CAREER: Solid-State NMR of Half-Integer Quadrupolar Vanadium Sites in Vanadium Haloperoxidases

University Of Delaware, Newark DE

Investigators

Abstract

In this CAREER project funded by the Experimental Physical Chemistry Program of the Chemistry Division, Polenova will study vanadium-containing enzymes and associated model compounds using a variety of NMR techniques. The NMR experiments will be interpreted using density matrix simulations of spectra, and the electric quadrupole gradients for the vanadium will be interpreted using parameterized electronic structure calculations. These methods will be applied to haloperoxidases as well as to studies of vanadyl model compounds with known crystal structure. Metal ions serve a number of purposes in proteins, including catalytic, storage, and structural functions. Many of the mechanistic aspects behind these functions are not well understood. The application of solid-state NMR to metal sites in proteins is an important application. In this work Polenova is able to gather data about metal complexes with high sensitivity and high resolution. These data should have an impact on understanding biologically relevant systems as well as helping advance the state of knowledge at the interface between spectroscopy, bioinorganic chemistry, and metallobiochemistry. The results have the potential to help develop more environmentally friendly methods of catalysis. In her research program Polenova involves not only graduate and undergraduate students, but she also performs outreach to high school students. In addition, her education activities encourage underrepresented groups to pursue careers in science.