In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduce...In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer(PET)effect.Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized,and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry(HRMS),nuclear magnetic resonance hydrogen and carbon spectroscopy(~1H and~(13)C NMR).The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration.The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process.Despite the similarities in chemical structures,the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine.In the direct irradiation experiments of ionizing radiation,the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4,respectively.Furthermore,density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 e V and 1.13 e V,respectively.A wider energy range has a stronger driving force on electrons,which is conducive to fluorescence quenching.Both femtosecond transient absorption spectroscopy(fs-TAS)and transient fluorescence spectroscopy(TFS)tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant.Although both isomers can significantly reduce LOD during PET process,PDI-B with aromatic amine has a wider detection range of 0.118—240 Gy due to its larger emission enhancement,which is a leap of three orders of magnitude.It breaks through the detection range of gamma radiation reported in existing studies,and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.展开更多
The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation ...The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.展开更多
In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morpholo...In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morphology and structure of N,S⁃CDs were characterized by transmission electron microscope,X⁃ray diffrac⁃tion,Fourier transform infrared spectroscopy,and X⁃ray photoelectron spectroscopy,and the basic photophysical properties were investigated via UV⁃Vis absorption spectra and fluorescence spectra.Meanwhile,the N,S⁃CDs have excellent luminescence stability with pH,ionic strength,radiation time,and storage time.Experimental results illus⁃trated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1.The quenching mechanism is proved to be the inner filter effect.In addition,this sensor can also detect baicalein in biofluids(serum and urine)with good accuracy and reproducibility.展开更多
基金financial support from the National Natural Science Foundation of China(Grant No.21801016)the Science and Technology on Applied Physical Chemistry Laboratory(Grant No.6142602220304)。
文摘In order to achieve a wider range of ionizing radiations detection,novel fluorescence sensing materials have been developed that utilize the fluorescence enhancement phenomenon caused by the intramolecular photoinduced electron transfer(PET)effect.Two perylene diimide isomers PDI-P and PDI-B were designed and synthesized,and their molecular structures were characterized by high-resolution Fourier transform mass spectrometry(HRMS),nuclear magnetic resonance hydrogen and carbon spectroscopy(~1H and~(13)C NMR).The interaction between ionizing radiation and fluorescent molecules was simulated by HCl titration.The results show that combining PDIs and HCl can improve fluorescence through the retro-PET process.Despite the similarities in chemical structures,the fluorescent enhancement multiple of PDI-B with aromatic amine as electron donor is much higher than that of PDI-P with alkyl amine.In the direct irradiation experiments of ionizing radiation,the emission enhancement multiples of PDI-P and PDI-B are 2.01 and 45.4,respectively.Furthermore,density functional theory(DFT)and time-dependent density functional theory(TDDFT)calculations indicate that the HOMO and HOMO-1 energy ranges of PDI-P and PDI-B are 0.54 e V and 1.13 e V,respectively.A wider energy range has a stronger driving force on electrons,which is conducive to fluorescence quenching.Both femtosecond transient absorption spectroscopy(fs-TAS)and transient fluorescence spectroscopy(TFS)tests show that PDI-B has shorter charge separation lifetime and higher electron transfer rate constant.Although both isomers can significantly reduce LOD during PET process,PDI-B with aromatic amine has a wider detection range of 0.118—240 Gy due to its larger emission enhancement,which is a leap of three orders of magnitude.It breaks through the detection range of gamma radiation reported in existing studies,and provides theoretical support for the further study of sensitive and effective new materials for ionizing radiation detection.
基金supported by Natural Science Foundation of Shandong Province(ZR2021MB075)Fundamental Research Funds for the Central Universities,Ocean University of China(202461021).
文摘The electrocatalytic nitrogen oxidation reaction(NOR)is a sustainable approach for converting N_(2)to NO_(3)^(-)under mild conditions.However,it still faces challenges including inefficient N_(2)absorption/activation and oxygen evolution competition,sluggish kinetics,low Faradaic efficiency,and limited nitrate yields.In this work,a novel two-dimensional(2D)layered MOF Mn-BCPPy(H_(2)BCPPy=3,5-di(4'-carboxyphenyl)pyridine)has been successfully synthesized.The framework is composed of a rod-manganese motifs and possesses abundant active sites including open metal sites(OMSs)and Lewis base sites(LBSs).The Mn-BCPPy is the first MOF catalyst applied in electrocatalytic NOR which NO_(3)^(-)exhibited relatively high activity with a yield of 99.75μg/(h·mg)and a Faraday efficiency(FE)of 32.09%.Furthermore,it can be used as fluorescent sensor for selectively and sensitively detect nitrofuran antibiotics(NFs).Therefore,this work explores the application of MOF materials in the field of electrocatalytic NOR,which reveals that manganese-based MOFs have great potential prospects.
文摘In this work,p⁃phenylenediamine and L⁃cysteine were used as raw materials,and water⁃soluble N,S co⁃doped carbon dots(N,S⁃CDs)with excellent performance were prepared through a one⁃step solvothermal method.The morphology and structure of N,S⁃CDs were characterized by transmission electron microscope,X⁃ray diffrac⁃tion,Fourier transform infrared spectroscopy,and X⁃ray photoelectron spectroscopy,and the basic photophysical properties were investigated via UV⁃Vis absorption spectra and fluorescence spectra.Meanwhile,the N,S⁃CDs have excellent luminescence stability with pH,ionic strength,radiation time,and storage time.Experimental results illus⁃trated the present sensor platform exhibited high sensitivity and selectivity in response to baicalein with a detection limit of 85 nmol·L-1.The quenching mechanism is proved to be the inner filter effect.In addition,this sensor can also detect baicalein in biofluids(serum and urine)with good accuracy and reproducibility.
