Metallo-Sulfur Complexes as Models for Electron Transfer Proteins

Paulson, Donald R.

Abstract

The chemistry of metal-dithiolate complexes and metal disulfide complexes will be studied as model systems for metallo-thiolate electron transport proteins such as the ubiquitous iron-sulfur proteins. It is proposed that these metalloproteins can obtain additional reducing power by the formation partial S.S bonds through interaction of two adjacent metal-bound thiolates. Evidence for this hypothesis comes from a number of examples of metal-thiolate complexes where the S.S separations are considerably smaller than the predicted nearest neighbor contact of non-bonded sulfur atoms. Metallosulfur complexes will be synthesized where the dithiolate/disulfide couple is reversible. Dithiolate complexes will be prepared with high-valent metal ions while disulfide complexes will be prepared with low-valent metal ions. The oxidation of the thiolate complexes and the reduction of the disulfide complexes will be studied in order to provide further evidence for the dithiolate/disulfide couple serving as a source of increased reducing power in electron transfer proteins.

Funding Agency

• Agency: National Institute of Health (NIH)
• Institute: National Institute of General Medical Sciences (NIGMS)
• Type: Minority Biomedical Research Support - MBRS (S06)
• Project #: 5S06GM008101-19
• Application #: 3877316
• Support Year: 19
• Fiscal Year: 1990

Institution

• Name: California State University Los Angeles
• City: Los Angeles
• State: CA
• Country: United States
• Zip Code: 90032

Publications

Durvasula, Ramani S (2017) Personality Disorders and Health: Lessons Learned and Future Directions. Behav Med 43:227-232

Crespo, Noe C; Yoo, Eun Jung; Hawkins, Steven A (2011) Anthropometric and lifestyle associations of bone mass in healthy pre-menopausal Mexican and Asian American women. J Immigr Minor Health 13:74-80

Kumar, Satish; Velasco, Kriya; McCurdy, Alison (2010) X-ray, kinetics and DFT studies of photochromic substituted benzothiazolinic spiropyrans. J Mol Struct 968:13-18

Jiang, Dianlu; Li, Xiangjun; Williams, Renee et al. (2009) Ternary complexes of iron, amyloid-beta, and nitrilotriacetic acid: binding affinities, redox properties, and relevance to iron-induced oxidative stress in Alzheimer's disease. Biochemistry 48:7939-47

Pech, Herbe; Henry, Amanda; Khachikian, Crist S et al. (2009) Detection of geothermal phosphite using high-performance liquid chromatography. Environ Sci Technol 43:7671-5

Jiang, Dianlu; Dinh, Kim Lien; Ruthenburg, Travis C et al. (2009) A kinetic model for beta-amyloid adsorption at the air/solution interface and its implication to the beta-amyloid aggregation process. J Phys Chem B 113:3160-8

Hong, Hyun-Seok; Rana, Sandeep; Barrigan, Lydia et al. (2009) Inhibition of Alzheimer's amyloid toxicity with a tricyclic pyrone molecule in vitro and in vivo. J Neurochem 108:1097-1108

Kumar, Satish; Chau, Cindy; Chau, Gordan et al. (2008) Synthesis and metal complexation properties of bisbenzospiropyran chelators in water. Tetrahedron 64:7097-7105

Kumar, Satish; Hernandez, David; Hoa, Brenda et al. (2008) Synthesis, photochromic properties, and light-controlled metal complexation of a naphthopyran derivative. Org Lett 10:3761-4

Valentine, Sonya C; Contreras, Deisy; Tan, Stephanie et al. (2008) Phenotypic and molecular characterization of Acinetobacter baumannii clinical isolates from nosocomial outbreaks in Los Angeles County, California. J Clin Microbiol 46:2499-507