Overview of Research Interests
Transition metal ions are essential components of many biological systems. In metalloenzymes, metal centers are used to catalyze numerous chemical processes. We are interested in understanding how these processes occur and how features associated with the metal center influence the overall observed chemistry. Our approach toward understanding metalloenzyme systems involves the synthesis of model complexes that are specifically designed to mimic fundamental structural, spectroscopic, and reactivity features of the metalloenzyme active site. Through comprehensive studies of these model complexes, we hope to gain an understanding of the chemical principles that control the structure and function of metalloenzymes.
Our research in bioinorganic chemistry involves both synthetic inorganic and organic chemistry. We employ numerous techniques to characterize our model complexes including X-ray crystallography and electronic, IR, NMR, and EPR spectroscopies. Finally, we examine the reactivity of the model complexes with biologically relevant substrates with an emphasis on identifying the chemical principles that control metalloenzyme structure and function.
Current Projects
1. Coordination chemistry of acireductone dioxygenase model substrates; model studies of nickel dioxygenase.
2. Thioester hydrolysis reactivity of binuclear metal complexes of relevance to glyoxalase II enzymes.
Recent Publications (ACS or Royal Society Journal Access Required for PDF files)
G. K. Ingle, R. W. Watkins, A. M. Arif, and Lisa M. Berreau, "Divalent Metal Complexes of an Amide-appended N3O-donor Ligand: Synthesis, Structural and Spectroscopic Features, and Amide Methanolysis Reactivity," J. Coord. Chem. 2008, 61, 61-77.
G. K. Ingle, M. M. Makowska-Grzyska, A. M. Arif, and L. M. Berreau, "Divalent Nickel, Cobalt, and Iron Complexes of an Amide-appended N2S2 Ligand: Synthesis, Characterization and Reactivity with Hydroxide Anion," Eur. J. Inorg. Chem. 2007, 5262-5269. (PDF)
L. M. Berreau, "Coordination and Bioinorganic Chemistry of Aryl-Appended Tris(2-pyridylmethyl)amine Ligands," Comments on Inorg. Chem. 2007, 28, 123-171. (Internet page)
E. Szajna-Fuller, G. K. Ingle, R. W. Watkins, A. M. Arif, and L. M. Berreau, "Amide Hydrolysis Reactivity of a N4O-ligated Zinc Complex: Comparison of Kinetic and Thermodynamic Parameters with those of the Corresponding Amide Methanolysis Reaction," Inorg. Chem. 2007, 46, 2353-2355. (PDF)
G. K. Ingle, M. M. Makowska-Grzyska, E. Szajna-Fuller, I. Sen, J. C. Price, A. M. Arif, and L. M. Berreau, "Influence of Chelate Ligand Structure on the Amide Methanolysis Reactivity of Mononuclear Zinc Complexes," Inorg. Chem. 2007, 46, 1471-1480. (PDF)
R. A. Allred, S. A. Huefner, K. Rudzka, A. M. Arif, and L. M. Berreau, "A Cadmium Hydroxide Complex of a N3S-donor Ligand Containing Two Hydrogen Bond Donors: Synthesis, Characterization, and CO2 Reactivity," Dalton Transactions 2007, 351-357. (HTML)
E. Szajna-Fuller, B. M. Chambers, A. M. Arif, and L. M. Berreau, "Carboxylate Coordination Chemistry of a Mononuclear Ni(II) Center in a Hydrophobic or Hydrogen Bond Donor Secondary Environment: Relvance to Acireductone Dioxygenase," Inorg. Chem. 2007, 46, 5486-5498. (PDF)
E. Szajna-Fuller, K. Rudzka, A. M. Arif, and L. M. Berreau, "Acireductone Dioxygenase (ARD)-type Reactivity of a Ni(II) Complex having Monoanionic Coordination of a Model Substrate: Product Identification and Comparisons to Unreactive Analogs," Inorg. Chem. 2007, 46, 5499-5507. (PDF)
K. Rudzka, A. M. Arif, and L. M. Berreau, "Glyoxalase I-type Hemithioacetal Isomerization Reactivity of a Mononuclear Ni(II) Deprotonated Amide Complex," J. Am. Chem. Soc. 2006, 128, 17018-17023. (HTML/PDF)
L. M. Berreau,"Kinetic and Mechanistic Studies of the Reactivity of Zn-OHn (n = 1 or 2) Species in Small Molecule Analogs of Zinc-containing Metalloenzymes," Advances in Physical Organic Chemistry 2006, 41, 79-181.
L. M. Berreau, "Water Activation: Catalytic Hydrolysis," in Activation of Small Molecules: Organometallic and Bioinorganic Perspectives, W. B. Tolman, Ed., 2006, Wiley. (Website)
R. A. Allred, K. Doyle, A. M. Arif, and L. M. Berreau, "Solvent Effects on the Structural and Formyl Substrate Reactivity Properties of a Nitrogen/Sulfur-ligated Zinc Hydroxide Complex," Inorg. Chem. 2006, 45, 4097-4108. (HTML/PDF)
L. M. Berreau, "Bioinorganic Chemistry of Group 12 Complexes Supported by Tetradentate Tripodal Ligands having Internal Hydrogen Bond Donors," Eur. J. Inorg. Chem. 2006, 273-283. (PDF)
L. M. Berreau, A. Saha, and A. M. Arif, "Thioester Hydrolysis Reactivity of Zinc Hydroxide Complexes: Investigating Reactivity Relevant to Glyoxalase II Enzymes," Dalton Trans. 2006, 183-192. (HTML/PDF)
A. L. Fuller, R. W. Watkins, A. M. Arif, and L. M. Berreau, "Synthesis and Characterization of a Series of N3O-ligated Mononuclear Mn(II) Halide Complexes," Inorg. Chim. Acta 2006, 359, 1282-1290.
E. Szajna, A. M. Arif, and L. M. Berreau, "Aliphatic Carbon-Carbon Bond Cleavage Reactivity of a Mononuclear Ni(II) Cis-B-Keto-Enolate Complex in the Presence of Base and O2: A Model Reaction for Acireductone Dioxygenase (ARD)," J. Am. Chem. Soc. 2005, 127, 17186-17187. (HTML/PDF)
K. Rudzka, A. M. Arif, and L. M. Berreau, "Chemistry of a Ni(II) Acetohydroxamic Acid Complex: Formation, Reactivity with Water, and Attempted Preparation of Zinc and Cobalt Analogs," Inorg. Chem. 2005, 44, 7234-7242. (PDF)
E. Szajna, M. M. Makowska-Grzyska, C. C. Wasden, A. M. Arif, and L. M. Berreau, "A Deprotonated Intermediate in the Amide Methanolysis Reaction of a N4O-ligated Mononuclear Zinc Complex," Inorg. Chem. 2005, 44, 7595-7605. (PDF)
A. L. Fuller, R. W. Watkins, K. R. Dunbar, A. V. Prosvirin, A. M. Arif, and L. M. Berreau, "Manganese(II) Chemistry of a New N3O-donor Chelate Ligand: Synthesis, X-ray Structures, and Magnetic Properties of Solvent- and Oxalate-bound Complexes," Dalton Transactions 2005, 1891-1896. (HTML) (Cover article)
M. M. Makowska-Grzyska, K. Doyle, R. A. Allred, A. M. Arif, D. C. Bebout, and L. M. Berreau, "Structural, Spectroscopic, and Reactivity Properties of N2S2(thioether)O(amide)-Ligated Hg(II) Complexes: The First Examples of Hg(II)-Mediated Amide Cleavage," Eur. J. Inorg. Chem. 2005, 822-827. (PDF)
K. Rudzka, M. M. Makowska-Grzyska, E. Szajna, A. M. Arif, and L. M. Berreau, "Neutral Acetohydroxamic Acid Coordination to a Mononuclear Ni(II) Center Stabilized by a Intramolecular Hydrogen-bonding Interaction," Chem. Commun. 2005, 489-491. (HTML/PDF)
K. J. Tubbs, E. Szajna, B. Bennett, J. A. Halfen, R. W. Watkins, A. M. Arif, L. M. Berreau, "Mononuclear Nitrogen/sulfur-Ligated Cobalt(II) Methoxide Complexes: Structural, EPR, Paramagnetic 1H NMR, and Electrochemical Investigations," Dalton Transactions 2004, 2398-2399. (HTML/PDF)
E. Szajna, P. Dobrowolski, A. L. Fuller, A. M. Arif, and L. M. Berreau, "NMR Studies of Mononuclear Octahedral Ni(II) Complexes of Tris((2-pyridyl)methyl)amine-type Ligands," Inorg. Chem. 2004, 43, 3988-3997. (PDF)
T. Chandra, R. A. Allred, B. J. Kraft, L. M. Berreau, and J. M. Zaleski, "Syntheses and Thermal Reactivities of Tetradententate Metalloenediynes of Cu(II) and Zn(II)," Inorg. Chem. 2004, 43, 411-420. (PDF) (Cover article)
Contact Lisa M. Berreau
Department of Chemistry and Biochemistry
Utah State University
0300 Old Main Hill
Logan, UT 84322-0300
Phone: (435) 797-1625
FAX: (435) 797-3390
E-mail: berreau@cc.usu.edu