Computational Investigation of the Role of Metal Center Identity in Cytochrome P450 Enzyme Model Reactivity.

Mononuclear Fe enzymes such as heme-containing cytochrome P450 enzymes catalyze a variety of C-H activation reactions under ambient conditions, and they represent an attractive platform for engineering reactivity through changes to the native enzyme. Using density functional theory, we study both native Fe and non-native group 8 (Ru, Os) and group 9 (Ir) metal centers in an active site model of P450. We quantify how changing the metal changes spin state preferences throughout the catalytic cycle.

No Bridge between Us: EXAFS and Computations Confirm Two Distant Iron Ions Comprise the Active Site of Alkane Monooxygenase (AlkB).

Alkane monooxygenase (AlkB) is the dominant enzyme that catalyzes the oxidation of liquid alkanes in the environment. Two recent structural models derived from cryo-electron microscopy (cryo-EM) reveal an unusual active site: a histidine-rich center that binds two iron ions without a bridging ligand. To ensure that potential photoreduction and radiation damage are not responsible for the absence of a bridging ligand in the cryo-EM structures, spectroscopic methods are needed.

Force-Activated Spin-Crossover in Fe and Co Transition Metal Mechanophores.

Transition metal mechanophores exhibiting force-activated spin-crossover are attractive design targets, yet large-scale discovery of them has not been pursued due in large part to the time-consuming nature of trial-and-error experiments. Instead, we leverage density functional theory (DFT) and external force explicitly included (EFEI) modeling to study a set of 395 feasible Fe and Co mechanophore candidates with tridentate ligands that we curate from the Cambridge Structural Database. Among nitrogen-coordinating low-spin complexes, we observe the prevalence of spin crossover at moderate force, and we identify 155 Fe and Co spin-crossover mechanophores and derive their threshold force for low-spin to high-spin transition ().

Tuning Metal-Organic Framework Linker Chemistry for Transition Metal Ion Separations.

The pressing demand for critical metals necessitates the development of advanced ion separation technologies for circular resource economies. To separate transition metal ions, which exhibit near-identical chemical properties, adsorbents and membranes must be designed with ultraselective chemistries. We leverage the customizability of metal-organic frameworks (MOFs) to systematically study the role of material chemistry in sorption and selectivity of Co, Ni, and Cu.