Spectroscopic definition of ferrous active sites in non-heme iron enzymes.

Non-heme iron enzymes play key roles in antibiotic, neurotransmitter, and natural product biosynthesis, DNA repair, hypoxia regulation, and disease states. These enzymes had been refractory to traditional bioinorganic spectroscopic methods. Thus, we developed variable-temperature variable-field magnetic circular dichroism (VTVH MCD) spectroscopy to experimentally define the excited and ground ligand field states of non-heme ferrous enzymes (Solomon et al.

Photoinduced Surface Charging in Iron-Carbonyl-Functionalized Colloidal Semiconductor Nanocrystals.

Organometallic surface functionalization of colloidal CdSe and CdS nanocrystals using iron tetracarbonyl moieties is demonstrated to enable study of in situ colloidal nanocrystal surface redox chemistry. Spectroscopic measurements of the surface-bound metal carbonyl C-O stretches were used to elucidate the coordination environments and local symmetry of surface sites. The C-O stretching frequencies of these fragments were correlated to the electric field induced by nanocrystal surface charges and shift in energy upon surface reduction or oxidation.