A titrant for the SARS-CoV-2 main protease(M^(pro))was developed that enables,for the first time,the exact determination of the concentration of the enzymatically active M^(pro) by active-site titration.The covalent b...A titrant for the SARS-CoV-2 main protease(M^(pro))was developed that enables,for the first time,the exact determination of the concentration of the enzymatically active M^(pro) by active-site titration.The covalent binding mode of the tetrapeptidic titrant was elucidated by the determination of the crystal structure of the enzyme–titrant complex.Four fluorogenic substrates of M^(pro),including a prototypical,internally quenched Dabcyl-EDANS peptide,were compared in terms of solubility under typical assay conditions.By exploiting the new titrant,key kinetic parameters for the M^(pro)-catalyzed cleavage of these substrates were determined.展开更多
Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction(NRR)of which the mechanism has been illustrated by ongoing investigations of single atom catalysis.However,it remains cha...Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction(NRR)of which the mechanism has been illustrated by ongoing investigations of single atom catalysis.However,it remains challenging to fully understand the size-dependent synergistic effect of active sites inherited in substantial nanocatalysts.In this work,four types of small iron clusters Fen(n=1–4)supported on nitrogen-doped graphene sheets are constructed to figure out the size dependence and synergistic effect of active sites for NRR catalytic activities.It is revealed that Fe3 and Fe4 clusters on N4G supports exhibit higher NRR activity than single-iron atom and iron dimer clusters,showing lowered limiting potential and restricted hydrogen evolution reaction(HER)which is a competitive reaction channel.In particular,the Fe4-N4G displays outstanding NRR performance for“side-on”adsorption of N2 with a small limiting potential(−0.45 V).Besides the specific structure and strong interface interaction within the Fe4-N4G itself,the high NRR activity is associated with the unique bonding/antibonding orbital interactions of N-N and N-Fe for the adsorptive N2 and NNH intermediates,as well as relatively large charge transfer between N2 and the cluster Fe4-N4G.展开更多
Hierarchical Pt-alloys enriched with active sites are highly desirable for efficient catalysis,but their syntheses generally need time-consuming and elaborate annealing treatment at high temperature.We herein report a...Hierarchical Pt-alloys enriched with active sites are highly desirable for efficient catalysis,but their syntheses generally need time-consuming and elaborate annealing treatment at high temperature.We herein report a surface active-site engineering strategy for constructing the hierarchical PtNi nanocatalysts with an atomic Pt-skin layer(PtNi@Pt-SL)towards efficient triiodide reduction reaction(TRR)via an acid-dealloying approach.The facile acid-dealloying process promotes the formation of surface Pt active sites on the hierarchical Pt-alloys,and thus results in good catalytic performance towards TRR.Theoretical calculation reveals that the enhanced catalytic property stems from the moderate energy barriers for iodide atoms on the surface Pt active-sites.The surface active-site engineering strategy paves a new way for the design of active and durable electrocatalysts.展开更多
基金The authors acknowledge support by Dr.Carina Lemke and Marion Schneider.Christa E.Müller and Michael Gütschow were supported by the Volkswagen Foundation(9A894)Rabea Voget,Christian Steinebach,Christa E.Müller and Michael Gütschow by the German Research Foundation(RTG 2873)Norbert Sträter by the Volkswagen Foundation(9A850).We acknowledge DESY(Hamburg,Germany),a member of the Helmholtz Association HGF,and the EMBL for the provision of experimental facilities at synchrotron beamlines P13 and P14 and the MX Laboratory at the Helmholtz Zentrum Berlin(BESSY II)for beam time.We would like to thank Selina Storm for assistance in using the EMBL beamlines.
文摘A titrant for the SARS-CoV-2 main protease(M^(pro))was developed that enables,for the first time,the exact determination of the concentration of the enzymatically active M^(pro) by active-site titration.The covalent binding mode of the tetrapeptidic titrant was elucidated by the determination of the crystal structure of the enzyme–titrant complex.Four fluorogenic substrates of M^(pro),including a prototypical,internally quenched Dabcyl-EDANS peptide,were compared in terms of solubility under typical assay conditions.By exploiting the new titrant,key kinetic parameters for the M^(pro)-catalyzed cleavage of these substrates were determined.
基金This work was financially supported by the National Natural Science Foundation of China(Nos.21802146 and 21722308)CAS Key Research Project of Frontier Science(No.QYZDB-SSW-SLH024)Frontier Cross Project of National Laboratory for Molecular Sciences(No.051Z011BZ3).
文摘Nonprecious metal catalysts are known of significance for electrochemical N2 reduction reaction(NRR)of which the mechanism has been illustrated by ongoing investigations of single atom catalysis.However,it remains challenging to fully understand the size-dependent synergistic effect of active sites inherited in substantial nanocatalysts.In this work,four types of small iron clusters Fen(n=1–4)supported on nitrogen-doped graphene sheets are constructed to figure out the size dependence and synergistic effect of active sites for NRR catalytic activities.It is revealed that Fe3 and Fe4 clusters on N4G supports exhibit higher NRR activity than single-iron atom and iron dimer clusters,showing lowered limiting potential and restricted hydrogen evolution reaction(HER)which is a competitive reaction channel.In particular,the Fe4-N4G displays outstanding NRR performance for“side-on”adsorption of N2 with a small limiting potential(−0.45 V).Besides the specific structure and strong interface interaction within the Fe4-N4G itself,the high NRR activity is associated with the unique bonding/antibonding orbital interactions of N-N and N-Fe for the adsorptive N2 and NNH intermediates,as well as relatively large charge transfer between N2 and the cluster Fe4-N4G.
基金The research was financially supported by the National Natural Science Foundation of China(No.21771019)the National Key Research and Development Program of China(No.2018YFA0702002)+1 种基金the Fundamental Research Funds for the Central Universities(Nos.XK1901 and buctrc202023)P.Ma is funded by China Postdoctoral Science Foundation(No.2020M672772)。
文摘Hierarchical Pt-alloys enriched with active sites are highly desirable for efficient catalysis,but their syntheses generally need time-consuming and elaborate annealing treatment at high temperature.We herein report a surface active-site engineering strategy for constructing the hierarchical PtNi nanocatalysts with an atomic Pt-skin layer(PtNi@Pt-SL)towards efficient triiodide reduction reaction(TRR)via an acid-dealloying approach.The facile acid-dealloying process promotes the formation of surface Pt active sites on the hierarchical Pt-alloys,and thus results in good catalytic performance towards TRR.Theoretical calculation reveals that the enhanced catalytic property stems from the moderate energy barriers for iodide atoms on the surface Pt active-sites.The surface active-site engineering strategy paves a new way for the design of active and durable electrocatalysts.