This project explores the chemistry of metalloporphyrins, spin coupling phenomena, and C60, all with the goal of discovering fundamental new chemistry that underpins the molecular level understanding of biology and medicine. The bioinorganic chemistry of superstructured metalloporphyrins and fullerenes will be investigated to uncover new multi-metal and multi- electron chemistry. Iron porphyrins with chelated copper or electron reservoir substituents (e.g. C60, ferrocene) will serve as models for cytochrome oxidase. A more diverse selection of metals and ligands (e.g. 'phosphine pincer porphyrin') will allow exploitation of chemistry unique to binucleating ligands. Spin coupling phenomena will be explored, particularly to test concepts of orthogonality of magnetic orbitals. Models for peroxidase Compound I will test the difference between a-1-u and a-2-u porphyrin radical spin coupling to iron and its relationship to porphyrin ruffling. The novel concept of a Magnetochemical Series will be explored with admixed spin iron(III) porphyrins. The fundamental chemistry of C60 will be explored to establish a chemical basis for potential biomedical applications. Emphasis in all of these studies will be placed on the definitive characterization of analytically pure materials by X-ray crystallography and spectroscopic methods, on the discovery of new chemistry, and on the demonstration of relationships to the molecular level chemistry of metalloproteins, particularly hemoproteins. An understanding of this fundamental bioinorganic chemistry must underlie medical approaches to the therapy of metalloprotein disorders (thalassemias, sickle cell anemia, etc.). New ligands and their metal complexes are finding applications as anti-arthritic drugs. C60 has potential applications in photodynamic therapy and as an anti-viral agent.

Agency
National Institute of Health (NIH)
Institute
National Institute of General Medical Sciences (NIGMS)
Type
Research Project (R01)
Project #
2R01GM023851-15
Application #
2174161
Study Section
Molecular and Cellular Biophysics Study Section (BBCA)
Project Start
1978-06-01
Project End
1999-06-30
Budget Start
1995-07-01
Budget End
1996-06-30
Support Year
15
Fiscal Year
1995
Total Cost
Indirect Cost
Name
University of Southern California
Department
Chemistry
Type
Schools of Arts and Sciences
DUNS #
041544081
City
Los Angeles
State
CA
Country
United States
Zip Code
90089
Nava, Matthew; Stoyanova, Irina V; Cummings, Steven et al. (2014) The strongest Brønsted acid: protonation of alkanes by H(CHB(11)F(11)) at room temperature. Angew Chem Int Ed Engl 53:1131-4
Reed, Christopher A; Stoyanov, Evgenii S; Tham, Fook S (2013) Hydrogen bonding versus hyperconjugation in condensed-phase carbocations. Org Biomol Chem 11:3797-802
Reed, Christopher A (2013) Myths about the proton. The nature of H+ in condensed media. Acc Chem Res 46:2567-75
Stoyanov, Evgenii S; Stoyanova, Irina V; Tham, Fook S et al. (2012) Evidence for C-H hydrogen bonding in salts of tert-butyl cation. Angew Chem Int Ed Engl 51:9149-51
Stoyanov, Evgenii S; Gunbas, Gorkem; Hafezi, Nema et al. (2012) The R3O+···H+ hydrogen bond: toward a tetracoordinate oxadionium(2+) ion. J Am Chem Soc 134:707-14
Nava, Matthew; Reed, Christopher A (2011) Triethylsilyl Perfluoro-Tetraphenylborate, [Et(3)Si][F(20)-BPh(4)], a widely used Non-Existent Compound. Organometallics 30:4798-4800
Nava, Matthew J; Reed, Christopher A (2010) High yield C-derivatization of weakly coordinating carborane anions. Inorg Chem 49:4726-8
Stoyanov, Evgenii S; Stoyanova, Irina V; Reed, Christopher A (2010) The structure of the hydrogen ion (H(aq)+) in water. J Am Chem Soc 132:1484-5
Reed, Christopher A (2010) H(+), CH(3)(+), and R(3)Si(+) carborane reagents: when triflates fail. Acc Chem Res 43:121-8
Stoyanov, Evgenii S; Stoyanova, Irina V; Tham, Fook S et al. (2009) H(aq)+ structures in proton wires inside nanotubes. J Am Chem Soc 131:17540-1

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