Source: http://chem.tufts.edu/faculty/rybak-akimova/
Timestamp: 2019-04-19 13:02:40+00:00

Document:
Inorganic Chemistry. Professor Rybak-Akimova's research was aimed at developing a better understanding of the selectivity of small-molecule binding and activation with transition metal complexes in order to design highly specific reagents and catalysts. This research was significant in solving fundamental problems in enzyme mimicry and to meeting industrial demand. Her effort focused on two bio-inspired approaches to the problem of selectivity in substrate binding and transformations: (1) introducing specific substrate binding sites onto transition metal platforms (design of molecular tweezers), and (2) investigating the mechanisms of small molecule activation at the metal centers and specific reactivities of transient metal containing intermediates formed in these processes. These principles are widely used by natural metalloenzymes and antibiotics. For example, bleomycin, a well known antibiotic and anticancer drug, binds to DNA and recruits iron to bind oxygen and to generate a highly reactive oxidant that mediates oxidative cleavage. This cleavage is believed to be responsible for biological activity of bleomycin.
"H2O2 activation with biomimetic non-haem iron complexes and AcOH: Connecting the g = 2.7 EPR signal with a visible chromophore", O.V. Makhlynets, W.N. Oloo, Y.S. Moroz, I.G. Belaya, T.D. Palluccio, A.S. Filatov, P. Müller, M.A. Cranswick, L. Que, Jr., E.V. Rybak-Akimova, Chem. Commun., 2014, 50, 645-648.
"Characterization of metastable intermediates formed in the reaction between a Mn(II) complex and dioxygen, including a crystallographic structure of a binuclear Mn(III)-peroxo species", M. K. Coggins, X. Sun, Y. Kwak, E.I. Solomon, E. Rybak-Akimova, J. A. Kovacs, J. Am. Chem. Soc., 2013, 135, 5631-5640.
"Thermodynamic and kinetic study of cleavage of the N-O bond of N-oxides by a vanadium(III) complex: Enhanced oxygen atom transfer reaction rates for adducts of nitrous oxide and mesityl nitrile oxide, T.D. Palluccio, E.V. Rybak-Akimova, S. Majumdar, X. Cai, M. Chui, M. Temprado, J.S. Silvia, A.F. Cozzolino, D. Tofan, A. Velian, C.C. Cummins, B. Captain, C.D. Hoff, J. Am. Chem. Soc., 2013, 135, 11357-11372.
"Mechanistic Studies of the O2-Dependent Aliphatic Carbon−Carbon Bond Cleavage Reaction of a Nickel Enolate Complex", L. M. Berreau, T. Borowski, K. Grubel, C. J. Allpress, J. P. Wikstrom, M. E. Germain, E. V. Rybak-Akimova, D. L. Tierney, Inorg. Chem., 2011, 50, 1047-1057.
"Oxygen Binding to [Pd(L)(L′)] (L=NHC, L′= NHC or PR3, NHC = N-Heterocyclic Carbene). Synthesis and Structure of a Paramagnetic trans-[Pd(NHC)2(η1-O2)2] Complex", X. Cai, S. Majumdar, G. C. Fortman, C. S. J. Cazin, A. M. Z. Slawin, C. Lhermitte, R. Prabhakar, M. E. Germain, T. Palluccio, S. P. Nolan, E. V. Rybak-Akimova, M. Temprado, B. Captain, C. D. Hoff, J. Am. Chem. Soc., 2011, 133, 1290-1293.
"Steric and counterion effects on the structure of dipicolylamine nickel complexes", J. P. Wikstrom, A. S. Filatov, R. J. Staples, C. R. Guifarro and E. V. Rybak-Akimova, Inor. Chim. Acta., 2010, 363, 884-890.
"Carbonate formation within a nickel dimer: synthesis of a coordinatively unsaturated bis(mu-hydroxo) dinickel complex and its reactivity toward carbon dioxide", J. P. Wikstrom, A. S. Filatov, E. A. Mikhalyova, M. Shatruk, B. M. Foxman, and E. V. Rybak-Akimova, Dalton Trans., 2010, 39, 2504-14.
"Condensation of nitriles with amides promoted by coordinatively unsaturated bis-nickel(II)-hydroxy complex: a new route to alkyl- and aryl-imidoylamidines", J. P. Wikstrom, A. S. Filatov, E. V. Rybak-Akimova, Chem. Comm., 2010, 46, 424-426.
"Coordination-Mode Control of Bound Nitrile Radical Complex Reactivity: Intercepting End-on Nitrile-Mo(III) Radicals at Low Temperature", M. E. Germain, M. Temprado, A. Castonguay, O. P. Kryatova, E. V. Rybak-Akimova, J. J. Curley, A. Mendiratta, Y-C. Tsai, C. C. Cummins, R. Prabhakar, J. E. McDonough, E. James, and C. D. Hoff, J. Am. Chem Soc., 2009, 131, 15412-15423.
"Nickel(II) Complexes of Monofunctionalized Pyridine-Azamacrocycles: Synthesis, Structures, Pendant Arm "On-Off" Coordination Equilibria, and Peroxidase-like Activity", V. G. Organo, A. S. Filatov, S. Alexander, J. S. Quartararo, , Z. M. Friedman, and E. V. Rybak-Akimova, Inorg. Chem., 2009, 48, 8456-8468.

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