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Nitroreductase: Evidence For A Fluxional Low-Temperature State And Its Possible Role In Enzyme Activity, Peng Zhang Jan 2007

Nitroreductase: Evidence For A Fluxional Low-Temperature State And Its Possible Role In Enzyme Activity, Peng Zhang

University of Kentucky Doctoral Dissertations

The enzyme nitroreductase (NR) catalyzes two-electron reduction of high explosives such as trinitrotoluene (TNT), a wide variety of other toxic nitroaromatic compounds, as well as riboflavin derivatives, using a tightly-bound flavin mononucleotide (FMN) cofactor. It has important environmental and clinical implications. Previous studies have focused on elucidating NRs catalytic mechanism and solving its crystal structure.

In this dissertation work, we first develop and implement new strategies for labeling NR with stable isotopes, and report a completely re-designed protocol for NRs purification. Then we report the successful assignment of over half of NRs backbone resonances using 3d-NMR methods. The most significant …


Polymorphism Of Four Enantiotropic Crystalline Systems Containing Ni(Ii), H2O, 15-Crown-5 And No3-, Maxime Andre Siegler Jan 2007

Polymorphism Of Four Enantiotropic Crystalline Systems Containing Ni(Ii), H2O, 15-Crown-5 And No3-, Maxime Andre Siegler

University of Kentucky Doctoral Dissertations

The series of compounds [M(H2O)2(15-crown-5)](NO3)2, M = Mg, Mn, Co, Cu and Zn, has been extended to include two new phases for M = Fe and two new phases for M = Ni. The system [M(H2O)2(15-crown-5)](NO3)2 is remarkable for having many high-Z’ phases (Z’ > 1) with similar packing and for having solid-solid phase transitions through which there is no significant loss of crystallinity. The synthesis of the analogous Ni complex was carried out. Single-crystal X-ray diffraction showed …