Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresse...Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresses the structural absence and configuration stability controversies of face-centered cubic(FCC)-configured RS-AuNCs in the large-size regime of 102–191 gold atoms by establishing an innovative theoretical analysis framework.Through density functional theory(DFT)calculations,we successfully predicted for the first time a twinned-FCC Au127(SR)48 structure with C_(2) symmetry(Au127-x),which exhibits a remarkably small energy difference of merely 0.03 eV compared to the lowest-energy Dh configuration(Au127-w).This discovery strongly confirms the thermodynamic feasibility of FCC configurations in the 102-144 atom range.By integrating the‘kernel-differentiated fusion’growth mechanism with the‘divideand-protected’assembly strategy,we systematically constructed three large-sized FCC cluster models:Au164(SR)60,Au_(182)(SR)_(66) and Au_(188)(SR)_(66).The calculated average formation energies(Eave)validate the exceptional structural stability of these clusters.Strikingly divergent evolution patterns in HOMO–LUMO gaps are observed between shell-structured and cubic FCC-type RS-AuNCs across varying sizes,unambiguously demonstrating configuration-governed electronic structure modulation.More crucially,UV-Vis absorption spectra unveil emergent metallic signatures in both Au_(182)(SR)_(66) and Au_(188)(SR)_(66) clusters,thereby fundamentally redefining the critical size threshold for incipient metallicity in FCC-type RS-AuNCs.Breaking through traditional theoretical frameworks centered on‘size-configuration preference’,this research first elucidates the potential stability of FCC-configured RS-AuNCs within controversial size ranges.It not only addresses the existing size gap in structural models of large RS-AuNCs but also establishes a novel configuration design paradigm based on a‘kernel-differentiated fusion’strategy.展开更多
The synthesis of gold nanoclusters within protein structures,such as TetX2 monooxygenase,presents a promising approach for obtaining nanostructures with enzyme-like activity.This is attributed to the presence of vario...The synthesis of gold nanoclusters within protein structures,such as TetX2 monooxygenase,presents a promising approach for obtaining nanostructures with enzyme-like activity.This is attributed to the presence of various amino acid groups that serve as biological templates for the formation and reduction of gold.The low toxicity,biocompatibility,solubility in aqueous systems,and specific fluorescence spectrum of these nanostructures enhance their utility in the detection of various analytes.The research involved expressing and purifying the recombinant enzyme TetX2,synthesizing gold on the TetX2 substrate,and investigating the effect of nanoclusters on the activity and structure of the TetX2 enzyme.The synthesis of gold nanoclusters(AuNCs)was carried out within the structure of TetX2.Finally,the accuracy of the AuNCs synthesis was verified by examining the morphology,size,spectroscopy,and catalytic activity.Results showed changes in the tertiary structure of the TetX2 enzyme in the presence of HAuCl4,loss of enzyme activity after the formation of gold nanoclusters,and successful incorporation of gold into the structure of TetX2.TetX2@AuNCs emitted blue light at 450 nm,and their catalytic properties were demonstrated through color changes in a chromogenic substrate(3,3′,5,5′-Tetramethylbenzidine-H2O2),indicating their authenticity.TetX2 is proposed as a new bio-template forthe synthesis of gold nanoclusters,with potential applications in biosensor design(Graphical abstract).展开更多
Protein protected gold nanoclusters have outstanding physical and chemical properties that make them excellent scaffolds for the construction of novel chemical and biological probes. In this study, a simple one-pot sy...Protein protected gold nanoclusters have outstanding physical and chemical properties that make them excellent scaffolds for the construction of novel chemical and biological probes. In this study, a simple one-pot synthesis method was proposed for the preparation of fluorescent probes based on ovalbumin-stabilized gold nanoclusters. This strategy allowed the generation of water-soluble gold nanoclusters within 5 min. The as-prepared fluorescent probe exhibited a red fluorescence emission at 625 nm, and good thermostability. The fluorescent probe was applied to measure glucose concentrations based on the hydrogen peroxide-induced fluorescence quenching principle, and showed favorable biocompatibility, high sensitivity and good selectivity. As a result of the advantageous properties and performance of this fluorescent probe, the present assay allowed for the selective determination of glucose in the range of 5.0×10-6 to 10.0×10-3 mol/L with a detection limit of 1.0×10?6 mol/L. Moreover, the glucose content in urinary samples was analyzed using the constructed fluorescent probe: this indicated the potential of the fluorescent gold nanoclusters for applications in biological and clinical diagnosis and therapy.展开更多
基金the financial support from the National Natural Science Foundation of China(Grant No.22203053)the Natural Science Foundation of Hunan Province(Grant No.2023JJ40606)+1 种基金Y.P.was financially supported by the National Natural Science Foundation of China(Grant No.22373082)the science and technology innovation program of Hunan Province(2023RC1055).
文摘Thiolate-protected gold nanoclusters(RS-AuNCs)have emerged as an ideal research system for unveiling intrinsic structure–property correlations due to their atomically precise structural tunability.This study addresses the structural absence and configuration stability controversies of face-centered cubic(FCC)-configured RS-AuNCs in the large-size regime of 102–191 gold atoms by establishing an innovative theoretical analysis framework.Through density functional theory(DFT)calculations,we successfully predicted for the first time a twinned-FCC Au127(SR)48 structure with C_(2) symmetry(Au127-x),which exhibits a remarkably small energy difference of merely 0.03 eV compared to the lowest-energy Dh configuration(Au127-w).This discovery strongly confirms the thermodynamic feasibility of FCC configurations in the 102-144 atom range.By integrating the‘kernel-differentiated fusion’growth mechanism with the‘divideand-protected’assembly strategy,we systematically constructed three large-sized FCC cluster models:Au164(SR)60,Au_(182)(SR)_(66) and Au_(188)(SR)_(66).The calculated average formation energies(Eave)validate the exceptional structural stability of these clusters.Strikingly divergent evolution patterns in HOMO–LUMO gaps are observed between shell-structured and cubic FCC-type RS-AuNCs across varying sizes,unambiguously demonstrating configuration-governed electronic structure modulation.More crucially,UV-Vis absorption spectra unveil emergent metallic signatures in both Au_(182)(SR)_(66) and Au_(188)(SR)_(66) clusters,thereby fundamentally redefining the critical size threshold for incipient metallicity in FCC-type RS-AuNCs.Breaking through traditional theoretical frameworks centered on‘size-configuration preference’,this research first elucidates the potential stability of FCC-configured RS-AuNCs within controversial size ranges.It not only addresses the existing size gap in structural models of large RS-AuNCs but also establishes a novel configuration design paradigm based on a‘kernel-differentiated fusion’strategy.
基金financially supported by Nora Gene Pishro Companythe support from the University of Tehran.
文摘The synthesis of gold nanoclusters within protein structures,such as TetX2 monooxygenase,presents a promising approach for obtaining nanostructures with enzyme-like activity.This is attributed to the presence of various amino acid groups that serve as biological templates for the formation and reduction of gold.The low toxicity,biocompatibility,solubility in aqueous systems,and specific fluorescence spectrum of these nanostructures enhance their utility in the detection of various analytes.The research involved expressing and purifying the recombinant enzyme TetX2,synthesizing gold on the TetX2 substrate,and investigating the effect of nanoclusters on the activity and structure of the TetX2 enzyme.The synthesis of gold nanoclusters(AuNCs)was carried out within the structure of TetX2.Finally,the accuracy of the AuNCs synthesis was verified by examining the morphology,size,spectroscopy,and catalytic activity.Results showed changes in the tertiary structure of the TetX2 enzyme in the presence of HAuCl4,loss of enzyme activity after the formation of gold nanoclusters,and successful incorporation of gold into the structure of TetX2.TetX2@AuNCs emitted blue light at 450 nm,and their catalytic properties were demonstrated through color changes in a chromogenic substrate(3,3′,5,5′-Tetramethylbenzidine-H2O2),indicating their authenticity.TetX2 is proposed as a new bio-template forthe synthesis of gold nanoclusters,with potential applications in biosensor design(Graphical abstract).
基金supported by the National Natural Science Foundation of China(21375132,21175138,21321003,21171114,91222202)the National Basic Research Program of China(2013CB834803)
文摘Protein protected gold nanoclusters have outstanding physical and chemical properties that make them excellent scaffolds for the construction of novel chemical and biological probes. In this study, a simple one-pot synthesis method was proposed for the preparation of fluorescent probes based on ovalbumin-stabilized gold nanoclusters. This strategy allowed the generation of water-soluble gold nanoclusters within 5 min. The as-prepared fluorescent probe exhibited a red fluorescence emission at 625 nm, and good thermostability. The fluorescent probe was applied to measure glucose concentrations based on the hydrogen peroxide-induced fluorescence quenching principle, and showed favorable biocompatibility, high sensitivity and good selectivity. As a result of the advantageous properties and performance of this fluorescent probe, the present assay allowed for the selective determination of glucose in the range of 5.0×10-6 to 10.0×10-3 mol/L with a detection limit of 1.0×10?6 mol/L. Moreover, the glucose content in urinary samples was analyzed using the constructed fluorescent probe: this indicated the potential of the fluorescent gold nanoclusters for applications in biological and clinical diagnosis and therapy.
