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  • Spectroscopic definition of ferrous active sites in non-heme iron enzymes. Methods in enzymology Solomon, E. I., Gipson, R. R. 2024; 703: 29-49

    Abstract

    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., 1995). This method provides detailed geometric and electronic structure insight and thus enables a molecular level understanding of catalytic mechanisms. Application of this method across the five classes of non-heme ferrous enzymes has defined that a general mechanistic strategy is utilized where O2 activation is controlled to occur only in the presence of all cosubstrates.

    View details for DOI 10.1016/bs.mie.2024.05.019

    View details for PubMedID 39261000

    View details for PubMedCentralID PMC11391101

  • Photoinduced Surface Charging in Iron-Carbonyl-Functionalized Colloidal Semiconductor Nanocrystals NANO LETTERS Schival, K. A., Gipson, R. R., Prather, K. V., Tsui, E. Y. 2019; 19 (11): 7770-7774

    Abstract

    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. These measurements revealed that CdSe nanocrystals can accumulate multiple surface electrons under supra-band gap photoexcitation, a process likely relevant to photoactivated nanocrystal processes such as photobrightening. These surface charges are stable for hours and decay extremely slowly under anaerobic conditions.

    View details for DOI 10.1021/acs.nanolett.9b02726

    View details for Web of Science ID 000497259300024

    View details for PubMedID 31596596