogeneous Fenton catalysts for thedegradation of28 anionicwater soluble azodyes inwater under visible irradiation. The multiple linear regression （MLR） methodwas employed todevelop the quantitative structure property relationship （QSPR） model equations for thedecoloration and mineralization of azodyes. Moreover, the predictive ability of the QSPR model equationswas assessed using Leave-one-out （LOO） and cross-validation （CV） methods. Additionally, the effect of Fe content of catalyst and the sodium chloride inwater on QSPR model equationswere also investigated. The results indicated that the heterogeneous photo-Fentondegradation of the azodyeswithdifferent structureswas conducted in the presence of the amidoximated PAN fiber Fe complex. The QSPR model equations for thedyedecoloration and mineralizationwere successfullydeveloped using MLR technique. MW/S （molecularweightdivided by the number of sulphonate groups） and N N=N （the number of azo linkage） are considered as the most importantdetermining factor for thedyedegradation and mineralization, and there is a significant negative correlation between MW/S or N N=N anddegradation percentage or total organic carbon （TOC） removal. Moreover, LOO and CV analysis suggested that the obtained QSPR model equations have the better prediction ability. The variation in Fe content of catalyst and the addition of sodium chloridedid not alter the nature of the QSPR model equations.
基金the National Natural Science Foundation of China(Nos.21877049,31871006)National Program for Support of Top-notch Young Professionals(No.W02070191)+1 种基金Major Program for Tackling Key Problems of Industrial Technology in Guangzhou(No.201902020013)Dedicated Fund for Promoting High-Quality Marine Economic Development in Guangdong Province(No.GDOE-2019-A31)。
文摘Tumor cell resistance is one of the big hurdles limiting the therapeutic efficacy of tumor necrosis factorrelated apoptosis-inducing ligand(TRAIL)-based cancer treatment.Therefore,the development of a sa fe and effective sensitizer agent is greatly desired for optimizing TRAIL therapy.Herein,we successfully developed a Se/Fe complex with low toxicity to highly effectively inhibit tumor cells proliferation and migration capabilities through down-regulating ER stress related selenoproteins.Furthermore,it could more efficiently damage tumor spheroids with good penetration capability.More importantly,it could synergize with TRAIL treatment to induce the robust generation of reactive oxygen species(ROS),downregulating ER stress related selenoproteins for triggering tumor cells apoptosis in extrinsic and intrinsic signaling pathways.Taken together,this study provides a potential chemo-drug and sensitizer agent to improve the therapeutic efficacy of TRAIL-based cancer treatment.
基金support from the National Outstanding Youth Foundation of China(No. 20525620)the Program for Changjiang Scholars and Innovative Research Team in University(No.IRT0711)
文摘A Fe-complexed dye containing crosslinkable polyamine groups was synthesized through diazotization and coupling reaction, chlorination, amination and metallization. The structure of the Fe-complexed crosslinking dye was characterized by FT-IR and Atomic Absorption Spectroscopic techniques. The dyeing and light fastness properties of the Fe-complex on silk and wool were tested, and the results showed that the novel Fe-complex exhibited both high fixation and good light fastness.
基金National Natural Science Foundation of China(No.20773093)Tianjin Municipal Science Programme Foundation,China(No.043605911)
文摘Two azo dyes,C.I.Reactive Red 195(RR195)and C.I.Acid Black 234(AB234)were degraded by photocatalysis of Fe(Ⅲ)-oxalate complexes/H2O2 in aqueous non-ionic surfactant,Triton X-100(TX-100)solution.Some factors affecting the dye degradation such as TX-100 concentration,irradiation intensity,and sodium chloride were investigated.The interaction and competition between dye and TX-100 during the degradation were also examined using spectrophotometry and maximum bubble pressure method,respectively.The results indicated that TX-100 showed a significant reduction effect on degradation of two azo dyes,but which was largely confined to TX-100 concentration below the Critical Micellar Concentration(CMC).And the reduction was considerably decreased above the CMC,especially in the case of AB234.Moreover,the reducing effect of TX-100 on dye degradation almost did not vary with irradiation intensity.And the impact of sodium chloride on dye degradation was limited by the addition of TX-100.
文摘Fe(Ⅱ) complex Fe[HB(pz)_3]_2(compound 1, pz=pyrazole) and Ni(Ⅱ) complex Ni[HB(pz)_3]_2(compound 2) have been obtained by the reaction of MCI_2(M=Fe and Ni) with NaHB(pz)_3 in MeOH. The two complexes(compounds 1 and 2) were characterized by IR, NMR, elemental analysis and X-ray diffraction. Compound 1 crystallizes in space group P2_1/c with a=1.224(3) nm, b=1.161(2) nm, c=1.648(3) nm, β=107.62(15)°, V=2.233(8) nm3, Z=2. Compound 2 crystallizes in space group P2_1/c with a=0.97926(18) nm, b= 1.7423(3) nm, c=1.3156(2) nm, β=97.055(16)°, V=2.2277(7) nm3, Z=4. The results of X-ray structural analyses show that both compounds 1 and 2 are monomeric neutral, possessing a similar coordination mode and a similar structure around the metal centers. The related spectral characterizations, steric effects and binding properties are discussed.
文摘The aqueous photodegradation of bisphenol A （BPA） in the presence of Fe（Ⅲ）-oxalate complexes （Fe（Ⅲ）-Ox）, which are common compositions of natural water, was investigated in this study. BPA underwent rapid indirect photolysis in Fe（Ⅲ）-Ox solution under simulated solar irradiation, proceeding pseudo-first-order kinetics. The photolysis rate increased with decreasing pH or initial BPA level and increasing Fe（Ⅲ）/oxalate concentration ratio. Hydroxyl radicals （·OH）, which were generated from the photochemical processes of Fe（Ⅲ）-Ox complexes and contributed to the photooxidation of BPA, were determined by molecular probe and electron spin resonance （ESR） methods with the steady-state concentration of 2.56 × 10^-14 mol/L. Superoxide anion radical （O2^·-） was considered as the precursor of. OH and qualitatively determined by adding nitro blue tetrazolium as well as ESR experiments. Based on the structural analysis of the intermediate photoproducts of BPA in Fe（Ⅲ）-Ox complexes solution, the possible degradation pathways of BPA were proposed, involving ·OH addition, alkyl scission and alky oxidation. The results indicate that the photochemical reactivity of Fe（Ⅲ） may affect the environmental fate of BPA in natural water significantly.
基金TheNationalNaturalScienceFoundationofChina (No .2 96 770 0 4)
文摘The effects of the calorimetric buffer solutions were investigated while the two colorimetric reactions of AI-ferron complex and Fe-ferron complex occurred individually, and the effects of the testing wavelength and the pH of the solutions were also investigated. A timed complexatian colorimetric analysis method of Al-Fe-ferron in view of the total concentration of {AI + Fe} was then established to determine the species distribution of polymeric Al-Fe. The testing wavelength was recommended at 362 net and the testing pH value was 5. With a comparison of the ratios of n(Al)/n(Fe), the standard adsorption curves of the polymeric Al-Fe solutions were derived from the experimental results. Furthermore, the solutions' composition were carious in both the molar n(Al)/n(Fe) ratios, i.e. 0/0, 5/5, 9/1 and 0/10, and the concentrations associated with the total ( Al + Fe which ranged from 10(-5) to 10(-4) mol/L..
文摘Concentrations of dissolved organic matter (DOM), dissolved humic substances (DHS), and DOM-complexed Fe (DOM-Fe) in Yamakuni and Oita Rivers, Japan, of which headstream is near in location, flow pass length is similar, but watershed soil type differs, were investigated. Soil organic matter level was higher in black Andosols distributing 67% of the watershed area of the Oita River than in Cambisols covering 90% of the watershed area of Yamakuni River. However, the DOM concentration in the Yamakuni River (0.44 - 1.62 mg·C·L-1) tended to be higher than that in the Oita River (0.13 - 1.37 mg·C·L-1). DHS accounted for 49% - 80% of DOM in both rivers. Fe and DOM-Fe concentrations showed a trend to increase toward downstream but decrease at the estuary in both rivers. DOM-Fe accounted for 26% - 90% and 55% - 93% of dissolved Fe in the Yamakuni and Oita Rivers, respectively. Correlation analysis suggested that the DOM-Fe concentration in the river water was controlled by the capacity for supplying Fe ions rather than that for supplying DOM. Although the ability to form a complex with Fe was suggested to be greater in the DOM in the Oita River than that in the Yamakuni River, the DOM-Fe concentration at the estuary was similar in the two rivers. Thus, the effect of soil organic matter level in the watershed area on the supply of Fe or DOM-Fe to the estuarine ecosystem was not significant.
基金The project was supported by Youth Science Foundation of Shandong University
文摘Reaction of ferrocenoyl chloride with [Et;NH] [（μ-CO）(μ-RS) Fe;=（CO）;] complexes gave bridging ferrocenoyl complexes（μ-FcCO）(μ-RS)Fe;（CO）;（Fc=ferrocenyl, R=Et, i-Pr, n-Bu, t-Bu, Ph）.The structures of all new complexes were characterised by;HNMR, IR and MS.
