AF@MOF-808 incorporating the acriflavine(AF)dye into the nanocages of MOF-808 was constructed by one-pot hydrothermal method,whose crystallization,morphology and stability were characterized by the X-ray powder diffra...AF@MOF-808 incorporating the acriflavine(AF)dye into the nanocages of MOF-808 was constructed by one-pot hydrothermal method,whose crystallization,morphology and stability were characterized by the X-ray powder diffractometer(XRD),scanning electron microscope(SEM)and thermogravimetric analysis(TGA).AF@MOF-808 exhibits bright green light emission with the high quantum yield of 38.27%and can selectively detect Fe^(3+)ion and Cr_(2)O_(7)^(2-)anion from 12 kinds of metal ions or anions in the aqueous solution.展开更多
To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO lo...To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.展开更多
Improving the highly selective and sensitive binding of chemosensor to target guest is always very challenging.In order to solve this issue,herein,the enrichment effect was introduced into the design of chemosensor mo...Improving the highly selective and sensitive binding of chemosensor to target guest is always very challenging.In order to solve this issue,herein,the enrichment effect was introduced into the design of chemosensor molecule.A novel bi-fused-macrocyclic host molecule BPN1 was synthesized by bridging a pillar[5]arene and a naphthalene diimide(NDI)group through hydrogen-bond-rich chain.In the BPN1,the naphthalimide side ring is outside the cavity of the pillar[5]arene.In addition,Cr(VI)greatly threat human health and the environment due to its severe toxicity,and it is very important to develop effective chemosensor for sensitive and selective detection of Cr_(2)O_(7)^(2-)or its ion pairs.In this paper,the novel bi-fused-macrocyclic host molecule BPN1 can recognize Cr_(2)O_(7)^(2-)with high selectivity and sensitivity.The mechanism of BPN1 recognition of Cr_(2)O_(7)^(2-)was studied through experiments and density functional theory(DFT),the results show that BPN1 could supply enrichment effect to bind Cr_(2)O_(7)^(2-)through multiple weak interactions such as hydrogen bonds and anion-π,and achieve highly sensitive and selective detection of Cr_(2)O_(7)^(2-).It is a significant and feasible strategy for improve high selectivity and sensitivity of host to specific objects by using the enrichment effect of fused bi-macrocyclic.展开更多
In this work,two new metal-organic frameworks(MOFs)based on a pyrazole-imidazole heterotopic ligand,namely,SCNU-Z8(Co)and SCNU-Z8(Ni),are constructed.They are isostructural,and the crystal structure of SCNU-Z8(Co)is f...In this work,two new metal-organic frameworks(MOFs)based on a pyrazole-imidazole heterotopic ligand,namely,SCNU-Z8(Co)and SCNU-Z8(Ni),are constructed.They are isostructural,and the crystal structure of SCNU-Z8(Co)is further analyzed by single-crystal X-ray diffraction.They are 3D cationic frameworks with 1D tubular channels and possess a highly(3,9)-connected binodal gfy network topology.SCNU-Z8(Ni)can be syn-thesized in high yield with high phase purity;thus,it is selected to be further explored.A stability study shows that its framework is stable in water at different pH values and in many organic solvents.It can be applied to capture Cr_(2)O_(7)^(2-)anions in water with a moderate adsorption capacity of 130 mg/g via anion-exchanged process.Iodine molecules in vapour phase and cyclohexane solution can also be captured by SCNU-Z8(Ni).In the case of iodine vapours and iodine cyclohexane solution,the adsorption capacity reaches up to 4.1 g/g and 640 mg/g,respectively,which are among the best in MOFs.Most of the absorbed iodine molecules are stably captured in the framework and hard to release,which may be conducive to allow the permanent storage of radioactive iodine.展开更多
Water-soluble b-alanine C60 adducts were synthesized, and the scavenging ability to superoxygen anion radical O2- and hydroxyl radical.OH were studied by autoxidation of pyrogallol and chemiluminescence, respectively....Water-soluble b-alanine C60 adducts were synthesized, and the scavenging ability to superoxygen anion radical O2- and hydroxyl radical.OH were studied by autoxidation of pyrogallol and chemiluminescence, respectively. It was found thatβ-alanine C60 adducts showed an excellent efficiency in eliminating superoxygen anion radical and hydroxyl radical. The 50% inhibition concentration (IC50) for superoxygen anion radical and hydroxyl radical were 0.15 mg/mL and 0.048 mg/mL, respectively. The difference should be mainly attributed to the different scavenging mechanisms.展开更多
Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM...Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM-5 support with a monolayer dispersion threshold of 0.061 mmol 100 m^(-2),equaling to a weight percentage around 4.5%.It has been revealed that the quantities of surface active oxygen(O_(2)^(-))and acid sites are crucial for the reaction,which can adsorb and activate NO_(x)and NH_(3)reactants effectively.Below the monolayer dispersion threshold,Co_(3)O_(4)is finely dispersed as sub-monolayers or monolayers and in an amorphous state,which is favorable to generate the two kinds of active sites,hence promoting the performance of ammonia selective catalytic reduction of nitrogen oxide.However,the formation of crystalline Co_(3)O_(4)above the capacity is harmful to the reaction performance.4%Co_(3)O_(4)/ZSM-5,the catalyst close to the monolayer dispersion capacity,possesses the most abundant active O_(2)^(-)species and acidic sites,thereby demonstrating the best reaction performance in all the samples.It is proposed the optimal Co_(3)O_(4)/ZSM-5 catalyst can be prepared by loading the capacity amount of Co_(3)O_(4)onto HZSM-5 support.展开更多
Athree-fold interpenetrated cadmium coordination polymer[Cd_(3)(BTC)_(2)(H_(2)O)_(9)]·2H_(2)O(CP 1)(H_(3)BTC=1,3,5-benzenetricarboxylic acid)was selected and synthesized to investigate its photoelectric propertie...Athree-fold interpenetrated cadmium coordination polymer[Cd_(3)(BTC)_(2)(H_(2)O)_(9)]·2H_(2)O(CP 1)(H_(3)BTC=1,3,5-benzenetricarboxylic acid)was selected and synthesized to investigate its photoelectric properties.CP 1 showed excellent sensitivity for Cr_(2)O_(7)^(2−)and Fe^(3+),low limit of detection(LOD:0.39µmol/L for Cr_(2)O_(7)^(2−)and 1.72µmol/L for Fe^(3+))and stability as electrochemical sensor.More importantly,fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe^(3+),Fe^(2+),and MnO_(4)−with good cyclic stability and selectivity.Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.展开更多
Photodynamic therapy(PDT)usually shows limited efficacy in solid tumors since traditional PDT is O_(2)^(-)dependent while solid tumors are inherently hypoxic.In addition,hypoxic tumor cells possess antiapoptotic pathw...Photodynamic therapy(PDT)usually shows limited efficacy in solid tumors since traditional PDT is O_(2)^(-)dependent while solid tumors are inherently hypoxic.In addition,hypoxic tumor cells possess antiapoptotic pathways that resist PDT-induced apoptosis.Therefore,developing photosensitizers(PSs)that show low O_(2)^(-)dependency and can induce nonapoptotic cell death pathways is critically needed.Herein,a series of Ru(II)polypyridine complex-based PSs,RuNMe,RuH,and RuCN,were synthesized,and their applications against hypoxic tumor cells through PDT were investigated.All three complexes showthe ability to generate the superoxide anion radical(·O_(2)^(-)),which is the type I photoreaction and less O_(2)^(-)dependent.RuNMe shows the best PDT performance against MCF-7 cells and three-dimensional multicellular spheroids,due to its higher cellular uptake and more reactive oxygen species generation.More importantly,RuNMe-incubated MCF-7 cells show photoinduced ferroptosis as evidenced by glutathione peroxidase 4 downregulation and lipid peroxide accumulation.This work not only develops a novel ferroptosis-inducing Ru(II)complex with the type I PDT process but also offers an effective strategy to solve tumor hypoxia in PDT.展开更多
The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide a...The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide anion O(?) was generated polarographically and the dismutation of the O(?) was catalyzed by MA to reproduce O_2 and H_2O_2. This explained chemically the scavenging of the O_2^- by MA im biomedical area. Based on the catalytic wave, a new method for the determination of MA by single-sweep polarography was developed.展开更多
文摘AF@MOF-808 incorporating the acriflavine(AF)dye into the nanocages of MOF-808 was constructed by one-pot hydrothermal method,whose crystallization,morphology and stability were characterized by the X-ray powder diffractometer(XRD),scanning electron microscope(SEM)and thermogravimetric analysis(TGA).AF@MOF-808 exhibits bright green light emission with the high quantum yield of 38.27%and can selectively detect Fe^(3+)ion and Cr_(2)O_(7)^(2-)anion from 12 kinds of metal ions or anions in the aqueous solution.
文摘To understand the dispersion behavior of metal oxides on composite oxide supports and with the expectation of developing more feasible catalysts for soot oxidation,CuO/La_(2)Sn_(2)O_(7)samples containing varied CuO loadings were fabricated and characterized by different techniques and density functional theory calculations.In these catalysts,a spontaneous dispersion of CuO on the La_(2)Sn_(2)O_(7)pyrochlore support formed,having a monolayer dispersion capacity of 1.90 mmol CuO/100 m^(2) La_(2)Sn_(2)O_(7)surface.When loaded below this capacity,CuO exists in a sub-monolayer or monolayer state.X-ray photoelectron spectroscopy(XPS),Raman spectroscopy,and Bader charge and density of states analyses indicate that there are strong interactions between the sub-monolayer/monolayer CuO and the La_(2)Sn_(2)O_(7)support,mainly through the donation of electrons from Cu to Sn at the B-sites of the structure.In contrast,Cu has negligible interactions with La at the A-sites.This suggests that,in composite oxide supports containing multiple metals,the supported metal oxide interacts preferentially with one kind of metal cation in the support.The Raman,in situ diffuse reflectance infrared Fourier transform spectroscopy,and XPS results confirmed the formation of both O2^(-)and O2^(2-)as the active sites on the surfaces of the CuO/La_(2)Sn_(2)O_(7)catalysts,and the concentration of these active species determines the soot combustion activity.The number of active oxygen anions increased with increase in CuO loading until the monolayer dispersion capacity was reached.Above the monolayer dispersion capacity,microsized CuO crystallites formed,and these had a negative effect on the generation of active surface oxygen sites.In summary,a highly active catalyst can be prepared by covering the surface of the La_(2)Sn_(2)O_(7)support with a CuO monolayer.
基金supported by the National Natural Science Foundation of China(NSFC,Nos.22065031,22061039,22001214,22165027)the top-notch talent project in Gansu province,the Key R&D Program of Gansu Province(No.21YF5GA066)+2 种基金Gansu Province College Industry Support Plan Project(No.2022CYZC-18)Natural Science Foundation of Gansu Province(Nos.2020–0405-JCC-630,20JR10RA088)The star of innovation(No.2023CXZX244)。
文摘Improving the highly selective and sensitive binding of chemosensor to target guest is always very challenging.In order to solve this issue,herein,the enrichment effect was introduced into the design of chemosensor molecule.A novel bi-fused-macrocyclic host molecule BPN1 was synthesized by bridging a pillar[5]arene and a naphthalene diimide(NDI)group through hydrogen-bond-rich chain.In the BPN1,the naphthalimide side ring is outside the cavity of the pillar[5]arene.In addition,Cr(VI)greatly threat human health and the environment due to its severe toxicity,and it is very important to develop effective chemosensor for sensitive and selective detection of Cr_(2)O_(7)^(2-)or its ion pairs.In this paper,the novel bi-fused-macrocyclic host molecule BPN1 can recognize Cr_(2)O_(7)^(2-)with high selectivity and sensitivity.The mechanism of BPN1 recognition of Cr_(2)O_(7)^(2-)was studied through experiments and density functional theory(DFT),the results show that BPN1 could supply enrichment effect to bind Cr_(2)O_(7)^(2-)through multiple weak interactions such as hydrogen bonds and anion-π,and achieve highly sensitive and selective detection of Cr_(2)O_(7)^(2-).It is a significant and feasible strategy for improve high selectivity and sensitivity of host to specific objects by using the enrichment effect of fused bi-macrocyclic.
基金supported by the National Natural Science Foundation of China(No.22073032)the Natural Science Foundation of Guangdong Province(No.2022A1515011243)Students'Extracurricular Scientific Research Project of South China Normal University.
文摘In this work,two new metal-organic frameworks(MOFs)based on a pyrazole-imidazole heterotopic ligand,namely,SCNU-Z8(Co)and SCNU-Z8(Ni),are constructed.They are isostructural,and the crystal structure of SCNU-Z8(Co)is further analyzed by single-crystal X-ray diffraction.They are 3D cationic frameworks with 1D tubular channels and possess a highly(3,9)-connected binodal gfy network topology.SCNU-Z8(Ni)can be syn-thesized in high yield with high phase purity;thus,it is selected to be further explored.A stability study shows that its framework is stable in water at different pH values and in many organic solvents.It can be applied to capture Cr_(2)O_(7)^(2-)anions in water with a moderate adsorption capacity of 130 mg/g via anion-exchanged process.Iodine molecules in vapour phase and cyclohexane solution can also be captured by SCNU-Z8(Ni).In the case of iodine vapours and iodine cyclohexane solution,the adsorption capacity reaches up to 4.1 g/g and 640 mg/g,respectively,which are among the best in MOFs.Most of the absorbed iodine molecules are stably captured in the framework and hard to release,which may be conducive to allow the permanent storage of radioactive iodine.
文摘Water-soluble b-alanine C60 adducts were synthesized, and the scavenging ability to superoxygen anion radical O2- and hydroxyl radical.OH were studied by autoxidation of pyrogallol and chemiluminescence, respectively. It was found thatβ-alanine C60 adducts showed an excellent efficiency in eliminating superoxygen anion radical and hydroxyl radical. The 50% inhibition concentration (IC50) for superoxygen anion radical and hydroxyl radical were 0.15 mg/mL and 0.048 mg/mL, respectively. The difference should be mainly attributed to the different scavenging mechanisms.
基金the financial supporting by the National Natural Science Foundation of China(Grant Nos.21962009,22172071,22102069,22062013)the Natural Science Foundation of Jiangxi Province(Grant Nos.20202BAB203006,20181ACB20005)the Key Laboratory Foundation of Jiangxi Province for Environment and Energy Catalysis(Grant No.20181BCD40004).
文摘Based on monolayer dispersion theory,Co_(3)O_(4)/ZSM-5 catalysts with different loadings have been prepared for selective catalytic reduction of nitrogen oxides by ammonia.Co_(3)O_(4)can spontaneously disperse on HZSM-5 support with a monolayer dispersion threshold of 0.061 mmol 100 m^(-2),equaling to a weight percentage around 4.5%.It has been revealed that the quantities of surface active oxygen(O_(2)^(-))and acid sites are crucial for the reaction,which can adsorb and activate NO_(x)and NH_(3)reactants effectively.Below the monolayer dispersion threshold,Co_(3)O_(4)is finely dispersed as sub-monolayers or monolayers and in an amorphous state,which is favorable to generate the two kinds of active sites,hence promoting the performance of ammonia selective catalytic reduction of nitrogen oxide.However,the formation of crystalline Co_(3)O_(4)above the capacity is harmful to the reaction performance.4%Co_(3)O_(4)/ZSM-5,the catalyst close to the monolayer dispersion capacity,possesses the most abundant active O_(2)^(-)species and acidic sites,thereby demonstrating the best reaction performance in all the samples.It is proposed the optimal Co_(3)O_(4)/ZSM-5 catalyst can be prepared by loading the capacity amount of Co_(3)O_(4)onto HZSM-5 support.
基金supported by the National Natural Science Foundation of China(Nos.21971024,21671025)the Liao Ning Revitalization Talents Program,China(No.XLYC1902011).
文摘Athree-fold interpenetrated cadmium coordination polymer[Cd_(3)(BTC)_(2)(H_(2)O)_(9)]·2H_(2)O(CP 1)(H_(3)BTC=1,3,5-benzenetricarboxylic acid)was selected and synthesized to investigate its photoelectric properties.CP 1 showed excellent sensitivity for Cr_(2)O_(7)^(2−)and Fe^(3+),low limit of detection(LOD:0.39µmol/L for Cr_(2)O_(7)^(2−)and 1.72µmol/L for Fe^(3+))and stability as electrochemical sensor.More importantly,fluorescence sensing studies indicated that CP 1 exhibits sensing activity for Fe^(3+),Fe^(2+),and MnO_(4)−with good cyclic stability and selectivity.Low LOD and high-sensitivity capability of CP 1 make it a potential multifunctional photoelectric sensor.
基金This work was financially supported by the National Natural Science Foundation of China(grant nos.22122701,21731004,91953201,92153303,21977044,and 21907050)the Natural Science Foundation of Jiangsu Province(grant nos.BK20202004 and BK20190282)the Excellent Research Program of Nanjing University(grant no.ZYJH004).
文摘Photodynamic therapy(PDT)usually shows limited efficacy in solid tumors since traditional PDT is O_(2)^(-)dependent while solid tumors are inherently hypoxic.In addition,hypoxic tumor cells possess antiapoptotic pathways that resist PDT-induced apoptosis.Therefore,developing photosensitizers(PSs)that show low O_(2)^(-)dependency and can induce nonapoptotic cell death pathways is critically needed.Herein,a series of Ru(II)polypyridine complex-based PSs,RuNMe,RuH,and RuCN,were synthesized,and their applications against hypoxic tumor cells through PDT were investigated.All three complexes showthe ability to generate the superoxide anion radical(·O_(2)^(-)),which is the type I photoreaction and less O_(2)^(-)dependent.RuNMe shows the best PDT performance against MCF-7 cells and three-dimensional multicellular spheroids,due to its higher cellular uptake and more reactive oxygen species generation.More importantly,RuNMe-incubated MCF-7 cells show photoinduced ferroptosis as evidenced by glutathione peroxidase 4 downregulation and lipid peroxide accumulation.This work not only develops a novel ferroptosis-inducing Ru(II)complex with the type I PDT process but also offers an effective strategy to solve tumor hypoxia in PDT.
文摘The polarographic catalytic wave of oxygen reduction caused by mefenamic acid (MA) with redox properties was reported in this paper. The electrochemical process of the catalytic wave was proposed that the superoxide anion O(?) was generated polarographically and the dismutation of the O(?) was catalyzed by MA to reproduce O_2 and H_2O_2. This explained chemically the scavenging of the O_2^- by MA im biomedical area. Based on the catalytic wave, a new method for the determination of MA by single-sweep polarography was developed.
