Developing ligands that improve the stability of G-quadruplex DNA(G4)is a promising anticancer strategy.We constructed a peptide-heme-NH_(3)/G4 hybrid complex possessing a unique NH_(3)axial ligand between the heme an...Developing ligands that improve the stability of G-quadruplex DNA(G4)is a promising anticancer strategy.We constructed a peptide-heme-NH_(3)/G4 hybrid complex possessing a unique NH_(3)axial ligand between the heme and G-quartet planes.The interface between the heme and G-quartet planes is well adapted to accommodate an NH_(3)molecule,with a ligand substituent constant(K_(s))from 98733±7141 to 18357±284 M^(−1) at 15–35℃.Compared with free peptide-heme-N_(2)O,complexation with G4 resulted in a 22–35-fold increase in K_(s) value.The binding constant(K_(a))between peptide-heme-NH_(3)and G4 was determined to be between 37.6±4.9 and 121.8±3.0μM^(−1 )at 15–35℃,21–30-fold higher than the value observed for the peptide-heme-N_(2)O/G4 hybrid complex.Thermodynamic analysis of experimental data showed that interactions between the heme and G-quartet planes are highly sensitive to Fe-bound NH_(3)and N_(2)O ligands,which significantly enhance the thermal stability of G4 through an enthalpy-driven ligand substituent reaction and an entropy-driven complexation reaction.These findings provide novel insights and mechanistic clues for designing anticancer metal complexes targeting G4.展开更多
The development of porous MOFs exhibiting highly selective C_(2)H_(2)/CH_(4)and CO_(2)/CH_(4)separations is quite important to meet the requirement of high-purity C_(2)H_(2)and CH_(4)in various industries.By employing...The development of porous MOFs exhibiting highly selective C_(2)H_(2)/CH_(4)and CO_(2)/CH_(4)separations is quite important to meet the requirement of high-purity C_(2)H_(2)and CH_(4)in various industries.By employing a ligand heterobifunctionalization strategy,we designed and synthesized an aminopyridine-functionalized diisophthalate ligand,and successfully targeted its corresponding copper-based NbO-type MOF ZJNU-98.Gas adsorption studies revealed that ZJNU-98 exhibited significantly enhanced adsorption of C_(2)H_(2)and CO_(2)over CH_(4)compared to its parent MOF,NOTT-101.At 298 K and 1 atm,C_(2)H_(2)and CO_(2)uptakes of ZJNU-98 are 10.0%and 16.7%higher than the corresponding values of NOTT-101,while 14.2%and 18.8%increases in C_(2)H_(2)/CH_(4)and CO_(2)/CH_(4)adsorption selectivities were observed for the equimolar gas mixtures in ZJNU-98 compared to NOTT-101.Furthermore,the contribution of the functional group effect on gas adsorption has been assessed,demonstrating that the amine group plays a more important role than the pyridinic-N atom despite its lower Lewis basicity.This work provided an effective way and significant experimental evidence for the design of new porous MOFs with highly enhanced gas adsorption performance.展开更多
The development of porous MOFs with novel structures and functional properties is a key research topic in the MOF chemistry and materials field.In this article,by employing a ligand conformation preorganization strate...The development of porous MOFs with novel structures and functional properties is a key research topic in the MOF chemistry and materials field.In this article,by employing a ligand conformation preorganization strategy,we designed a nonplanar methyl-substituted triisophthalate ligand,which was used to successfully construct a copper-hexacarboxylate framework with a novel topological structure.More importantly,the obtained MOF not only exhibits good hydrolytic stability but also shows utility as an adsorbent for efficient separation and purification of C_(2)H_(2)and natural gas under ambient conditions.At ambient temperature and atmospheric pressure,the C_(2)H_(2)and CO_(2)uptake capacities reach up to 149.1 and 83.1 cm^(3)(STP)g^(−1),while the IAST-predicted C_(2)H_(2)/CH_(4)(50/50,v/v),C_(2)H_(2)/CO_(2)(50/50,v/v),and CO_(2)/CH_(4)(50/50,v/v)adsorption selectivities are as high as 22.2,3.81,and 5.13.展开更多
基金supported by the National Natural Science Foundation of China(22467021 and 21977125 to H.T.)the Higher Education Discipline Innovation Project(D18012 to H.T.).
文摘Developing ligands that improve the stability of G-quadruplex DNA(G4)is a promising anticancer strategy.We constructed a peptide-heme-NH_(3)/G4 hybrid complex possessing a unique NH_(3)axial ligand between the heme and G-quartet planes.The interface between the heme and G-quartet planes is well adapted to accommodate an NH_(3)molecule,with a ligand substituent constant(K_(s))from 98733±7141 to 18357±284 M^(−1) at 15–35℃.Compared with free peptide-heme-N_(2)O,complexation with G4 resulted in a 22–35-fold increase in K_(s) value.The binding constant(K_(a))between peptide-heme-NH_(3)and G4 was determined to be between 37.6±4.9 and 121.8±3.0μM^(−1 )at 15–35℃,21–30-fold higher than the value observed for the peptide-heme-N_(2)O/G4 hybrid complex.Thermodynamic analysis of experimental data showed that interactions between the heme and G-quartet planes are highly sensitive to Fe-bound NH_(3)and N_(2)O ligands,which significantly enhance the thermal stability of G4 through an enthalpy-driven ligand substituent reaction and an entropy-driven complexation reaction.These findings provide novel insights and mechanistic clues for designing anticancer metal complexes targeting G4.
基金the Natural Science Foundation of China(No.21771162)the Natural Science Foundation of Zhejiang Province,China(LR16B010001)for financial support.
文摘The development of porous MOFs exhibiting highly selective C_(2)H_(2)/CH_(4)and CO_(2)/CH_(4)separations is quite important to meet the requirement of high-purity C_(2)H_(2)and CH_(4)in various industries.By employing a ligand heterobifunctionalization strategy,we designed and synthesized an aminopyridine-functionalized diisophthalate ligand,and successfully targeted its corresponding copper-based NbO-type MOF ZJNU-98.Gas adsorption studies revealed that ZJNU-98 exhibited significantly enhanced adsorption of C_(2)H_(2)and CO_(2)over CH_(4)compared to its parent MOF,NOTT-101.At 298 K and 1 atm,C_(2)H_(2)and CO_(2)uptakes of ZJNU-98 are 10.0%and 16.7%higher than the corresponding values of NOTT-101,while 14.2%and 18.8%increases in C_(2)H_(2)/CH_(4)and CO_(2)/CH_(4)adsorption selectivities were observed for the equimolar gas mixtures in ZJNU-98 compared to NOTT-101.Furthermore,the contribution of the functional group effect on gas adsorption has been assessed,demonstrating that the amine group plays a more important role than the pyridinic-N atom despite its lower Lewis basicity.This work provided an effective way and significant experimental evidence for the design of new porous MOFs with highly enhanced gas adsorption performance.
基金supported by the Natural Science Foundation of China(No.21771162,21761003)the Natural Science Foundation of Zhejiang Province,China(LR16B010001)the Qianjiang Talents Project in Zhejiang Province(ZC304015017).
文摘The development of porous MOFs with novel structures and functional properties is a key research topic in the MOF chemistry and materials field.In this article,by employing a ligand conformation preorganization strategy,we designed a nonplanar methyl-substituted triisophthalate ligand,which was used to successfully construct a copper-hexacarboxylate framework with a novel topological structure.More importantly,the obtained MOF not only exhibits good hydrolytic stability but also shows utility as an adsorbent for efficient separation and purification of C_(2)H_(2)and natural gas under ambient conditions.At ambient temperature and atmospheric pressure,the C_(2)H_(2)and CO_(2)uptake capacities reach up to 149.1 and 83.1 cm^(3)(STP)g^(−1),while the IAST-predicted C_(2)H_(2)/CH_(4)(50/50,v/v),C_(2)H_(2)/CO_(2)(50/50,v/v),and CO_(2)/CH_(4)(50/50,v/v)adsorption selectivities are as high as 22.2,3.81,and 5.13.
