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Photoinduced Electron Transfer from PbS Quantum Dots to Cobalt(III) Schiff Base Complexes: Light Activation of a Protein Inhibitor

Peterson, Mark D., Holbrook, Robert J., Meade, Thomas J., Weiss, Emily A.
Journal of the American Chemical Society 2013 v.135 no.35 pp. 13162-13167
active sites, cobalt, electron transfer, energy, histidine, ligands, quantum dots, schiff bases
This paper describes the activation of a biologically inert Co(III) Schiff base [Co(III)-SB] complex to its protein inhibitor form by photoinduced electron transfer (PET) from a colloidal PbS quantum dot (QD, radii of 1.5–1.7 nm) to the cobalt center, with a charge separation time constant of 125 ns. Reduction of the Co(III)-SB complex initiates release of the native axial ligands, promoting replacement with the histidine mimic 4-methylimidazole. The rate of ligand displacement increases by a factor of approximately 8 upon exposure of the PbS QD/Co(III)-SB mixture to light with an energy greater than the energy of the first excitonic state of the QDs, from which PET occurs. These results suggest an approach for the preparation of inorganic therapeutic agents that can be specifically coupled to a biologically active site by cooperative redox binding ligation.