A proposed strategy for constructing the nine-membered azonane ring system embedded in the isotwistane framework of palhinine A has been preliminarily studied on the basis of an azidoketol fragmentation reaction toget...A proposed strategy for constructing the nine-membered azonane ring system embedded in the isotwistane framework of palhinine A has been preliminarily studied on the basis of an azidoketol fragmentation reaction together with a SmI2-mediated pinacol coupling. Albeit negative results for building the azonane ring scaffold via a tertiary azidoketol fragmentation, the present exploration strategically provided an endeavor to probe the synthetically challenging issue in the synthetic study of palhinine A.展开更多
Chloride is the most abundant anion in living systems.Most natural or synthetic chloride anionophores function via hydrogen-bonding interactions.However,dynamic metal-anion coordination can also be an efficient way of...Chloride is the most abundant anion in living systems.Most natural or synthetic chloride anionophores function via hydrogen-bonding interactions.However,dynamic metal-anion coordination can also be an efficient way of transporting chloride across membranes.Here,we investigate anion transport by manganese(Ⅲ)meso-tetraphenylporphyrin chloride{[Mn(TPP)Cl],TPP=meso-tetraphenylporphyrin}complex that exhibits labile axial coordination.[Mn(TPP)Cl]showed high chloride transport activity in a bilayer vesicle model with an EC_(50) value of 4.42×10^(−3) mol%.In living cells,[Mn(TPP)Cl]induced rapid chloride influx and autophagy.The release of Ca^(2+)and adenosine 5′-triphosphate(ATP),as well as the relocation of calreticulin,revealed that[Mn(TPP)Cl]caused immunogenic cell death.Proteomic analysis indicated that[Mn(TPP)Cl]impaired several physiological processes,including DNA synthesis,transcription,mitochondrial respiration,RNA translation,and immune response.Our study suggests that dynamic metal-anion interactions across membranes might provide a practical strategy for the interference of chloride homeostasis.展开更多
基金supported by the National Natural Science Foundation of China (21572083, 21322201, 21290180)the Fundamental Research Funds for the Central Universities (lzujbky-2015-48, lzujbky2016-ct07)+1 种基金Program for Changjiang Scholars and Innovative Research Team in University (IRT_15R28)the 111 Project of MOE of China (111-2-17)
文摘A proposed strategy for constructing the nine-membered azonane ring system embedded in the isotwistane framework of palhinine A has been preliminarily studied on the basis of an azidoketol fragmentation reaction together with a SmI2-mediated pinacol coupling. Albeit negative results for building the azonane ring scaffold via a tertiary azidoketol fragmentation, the present exploration strategically provided an endeavor to probe the synthetically challenging issue in the synthetic study of palhinine A.
基金supported by the National Natural Science Foundation of China(grant nos.22022707,21778078,21877057,91953117,21837006,and 21773314)the innovative team of Ministry of Education(grant no.IRT_17R111)+3 种基金the Fundamental Research Funds for the Central Universitiesthe Guangdong Natural Science Funds for Distinguished Young Scholar(2019B151502017)EPSRC(no.EP/P030572/1)Chinese Scholarship Council(to F.-X.W.).
文摘Chloride is the most abundant anion in living systems.Most natural or synthetic chloride anionophores function via hydrogen-bonding interactions.However,dynamic metal-anion coordination can also be an efficient way of transporting chloride across membranes.Here,we investigate anion transport by manganese(Ⅲ)meso-tetraphenylporphyrin chloride{[Mn(TPP)Cl],TPP=meso-tetraphenylporphyrin}complex that exhibits labile axial coordination.[Mn(TPP)Cl]showed high chloride transport activity in a bilayer vesicle model with an EC_(50) value of 4.42×10^(−3) mol%.In living cells,[Mn(TPP)Cl]induced rapid chloride influx and autophagy.The release of Ca^(2+)and adenosine 5′-triphosphate(ATP),as well as the relocation of calreticulin,revealed that[Mn(TPP)Cl]caused immunogenic cell death.Proteomic analysis indicated that[Mn(TPP)Cl]impaired several physiological processes,including DNA synthesis,transcription,mitochondrial respiration,RNA translation,and immune response.Our study suggests that dynamic metal-anion interactions across membranes might provide a practical strategy for the interference of chloride homeostasis.
