Associate Professor
Ph.D., 1985, Columbia University
Inorganic and Organometallic Chemistry
Voice: (207)-581-1182
E-mail: abruce@maine.edu
Research in my group focuses on the structure and reactivity of transition metal complexes and their applications to bioinorganic and organometallic chemistry. Current activity in the group centers around two areas: 1) the medicinal chemistry of gold(I) complexes and 2) the synthesis of new gold(I complexes with liquid crystalline or non-linear optical properties.
Gold complexes have been used for about 70 years to treat rheumatoid arthritis. Despite this long history, the mechanism of action is unknown. It is becoming increasingly apparent that gold drugs are "prodrugs" that undergo ligand displacement reactions with for example cysteine sulfur sites in the body. Cysteine disulfide bonds may also be involved in redox chemistry with gold drugs. In addition, cells in inflamed tissues experience oxidative bursts and Au(I) localized in these cells may be oxidized to Au(III). Visit our bioinorganic chemistry page for information.
The redox chemistry of Au(I) complexes has received little attention. For the past several years we have been studying the oxidation chemistry of gold(I) complexes containing phosphine and thiolate ligands. In recent papers, we describe how one-electron oxidation of Au(I) phosphine thiolate complexes leads to formation of disulfide and gold clusters - varying from four golds to the unusually nine gold cluster. We have also been studying the oxidation chemistry of Auranofin, an orally active drug that was approved for treatment of rheumatoid arthritis in the 1980's.
Recently we began collaborating with chemists from Moscow State University in Russia on a research project funded by the National Science Foundation. In this research, we are synthesizing new organogold complexes that are expected to show interesting liquid crystalline or non-linear optical properties. Interest in developing metallomesogens, or metal-containing liquid crystals, is motivated in general by the promise of new and useful electrical, optical or magnetic properties as a result of introducing metals into liquid crystals. We have begun our investigations by introducing two-coordinate gold(I) into organic molecules that incorporate traditional features common to non-metal containing liquid crystals. We anticipate that Au(I)-Au(I) bonds, which are on the order of hydrogen bonds, may serve as additional interactions to help organize the structures. Visit our metallomesogens projects for recent results involving long chained thiols (precursors of metallomesogens) and gold metallomesogens.
Recent Publications
Jinhua Chen, Ahmed A. Mohamed, Hanan E. Abdou, Jeanette A. Krause Bauer, John P. Fackler, Jr., Alice E. Bruce and Mitchell R. M. Bruce "Novel metallamacrocyclic gold(I) thiolate cluster complex: structure and luminescence of [Au9(µ-dppm)4(µ-p-tc)6](PF6)3" Chem. Comm. 2005, 1575-1577.
Larkin, Scott A.; Krause Bauer, Jeanette A.; Konoplev, V. E.; Dyadchenko, Victor P.; Lemenovskii, Dmitrii A.; Bruce, Mitchell R. M.; Bruce, Alice E. "µ-Biphenyl-2,2'-dithiolato-k2S:S'-bis[(triphenylphosphine-kP)gold(I)]"Acta Crystallographica, Section C: Crystal Structure Communications, 2004, C60(9), m440-m442.
Mohamed, A. A.; Krause Bauer, J. A.; Bruce, A. E.; Bruce, M. R. M. "[µ-o-Phenylenebis(diphenylphosphine)-k2P:P']bis[chlorogold(I)],dppbz(AuCl)2." Acta Crystallographica, Section C: Crystal Structure Communications, 2003, C59(3), m84-m86.
Mohamed, A. A.; Chen, J.; Bruce, A. E.; Bruce, M. R. M.; Krause Bauer, J. A.; Hill, D. T. "Formation of a Cationic Gold(I) Complex and Disulfide by Oxidation of the Antiarthritic Gold Drug Auranofin."; Inorganic Chemistry, 2003, 42(7), 2203-2205.
Lemenovskii, D. A.; Makarov, M. V.; Dyadchenko, V. P.; Bruce, A. E.; Bruce, M. R. M.; Larkin, S.; Averkiev, B. B.; Starikova, Z. A.; Antipin, M. Yu. "Ferrocenyl Derivatives of Biphenyl. Synthesis and Crystal Structure."; Russian Chemical Bulletin, 2003, 52(3), 607-615.
Mohamed, A. A.; Abdou, H. E.; Chen, J.; Krause Bauer, J. A.; Bruce, A. E.; Bruce, M. R. M. "Perspectives in Inorganic and Bioinorganic Gold Sulfur Chemistry." Comments on Inorganic Chemistry, 2002, 23(5), 321-334.
Chadwick, S.; Englich, U.; Ruhlandt-Senge, K.; Watson, C. Bruce, A.E.; Bruce, M.R.M."Formation of Separated versus Contact Ion-Pairs in Alkali Thiolates and Selenolates", Journal of the Chemical Society, Dalton Transactions, 2000, 2167-2173.
Chen, J.; Jiang, T.; Wei, G.; Mohamed, A.A.; Homrighausen, C.; Krause Bauer, J.A.; Bruce, A.E.; Bruce, M.R.M. "Electrochemical and Chemical Oxidation of Gold(I) Thiolate Phosphine Complexes: Formation of Gold Clusters and Disulfide", Journal of the American Chemical Society, 1999, 121, 9225.
Watson, C. M.; Dwyer, D. J.; Andle, J.; Bruce, A.E.; Bruce, M.R.M. "Stripping Analyses of Mercury Using Gold Electrodes: Irreversible Adsorption of Mercury", Analytical Chemistry, 1999, 71, 3181.
Foley, J. B.; Gay, S.E.; Turmel, C.; Wei, G.; Jiang, T.; Narayanaswamy, R.; Foxman, B.M.; Vela, M.J.; Bruce, A.E.; Bruce, M.R.M. "Electronic Structure of Dinuclear Gold(I) Complexes", Metal-Based Drugs, 1999, 6, 255.
DiLorenzo, M.; Ganesh, S.; Tadayon, L.; Bruce, M.R.M.; Bruce, A.E. "Reactions of Organic Disulfides and Gold(I) Complexes", Metal-Based Drugs, 1999, 6, 247.
Mohamed, A.A.; Bruce, A.E.; Bruce, M.R.M. "Cyclic Voltammetry of Auranofin", Metal-Based Drugs, 1999, 6, 233.
Mohamed, A.A.; Bruce, A.E.; Bruce, M.R.M. "Electrochemistry of Gold and Silver Complexes", in Organic Derivatives of Silver and Gold, Patai, S. and Rappaport, Z., Eds., John Wiley & Sons, England, 1998.
Schwerdtfeger, P.; Bruce, A.E.; Bruce, M.R.M. "Theoretical Studies on the Photochemistry of the cis to trans Conversion in Dinuclear Gold Halide Bis(diphenylphosphino)ethylene Complexes", Journal of the American Chemical Society, 1998, 120, 6587.
Foley, J.B.; Bruce, A.E.; Bruce, M.R.M. "An Unprecedented Photochemical Cis to Trans Isomerization of Dinuclear Gold(I) Bis(diphenylphosphino)ethylene Complexes." Journal of the American Chemical Society, 1995, 117, 9596.
Jones, W.B.; Yuan, J.; Narayanaswamy, R.; Young, M.A.; Elder, R.C.; Bruce, A.E.; Bruce, M.R.M. "Solid State EXAFS and Luminescence Studies of Neutral, Dinuclear Gold(I) Complexes. Gold(I)-Gold(I) Interactions in the Solid State." Inorganic Chemistry, 1995, 34, 1996.
Jiang, T.; Wei, G.; Turmel, C.; Bruce, A.E.; Bruce, M.R.M.; "Redox Chemistry of Gold(I) Phosphine Thiolates: Sulfur-Based Oxidation." Metal Based Drugs, 1994, 1, 419. Foley, J.; Fort, R.C., Jr.; McDougal, K.; Bruce, M.R.M.; Bruce, A.E. "Electronic and Steric Effects in Gold(I) Phosphine Thiolate Complexes." Metal Based Drugs, 1994, 1, 405.
Narayanaswamy, R.; Young, M.A.; Parkhurst, E.; Ouellette, M.; Kerr, M.E.; Ho, D.; Elder, R.C.; Bruce, A.E.; Bruce, M.R.M. "Synthesis, Structure Determination, and Electronic Spectroscopy of Neutral, Dimeric Gold(I) Complexes. Gold(I)-Gold(I) Interactions in Solution and in the Solid State." Inorganic Chemistry, 1993, 32, 2506.
