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
Chlorosulfonyl-containing pyrazolone azo compounds (2a, 2b) have been prepared by reaction of the corresponding sodium sulfonate (1a, 1b) with thionyl chloride in the presence of a catalytic quantity of N,Ndimethylfor...Chlorosulfonyl-containing pyrazolone azo compounds (2a, 2b) have been prepared by reaction of the corresponding sodium sulfonate (1a, 1b) with thionyl chloride in the presence of a catalytic quantity of N,Ndimethylformamide in dry benzene. The effects of reaction temperature, time, catalyst and solvent amount on the yield of 2a and 2b were investigated. The results show that chlorination of 1a and 1b under optimal conditions gives 2a and 2b in 95.5% and 99.2% yield respectively. The given method is facile and suitable for large-scale synthesis.展开更多
Eleven new-typed azo compounds were synthesized in good yields by dehydrogenating the corresponding aryl substituted semicarbazides using potassium ferricyanide and sodium hydroxide system under solid-state conditions.
Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides f...Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.展开更多
Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,...Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N＇-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N＇-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.展开更多
A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p-hydroxyazobenzene, 4,4＇-dihydroxyazobenzene and cyanuric chlor...A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p-hydroxyazobenzene, 4,4＇-dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV-vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV-vis absorption ability of the synthesized compounds greatly im- proved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.展开更多
Asymmetric synthesis of enantioenriched azo compounds bearing tetrasubstituted stereocenter was achieved through chiral N,N′-dioxide/metal Lewis acid promoted interrupted Japp-Klingemann reaction of aryldiazonium tet...Asymmetric synthesis of enantioenriched azo compounds bearing tetrasubstituted stereocenter was achieved through chiral N,N′-dioxide/metal Lewis acid promoted interrupted Japp-Klingemann reaction of aryldiazonium tetrafluoroborate salts with nucleophiles under mild conditions. This protocol features wide substrate scope and good functional group compatibility.Azaarene-containing chiral azo compounds were stable enough in Japp-Klingemann reaction condition. The key to success of the reaction was the employment of metal salt/N,N′-dioxide ligand and the dual-task roles of the base. Moreover, the X-ray crystal structure of Ni(II)/N,N′-dioxide/substrate complex confirmed that the substrate was activated by bidentate coordination, which shed light on the origin of chiral control of the reaction.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
Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydrox...Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.展开更多
Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was ...Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was characterized by single-crystal X-ray diffraction, IR spectroscopy, Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry（DSC）. With the calculated（CBS-4M） heat of formation（617.0 kJ/mol） and the room temperature X-ray density（2.11 g/cm^3）, impressive values for the detonation parameters such as detonation velocity（8367 m/s） and pressure（31.5 GPa） were computed using the EXPLO5 program. The superior calculated energetic performance show it could serve as a green replacement for the widely used primary explosive,lead（II） azide, which contains toxic ingredient.展开更多
A novel palladium-coordinating Azo-type liquid crystalline polysiloxane （Pd-AZLCP） has been synthesized by chelation reaction of polymeric ligand, Azo-type liquid crystalline polysiloxane（AZLCP）, with palladium di...A novel palladium-coordinating Azo-type liquid crystalline polysiloxane （Pd-AZLCP） has been synthesized by chelation reaction of polymeric ligand, Azo-type liquid crystalline polysiloxane（AZLCP）, with palladium dichloride and potassium chloride in the presence of tetrahydrofuran （THF） as reaction medium instead of dioxane/water system, which has been used since Cope first reported the synthesis of palladium-azobenzene in 1965 . The mesogenic behaviors examined by DSC, temperature-variable X-ray diffraction and polarizing microscopy indicate that the incorporation of Pd ions into the liquid crystal polymer can play a positive effect on the mesogenic property of the parent polymeric ligand. It is exhibited that the isotropization temperature T;is increased and the mesophase range ΔT has been widened, too.展开更多
In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts...In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts, have been presented focusing on the most recent investigations. These classes of compounds, known as high nitrogen compounds, are generally high energy density materials. Therefore, if available some of their ballistic properties were included.展开更多
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.
文摘Chlorosulfonyl-containing pyrazolone azo compounds (2a, 2b) have been prepared by reaction of the corresponding sodium sulfonate (1a, 1b) with thionyl chloride in the presence of a catalytic quantity of N,Ndimethylformamide in dry benzene. The effects of reaction temperature, time, catalyst and solvent amount on the yield of 2a and 2b were investigated. The results show that chlorination of 1a and 1b under optimal conditions gives 2a and 2b in 95.5% and 99.2% yield respectively. The given method is facile and suitable for large-scale synthesis.
文摘Eleven new-typed azo compounds were synthesized in good yields by dehydrogenating the corresponding aryl substituted semicarbazides using potassium ferricyanide and sodium hydroxide system under solid-state conditions.
基金Project (No. 20072033) supported by the National Natural ScienceFoundation of China and Specialized Research Fund for the DoctoralProgram of Higher Education of China
文摘Amides can be obtained in good to excellent yield by Sm/TiCl4 mediated reductive cleavage of N=N bond in azo compounds and successive acylation in one pot. It offers an alternative method for the synthesis of amides from very simple starting materials directly.
基金Supported by the Science Foundation of Education Department of Heilongjiang Province(12511142)
文摘Reduction of a series of N,N＇-diaryl adipyl bis-azo compounds using hydrazine hydrate as reductant was investigated. The products were characterized by elemental analysis, IR and 1H NMR methods and confirmed to be N,N＇-diaryl adipyl dihydrazine. The results show that hydrazine hydrate can selectively reduce azo bonds with other potential reducible bonds intact in the N,N＇-diaryl adipyl bis-azo compounds. The yields are high up to 92% under mild reaction conditions. According to the previous reports, this reduction process was attributed to an indirect reduction mechanism through an intermediate diimide.
文摘A new series of aromatic azo compounds with one, two, three and five azobenzene units were facilely constructed by dehydrochlorination reaction between p-hydroxyazobenzene, 4,4＇-dihydroxyazobenzene and cyanuric chloride under very mild conditions. Their solubility, crystallinity, thermostability, UV-vis absorption properties and photoisomerization behaviors were carefully examined. When the number of azobenzene unit grew, the solubility of the synthesized compounds basically decreased, the crystallinity of the synthesized compounds firstly rose then dropped, while the thermostability and UV-vis absorption ability of the synthesized compounds greatly im- proved. All the aromatic azo compounds exhibited typical reversible photoisomerization behaviors and were expected to be applied in photosensitive material areas.
基金supported by the National Natural Science Foundation of China(21890723,21921002)。
文摘Asymmetric synthesis of enantioenriched azo compounds bearing tetrasubstituted stereocenter was achieved through chiral N,N′-dioxide/metal Lewis acid promoted interrupted Japp-Klingemann reaction of aryldiazonium tetrafluoroborate salts with nucleophiles under mild conditions. This protocol features wide substrate scope and good functional group compatibility.Azaarene-containing chiral azo compounds were stable enough in Japp-Klingemann reaction condition. The key to success of the reaction was the employment of metal salt/N,N′-dioxide ligand and the dual-task roles of the base. Moreover, the X-ray crystal structure of Ni(II)/N,N′-dioxide/substrate complex confirmed that the substrate was activated by bidentate coordination, which shed light on the origin of chiral control of the reaction.
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sponsored by Isfahan University of technology(IUT)
文摘Fully conjugated Schiff base macrocycle has been prepared through a simple and mild condition,a one-pot cyclization procedure of four-component without using a template.The condensation reaction of related bis（hydroxybenzaldehyde） with phenylenediamines to prepare a conjugated[2 ＋ 2]Schiff base macrocycle has been investigated and fluorescent[2 ＋ 2]Schiff base macrocycles with N_2O_2 binding pockets has been prepared and characterized by elemental analysis,^1H NMR,IR,fluorescent,UV-visible and MALDI mass spectroscopies.
基金the National Natural Science Foundation of China (No. 21373157)
文摘Potassium 5,5＇-azobis（1-nitraminotetrazolate）,（K2ABNAT）, a new green primary explosive, was synthesized via a safe and convenient synthetic procedure based on methylcarbazate and cyanogen azide. The compound was characterized by single-crystal X-ray diffraction, IR spectroscopy, Raman spectroscopy, multinuclear NMR spectroscopy, elemental analysis, and differential scanning calorimetry（DSC）. With the calculated（CBS-4M） heat of formation（617.0 kJ/mol） and the room temperature X-ray density（2.11 g/cm^3）, impressive values for the detonation parameters such as detonation velocity（8367 m/s） and pressure（31.5 GPa） were computed using the EXPLO5 program. The superior calculated energetic performance show it could serve as a green replacement for the widely used primary explosive,lead（II） azide, which contains toxic ingredient.
基金This project was supported by the Natural Science Foundation of Henan province, China.
文摘A novel palladium-coordinating Azo-type liquid crystalline polysiloxane （Pd-AZLCP） has been synthesized by chelation reaction of polymeric ligand, Azo-type liquid crystalline polysiloxane（AZLCP）, with palladium dichloride and potassium chloride in the presence of tetrahydrofuran （THF） as reaction medium instead of dioxane/water system, which has been used since Cope first reported the synthesis of palladium-azobenzene in 1965 . The mesogenic behaviors examined by DSC, temperature-variable X-ray diffraction and polarizing microscopy indicate that the incorporation of Pd ions into the liquid crystal polymer can play a positive effect on the mesogenic property of the parent polymeric ligand. It is exhibited that the isotropization temperature T;is increased and the mesophase range ΔT has been widened, too.
文摘In this short review, excerpts from the literature of azo-bridged triazoles(mainly 1,2,4-triazoles), some of their derivatives(chloromethyl,dinitro and trinitro pyrazole substituted ones, etc.) and some of their salts, have been presented focusing on the most recent investigations. These classes of compounds, known as high nitrogen compounds, are generally high energy density materials. Therefore, if available some of their ballistic properties were included.
