Development of a heme protein structure-electrochemical function database.

Proteins containing heme, iron(protoporphyrin IX) and its variants, continue to be one of the most-studied classes of biomolecules due to their diverse range of biological functions. The literature is abundant with reports of structural and functional characterization of individual heme proteins which demonstrate that heme protein reduction potential values, E(m), span the range from -550 mV to +450 mV versus SHE. In order to unite these data for the purposes of global analysis, a new web-based resource of heme protein structure-function relationships is presented: the Heme Protein Database (HPD).

Thermodynamic investigation into the mechanisms of proton-coupled electron transfer events in heme protein maquettes.

To study the engineering requirements for proton pumping in energy-converting enzymes such as cytochrome c oxidase, the thermodynamics and mechanisms of proton-coupled electron transfer in two designed heme proteins are elucidated. Both heme protein maquettes chosen, heme b-[H10A24]2 and heme b-[delta7-His]2, are four-alpha-helix bundles that display pH-dependent heme midpoint potential modulations, or redox-Bohr effects. Detailed equilibrium binding studies of ferric and ferrous heme b with these maquettes allow the individual contributions of heme-protein association, iron-histidine ligation, and heme-protein electrostatics to be elucidated.

Thermodynamic characterization of ferric and ferrous haem binding to a designed four-alpha-helix protein.

The thermodynamics of ferric and ferrous haem affinity of a de novo designed four-alpha-helix bundle protein and the associated haem electrochemistry is described.

Nonnatural amino acid ligands in heme protein design.

The de novo design, synthesis, and characterization of a four-alpha-helix bundle scaffold containing heme ligated by 4-beta-(pyridyl)-l-alanine (Pal) is presented. The protein scaffold is highly helical, stable, and conformationally specific in the apo-state. Incorporation of heme using the designed bis-Pal axial ligation is shown using UV-visible and EPR spectroscopies.

Approaches to Alkaline Earth Metal-Organic Chemical Vapor Deposition Precursors. Synthesis and Characterization of Barium Fluoro-beta-ketoiminate Complexes Having Appended Polyether "Lariats".

The synthesis and characterization of a family of beta-ketoimines derived from 1,1,1,5,5,5-hexafluoro-2,4-pentanedione (hfa) and the corresponding volatile barium beta-ketoiminate-polyether complexes having the general formula Ba[CF(3)COCHC(NR)CF(3)](2) where R = (CH(2)CH(2)O)(2)CH(3), (CH(2)CH(2)O)(2)CH(2)CH(3), and (CH(2)CH(2)O)(3)CH(2)CH(3) is reported. These complexes can be transported in the vapor phase at 160 degrees C/0.05 Torr without decomposition.