Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated el...Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.展开更多
The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen...The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.展开更多
The abnormal metabolic activity of the tumor can increase the oxygen consumption in tumor cells,and the poor blood perfusion often happens in tumor regions as well,which are the main reasons that result in a hypoxic s...The abnormal metabolic activity of the tumor can increase the oxygen consumption in tumor cells,and the poor blood perfusion often happens in tumor regions as well,which are the main reasons that result in a hypoxic situation in the tumor.A fluorescence probe,AQD,with selective response toward hypoxia was designed for the detection of hypoxic tumor cells,which was obtained by the covalent connection of a large planar conjugated fluorophore with good fluorescence stability and a N,N-dimethylaniline moiety via the azo bond.The introduction of the azo bond in AQD caused significant fluorescence emission quenching,and the probe was reduced under hypoxic conditions to release the fluorophore via breaking the azo bond,resulting in the gradual recovery of fluorescence emission.Probe AQD exhibited a remarkable fluorescence response in hypoxic conditions,high selectivity,and good biocompatibility,which was successfully used for the imaging of hypoxic tumor cells and realized the detection of hypoxic A549 cells.展开更多
Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor(CMOS) image sensors.Herein,a series of azo dyes utilizing 5-methyl-2-phe...Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor(CMOS) image sensors.Herein,a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups(NO_(2),CN,Br) as diazo components were designed and synthesized.The presence of intermolecular hydrogen bonding between the hydrogen atom on the N-H group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring.Additionally,the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure.As a result,these azo dyes(P-2,P-3,P-4,P-5)exhibit not only excellent light stability but also ultra-highly thermal stability(T_(d)> 260℃).Therein,the synthesized dyes P-2 and P-3 with great bright yellow color(~400 nm),proper solubility(~6.00g/100 g)were selected to make for color films.And their dye-based color films displayed ultra-highly thermal and light stability(color difference ΔE<3).Notably,the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance(>90%) in the 550-780 nm wavelength range and the solvent resistance of the dye-based color films.This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.展开更多
Bioremediation has gained significant attention due to its potential to remove azo dyes.However,the challenges microor-ganisms face in surviving when azo dyes are the sole carbon source limit its widespread applicatio...Bioremediation has gained significant attention due to its potential to remove azo dyes.However,the challenges microor-ganisms face in surviving when azo dyes are the sole carbon source limit its widespread application.This study aimed to improve the biodegradation of azo dyes by utilizing Baijiu distiller’s grains leachate(BDGL)as a co-substrate.The experimental results demon-strated that BDGL significantly enhanced Providencia rettgeri’s ability to degrade the model pollutant Acid Black 210(AB210),achieving a decolorization efficiency of 94.5%.This may be attributed to the nutrient-rich composition of BDGL,which includes ethanol and protein,providing a favorable substrate for bacterial growth and activity.The higher biomass and increased activities of azoreductase and quinone oxidoreductase in the BDGL group further supported these findings.Additionally,this method demonstra-ted broad-spectrum degradation of azo dyes(Direct Red 5B,Acid Red 73,and Congo Red)with different structures,highlighting its potential applicability.Metabolite assays combined with transcriptomics analyses revealed that the expression of functional genes re-lated to redox reactions,azo bond cleavage,and hydrolysis increased under the co-metabolic conditions of BDGL,resulting in stronger reducing power that further mineralized the dye into smaller metabolites.Our study offers a practical strategy for the simulta-neous treatment of dye-containing wastewater and Baijiu distiller’s grains,with significant environmental and industrial applications.展开更多
Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants f...Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.展开更多
A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationc...A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationchromatography.This approach is more facile compared with the direct polymerization of corresponding functionalmonomer.The polymers prepared have weight average molecular weight of higher than 1.5×10~4 and are easily soluble incommon organic solvents like chloroform and tetrahydrofuran,polymer films with high optical quality could be easilyfabricated through solution casting.Glass transition temperature (T_(?)) of the polymers ranges from 60℃ to 182℃,dependingon the alkylene spacer length between the functional side group and the polymer backbone,and the polymers are relativelystable under 300℃.展开更多
A number of tetrazoles derivatives were prepared by series of steps, the first step includes react （4,5-dichloroimidazole） with （4-aminoacetophenone） to form 1-（4-（（4,5-dichloro-lH-imidazol-2yl）diazenyl）ethan...A number of tetrazoles derivatives were prepared by series of steps, the first step includes react （4,5-dichloroimidazole） with （4-aminoacetophenone） to form 1-（4-（（4,5-dichloro-lH-imidazol-2yl）diazenyl）ethanone （1）. The second step was （1） reaction with （Amines derivatives） to get Schiff bases （2-7）. The third step was reaction of Shciff base with sodiumazide to form tetrazoles derivatives （8-13）. then study the biological activity for all compounds to word two type of bacteria.展开更多
基金supported by the National Key R&D Program of China(2024YFA1211004)the National Natural Science Foundation of China(22402150,22072107)+1 种基金the Natural Science Foundation of Shanghai(23ZR1464800,24ZR1470200)the Foundation of State Key Laboratory of Pollution Control and Resource Reuse(Tongji University)。
文摘Azoxy aromatics are extensively utilized in materials science,pharmaceuticals,and synthetic chemistry,but their controlled and environmentally-friendly synthesis has rarely been reported.Herein,a potential-mediated electrosynthesis strategy was developed by selective reduction of 4-nitrobenzyl alcohol(4-NBA)on Mn-doped Ni_(2)P nanosheets@nickel foam(Mn-Ni_(2)P/NF),enabling efficient N−N coupling to produce Azoxy with 100%selectivity at potentials of−0.6 to−0.8 V(vs.Hg/HgO).At more cathodic potentials,the product was converted to Azo and then to amino aromatics due to facilitated nitrogen hydrogenation.Additionally,the organic energetic material,5,5′-azotetrazolate,was also synthesized by anodic N−N coupling of 5-amino-1H-tetrazole on Cu(OH)_(2)nanowires@copper foam(Cu(OH)_(2)/CF).It bypassed harsh conditions(strong oxidants,high temperature,by-products separation,etc.)for the traditional synthesis of this class of materials.As a consequence,a two-electrode electrolyzer Cu(OH)_(2)/CF||Mn-Ni_(2)P/NF was assembled,allowing paired electrochemical N−N coupling into Azoxy and 5,5′-azotetrazolate.It achieves a current density of 50 mA cm^(−2)at a voltage of only 1.19 V,880 mV lower than the competitive water splitting.This electrolyzer can be efficiently driven by a 1.2 V solar panel with excellent yield and selectivity,paving the way for green synthesis of valuable chemicals through electrochemical N−N coupling strategies.
文摘The triple bond in N_(2)has an extremely high bond energy and is thus difficult to break.N_(2)is commonly converted into NH3 artificially via the Haber-Bosch process,and NH_(3)can be utilized to produce other nitrogen-containing chemicals.Here,we developed an electron catalyzed method to directly fix N_(2)into azos,by pushing and pulling the electron into and from the aromatic halide with the cyclic voltammetry method.The round-trip journey of electron can successfully weaken the triple bond in N_(2)through the electron pushing-induced aryl radical via a“brick trowel”transition state,and then produce the diazonium ions by pulling the electron out from the diazo radical intermediate.Different azos can be synthesized with this developed electron catalyzed approach.This approach provides a novel concept and practical route for the fixation of N_(2)at atmospheric pressure into chemical products valuable for industrial and commercial applications.
文摘The abnormal metabolic activity of the tumor can increase the oxygen consumption in tumor cells,and the poor blood perfusion often happens in tumor regions as well,which are the main reasons that result in a hypoxic situation in the tumor.A fluorescence probe,AQD,with selective response toward hypoxia was designed for the detection of hypoxic tumor cells,which was obtained by the covalent connection of a large planar conjugated fluorophore with good fluorescence stability and a N,N-dimethylaniline moiety via the azo bond.The introduction of the azo bond in AQD caused significant fluorescence emission quenching,and the probe was reduced under hypoxic conditions to release the fluorophore via breaking the azo bond,resulting in the gradual recovery of fluorescence emission.Probe AQD exhibited a remarkable fluorescence response in hypoxic conditions,high selectivity,and good biocompatibility,which was successfully used for the imaging of hypoxic tumor cells and realized the detection of hypoxic A549 cells.
基金supported by the Program of the National Natural Science Foundation of China(No.22238002)the Fundamental Research Funds for the Central Universities(No.DUT22LAB610)+1 种基金Research and Innovation Team Project of Dalian University of Technology(No.DUT2022TB10)China Postdoctoral Science Foundation(No.2022M720639)。
文摘Dye-based color films are increasingly considered as viable alternatives to pigment-based color films in complementary metal-oxide-semiconductor(CMOS) image sensors.Herein,a series of azo dyes utilizing 5-methyl-2-phenyl-4-(2-phenylhydrazono)-2,4-dihydro-3H-pyrazol-3-one as the coupling component and aromatic amines with various electron-withdrawing groups(NO_(2),CN,Br) as diazo components were designed and synthesized.The presence of intermolecular hydrogen bonding between the hydrogen atom on the N-H group and the oxygen atom of the C=O group of the hydrazo structure facilitates the formation of a stable six-membered ring.Additionally,the electron-withdrawing groups in the diazo component further stabilize this hydrogen-bonded structure.As a result,these azo dyes(P-2,P-3,P-4,P-5)exhibit not only excellent light stability but also ultra-highly thermal stability(T_(d)> 260℃).Therein,the synthesized dyes P-2 and P-3 with great bright yellow color(~400 nm),proper solubility(~6.00g/100 g)were selected to make for color films.And their dye-based color films displayed ultra-highly thermal and light stability(color difference ΔE<3).Notably,the increased planarity of the molecular structure by hydrogen bonding for the novel dyes ensures a balance between high transmittance(>90%) in the 550-780 nm wavelength range and the solvent resistance of the dye-based color films.This work contributes to the advancement of next-generation smart CMOS devices and offers valuable insights into the design of azo dyes for applications in the field of organic electronics.
基金supported by the National Key Re-search and Development Project of China(No.2023YFC3108400).
文摘Bioremediation has gained significant attention due to its potential to remove azo dyes.However,the challenges microor-ganisms face in surviving when azo dyes are the sole carbon source limit its widespread application.This study aimed to improve the biodegradation of azo dyes by utilizing Baijiu distiller’s grains leachate(BDGL)as a co-substrate.The experimental results demon-strated that BDGL significantly enhanced Providencia rettgeri’s ability to degrade the model pollutant Acid Black 210(AB210),achieving a decolorization efficiency of 94.5%.This may be attributed to the nutrient-rich composition of BDGL,which includes ethanol and protein,providing a favorable substrate for bacterial growth and activity.The higher biomass and increased activities of azoreductase and quinone oxidoreductase in the BDGL group further supported these findings.Additionally,this method demonstra-ted broad-spectrum degradation of azo dyes(Direct Red 5B,Acid Red 73,and Congo Red)with different structures,highlighting its potential applicability.Metabolite assays combined with transcriptomics analyses revealed that the expression of functional genes re-lated to redox reactions,azo bond cleavage,and hydrolysis increased under the co-metabolic conditions of BDGL,resulting in stronger reducing power that further mineralized the dye into smaller metabolites.Our study offers a practical strategy for the simulta-neous treatment of dye-containing wastewater and Baijiu distiller’s grains,with significant environmental and industrial applications.
基金supported by the Natural Science Foundation of Jiangsu Province(BK20221541)National Natural Science Foundation of China(21707052)Jiangsu Agriculture Science and Technology Innovation Fund(CX(20)3108).
文摘Herein,an oxygen-doped porous g-C_(3)N_(4)photocatalyst modified with atomically dispersed Fe(Fe_(1)/OPCN)issuccessfully prepared and exhibits significant superiority in removing refractory sulfonic azo contaminants fromwater via catalyst-contaminant interaction.The elimination performance of Fe_(1)/OPCN towards acid red 9,acidred 13 and amaranth containing similar azonaphthalene structure and increasing sulfonic acid groups increasesgradually.The amaranth degradation rate of Fe_(1)/OPCN is 17.7 and 6.1 times as that of homogeneous Fenton andOPCN,respectively.In addition,Fe_(1)/OPCN also has more outstanding removal activities towards other con-taminantswith sulfonic acid and azo groups alone.The considerable enhancement for removing sulfonic azocontaminants of Fe_(1)/OPCN is mainly ascribed to the following aspects:(1)The modified Fe could enhance theadsorption towards sulfonic azo compounds to accelerate the mass transfer,act as e^(-)acceptor to promoteinterfacial charge separation,and trigger the self-Fenton reaction to convert in-situ generated H_(2)O_(2)into·OH.(2)Fe(Ⅲ)could coordinate with-N=N-to form d-πconjugation,which could attract e^(-)transfer to attack-N=N-bond.Meanwhile,the inhibited charge recombination could release more free h^(þ)to oxidize sulfonicacid groups into SO4^(-)·.(3)Under the cooperation of abundant multiple active species(·O_(2)^(-),h^(þ),e^(-),·OH,SO4^(-)·)formed during the degradation reaction,sulfonic azo compounds could be completely mineralized into harmlesssmall molecules(CO_(2),H_(2)O,etc.)by means of-N=N-cleavage,hydroxyl substitution,and aromatic ringopening.This work offers a novel approach for effectively eliminating refractory sulfonic azo compounds fromwastewater.
基金This work was supported by the National Natural Science Foundation of China(No.20274042)
文摘A series of polymers bearing azobenzene and carbazole groups for photorefractive purpose were prepared viapost-azo-coupling reaction.The successful reaction was identified by spectroscopic analysis and gel permeationchromatography.This approach is more facile compared with the direct polymerization of corresponding functionalmonomer.The polymers prepared have weight average molecular weight of higher than 1.5×10~4 and are easily soluble incommon organic solvents like chloroform and tetrahydrofuran,polymer films with high optical quality could be easilyfabricated through solution casting.Glass transition temperature (T_(?)) of the polymers ranges from 60℃ to 182℃,dependingon the alkylene spacer length between the functional side group and the polymer backbone,and the polymers are relativelystable under 300℃.
文摘A number of tetrazoles derivatives were prepared by series of steps, the first step includes react （4,5-dichloroimidazole） with （4-aminoacetophenone） to form 1-（4-（（4,5-dichloro-lH-imidazol-2yl）diazenyl）ethanone （1）. The second step was （1） reaction with （Amines derivatives） to get Schiff bases （2-7）. The third step was reaction of Shciff base with sodiumazide to form tetrazoles derivatives （8-13）. then study the biological activity for all compounds to word two type of bacteria.
