Modulation by Co (II) Ion of Optical Activities of L/D-glutathione (GSH)-modified Chiral Copper Nanoclusters for Sensitive Adenosine Triphosphate Detection.

Chiral nanoscale enantiomers exhibit different biological effects in living systems. However, their chirality effect on the detection sensitivity for chiral biological targets still needs to be explored. Here, we discovered that Co2+ can modulate the luminescence performance of L/D-glutathione (GSH)-modified copper nanoclusters (L/D-Cu NCs) and induce strong chiroptical activities as the asymmetric factor was enhanced 223-fold with their distribution regulating from the ultraviolet to visible region. One Co2+ coordinated with two GSH molecules that modified on the surface of Cu NCs in the way of CoN2O2. On this basis, dual-modal chiral and luminescent signals of Co2+ coordinated L/D-Cu NCs (L/D-Co-Cu NCs) were used to detect the chiral adenosine triphosphate (ATP) based on the competitive interaction between surficial GSH and ATP molecules with Co2+. The limits of detection of ATP obtained with fluorescence and circular dichroism intensity were 9.15 µM and 15.75 nM for L-Co-Cu NCs, and 5.35 µM and 4.69 nM for D-Co-Cu NCs. This demonstrated that selecting suitable chiral configurations of nanoprobes effectively enhances detection sensitivity. This study presents not only a novel method to modulate and enhance the chiroptical activity of nanomaterials but also a unique perspective of chirality effects on the detection performances for bio-targets.

Activation-Induced Senescent Cell Death based on Chiral CoHAu Nanoassemblies with Enantioselective Cascade-Catalytic Ability.

Chirality is common in nature, which determines the high enantioselectivity of living systems. Selecting suitable chiral configurations is of great meaning for nanostructures to function better in biological systems. In this study, chiral Co3O4-H2TPPS-Au (CoHAu) nanoassemblies are constructed to accelerate the production ∙OH by consuming D-glucose (D-Glu, widely spread in nature) based on their outstanding enantioselective cascade-catalytic abilities. In particular, D-CoHAu nanoassemblies are more effective in the catalytic conversion of D-Glu than L-CoHAu nanoassemblies. This phenomenon is due to the stronger binding affinity of D-CoHAu nanoassemblies indicated by the lower Km value. Moreover, D-CoHAu nanoassemblies display excellent consumption-ability of D-Glu and production of ∙OH in living cells, which can eliminate senescent cells effectively based on their intracellular enantioselective cascade-catalysis. This research establishes the foundation for bio-mimicking nanostructures with unique functionalities to regulate abnormal biological activities better.