Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,mai...Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions,so its accurately detection remains a challenge.With this research,we developed an activable fiuorescence switching platform by incorporating different conjugate acceptors to a fiuorophore using ester bonds and resulting in fiuorescence quenching due to donor-excited photo-induced electron transfer(d-Pe T),which was confirmed through density functional theory calculations.The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species(RSS),including H_(2)S,cysteine(Cys),homocysteine(Hcy),glutathione(GSH),and protein free thiols.The quenched fiuorescence was significantly recovered by RSS,through releasing the fiuorophore and diminishing the d-Pe T effect.Furthermore,the fiuorescent probe was used for the sensing and imaging RSS in living cells,demonstrating good cell-permeability,low cytotoxicity,and negative correlation with reactive oxygen species content,enabling the evaluating of global thiols redox state in Hep G2 cellular lines during ferroptosis processes.展开更多
KAg_(3)Te_(2)with a layered crystal structure has been predicted to be a possible topological insulator.Through electrical transport measurements,we revealed its semiconducting behavior with a narrow band gap of~0.4 e...KAg_(3)Te_(2)with a layered crystal structure has been predicted to be a possible topological insulator.Through electrical transport measurements,we revealed its semiconducting behavior with a narrow band gap of~0.4 eV and p-type character.The infrared transmission spectra of single crystals yielded an optical band gap of~0.3 eV.Angle-resolved photoemission spectroscopy reveals a bulk energy gap at the Brillouin zone center,with no observable surface state,suggesting that KAg_(3)Te_(2)is a topological trivial narrow-gap semiconductor.The experimentally determined effective mass of the holes in KAg_(3)Te_(2)is very small(~0.12 me).The valence band maximum is quasi-two-dimensional,while the conduction band minimum is fully three-dimensional.Such intriguing dimensional anisotropy can be attributed to the distinct orbital contributions from K,Ag,and Te atoms to the respective bands.展开更多
Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electr...Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.展开更多
基金the National Natural Science Foundation of China(Nos.21907080,22278330)Youth Innovative Team(No.xtr052022012)+3 种基金Fundamental Research Funds for the Central University(No.xzy012023010)from Xi’an Jiaotong Universitysupported by Natural Science Basic Research Program of Shaanxi(No.2023-JC-QN-0246)China/Shaanxi Postdoctoral Science Foundation(Nos.2023M732811,2023BSHEDZZ20)the University of Bath and the Open Research Fund of the School of Chemistry and Chemical Engineering,Henan Normal University(No.2020ZD01)for support。
文摘Redox dyshomeostasis is a critical factor in the initiation of numerous diseases,making the accurate evaluation of the redox status of the cellular environment an important aspect of physiological research.However,maintaining redox homeostasis relies on a complex and dynamic physiological system involving multiple substrate-enzyme interactions,so its accurately detection remains a challenge.With this research,we developed an activable fiuorescence switching platform by incorporating different conjugate acceptors to a fiuorophore using ester bonds and resulting in fiuorescence quenching due to donor-excited photo-induced electron transfer(d-Pe T),which was confirmed through density functional theory calculations.The reaction-based probe was deployed for recognizing all major intracellular reducing sulfur species(RSS),including H_(2)S,cysteine(Cys),homocysteine(Hcy),glutathione(GSH),and protein free thiols.The quenched fiuorescence was significantly recovered by RSS,through releasing the fiuorophore and diminishing the d-Pe T effect.Furthermore,the fiuorescent probe was used for the sensing and imaging RSS in living cells,demonstrating good cell-permeability,low cytotoxicity,and negative correlation with reactive oxygen species content,enabling the evaluating of global thiols redox state in Hep G2 cellular lines during ferroptosis processes.
基金Project supported by the National Key Research and Development Program of China and the National Natural Science Foundation of China.
文摘KAg_(3)Te_(2)with a layered crystal structure has been predicted to be a possible topological insulator.Through electrical transport measurements,we revealed its semiconducting behavior with a narrow band gap of~0.4 eV and p-type character.The infrared transmission spectra of single crystals yielded an optical band gap of~0.3 eV.Angle-resolved photoemission spectroscopy reveals a bulk energy gap at the Brillouin zone center,with no observable surface state,suggesting that KAg_(3)Te_(2)is a topological trivial narrow-gap semiconductor.The experimentally determined effective mass of the holes in KAg_(3)Te_(2)is very small(~0.12 me).The valence band maximum is quasi-two-dimensional,while the conduction band minimum is fully three-dimensional.Such intriguing dimensional anisotropy can be attributed to the distinct orbital contributions from K,Ag,and Te atoms to the respective bands.
基金funded by the National Natural Science Foundation of China(61701288,51706128)the Natural Science Basic Research Program of Shaanxi Province(2021JM-485)+2 种基金the Key Scientific Research Project of Shaanxi Provincial Education Department(20JS019)the High-level Achievement Cultivation Project of Collaborative Innovation Center for Comprehensive Development of Qinba Biological Resources(QBXT-17-8)the Postgraduate Innovation Project of Shaanxi University of Technology(SLGYCX2410).
文摘Single-atom catalysts(SACs)have attracted considerable interest in the fields of energy and environmental science due to their adjustable catalytic activity.In this study,we investigated the matching of valence electron numbers between single atoms and adsorbed intermediates(O,N,C,and H)in MXene-anchored SACs(M-Ti_(2)C/M-Ti_(2)CO_(2)).The density functional theory results demonstrated that the sum of the valence electron number(VM)of the interface-doped metal and the valence electron number(VA)of the adsorbed intermediates in M-Ti_(2)C followed the 10-valence electron matching law.Furthermore,based on the 10-valence electron matching law,we deduced that the sum of the valence electron number(k)and VMfor the molecular adsorption intermediate interactions in M-Ti_(2)CO_(2)adhered to the 11-valence electron matching law.Electrostatic repulsion between the interface electrons in M-Ti_(2)CO_(2)and H_(2)O weakened the adsorption of intermediates,Furthermore,we applied the 11-valence electron matching law to guide the design of catalysts for nitrogen reduction reaction,specifically for N_(2)→NNH conversion,in the MTi_(2)CO_(2)structure.The sure independence screening and sparsifying operator algorithm was used to fit a simple three-dimensional descriptor of the adsorbate(R_(2)up to 0.970)for catalyst design.Our study introduced a valence electron matching principle between doped metals(single atoms)and adsorbed intermediates(atomic and molecular)for MXene-based catalysts,providing new insights into the design of high-performance SACs.
