Alexey Silakov

Professional Appointments and Affiliations

Associate Professor of Chemistry

Office

330 Chemistry Building
University Park, PA 16802

Mailing Address

104 Chemistry Building

Education

Ph.D., Physical Chemistry, Heinrich-Heine-Universität Düsseldorf/ Max-Planck Institute for Bioinorganic Chemistry, Germany, 2007

M.S., Physics, Kazan State University, Russia, 2003

Honors and Awards

John Weil Young Investigator Award, International EPR Society, 2011

58th Lindau Nobel Laureate Meeting, Physics, 2008

Selected Publications

Blaesi E.J., Palowitch G.M., Hu K., Kim, A.J. Rose H.R., Alapati R.B, Lougee M.G., Kim H.J, Taguchi A.T., Tan K.O., Laremore T.N., Griffin R.G., Krebs C., Matthews M.L.*, Silakov A*., Bollinger Jr. J.M.*, Allen B.D.*, Boal A.K.* Metal-free class Ie ribonucleotide reductase from pathogens initiates catalysis with a tyrosine-derived dihydroxyphenylalanine radical

PNAS. 2018, 115 (40), 10022-10027

Dunham, N.P., Chang W.-C., Mitchell A.J., Martinie R.J., Zhang B., Bergman J.A., Rajakovich L.J., Wang B., Silakov A.*, Krebs, C.*, Boal A.K.*, Bollinger, Jr J.M.* Two Distinct Mechanisms for C–C Desaturation by Iron (II)-and 2-(Oxo) glutarate-Dependent Oxygenases: Importance of α-Heteroatom Assistance

J. Am. Chem. Soc. 2018 140 (23), 7116-7126

Martinie R.J., Pollock C.P., Matthews M.L., Bollinger, Jr. J.M., Krebs C., Silakov A.
Vanadyl as a Stable Structural Mimic of Reactive Ferryl Intermediates in Mononuclear Nonheme-Iron Enzymes Inorg. Chem 2017, 2017, 56 (21), 13382–13389
*Theme of the article is also featured on the cover of the corresponding issue.

Efficient methylation of C2 in l-tryptophan by the cobalamin-dependent radical S-adenosylmethionine methylase TsrM requires an unmodified N1 amine
Blaszczyk A.J., Wang B., Silakov A., Ho J.V., Booker S.J.
J. Biol. Chem. 2017, 292 (37): 15456-15467

Mitchell A.J., Dunham N.P., Martinie R.J., Bergman J.A., Pollock C.J., Hu K, Allen B.D., Chang W., Silakov A., Bollinger Jr J.M., Krebs C., Boal A.K.
Visualizing the reaction cycle in an iron (II)-and 2-(oxo)-glutarate-dependent hydroxylase
J. Am. Chem. Soc. 2017 doi: 10.1021/jacs.7b07374

Onderko E.L., Silakov A., Yosca T.H., Green M.T.
Characterization of a selenocysteine-ligated P450 compound I reveals direct link between electron donation and reactivity
Nature Chemistry 2017, 9: 623-628

Pistner A.J., Moon H.W., Silakov A., Yennawar H.P., Radosevich A.T.
Stable Open-Shell Phosphorane Based on a Redox-Active Amidodiphenoxide Scaffold<
Inorganic Chemistry 56 (15): 8661-8668

Martinie R.J., Blaesi E.J., Krebs C., Bollinger, Jr. J.M., Silakov A., Pollock C.J., 
Evidence for a Di- μ -oxo Diamond Core in the Mn(IV)/Fe(IV) Activation Intermediate of Ribonucleotide Reductase from Chlamydia trachomatis
J. Am. Chem. Soc. 2017, 139: 1950–1957

Kusler K., Odoh S.O., Silakov A., Poyton M.F., Pullanchery S., Cremer P.S., Gagliardi L.
What is the Preferred Conformation of Phosphatidylserine-Copper (II) Complexes? A Combined Theoretical and Experimental Investigation.
J. Phys. Chem. B 2016, 120 (50): 12883–12889

Cirri A., Silakov A., Jensen L., Lear B. J.
Probing ligand-induced modulation of metallic states in small gold nanoparticles using conduction electron spin resonance. Phys. Chem. Chem. Phys. 2016 in press

Esakova, O; Silakov, A; Grove, T; Saunders, A; McLaughlin, M; Yennawar, N; Booker, 
Structure of Quinolinate Synthase from Pyrococcus horikoshii in the Presence of Its Product, Quinolinic AcidJ Am Chem Soc. 2016, 138 (23): 7224–7227

Speelman, A; Zhang, B; Silakov, A; Skodje, K; Alp, E.; Zhao, J; Hu, M; Kim, E; Krebs, C; Lehnert, N
"An Unusual Synthetic Pathway for an {Fe(NO)2}9 Dinitrosyl Iron Complex (DNIC) and Insight into DNIC Electronic Structure via Nuclear Resonance Vibrational Spectroscopy"
Inorg. Chem. 2016, 55 (11): 5485–5501

Blaszczyk AJ, Silakov A, Zhang B, Maiocco SJ, Lanz ND, Kelly WL, Elliott SJ, Krebs C, Booker SJ.
Spectroscopic and Electrochemical Characterization of the Iron-Sulfur and Cobalamin Cofactors of TsrM, an Unusual Radical S-Adenosylmethionine Methylase.
J Am Chem Soc. 2016 138(10):3416-26

Livada J., Martinie R.J.¸ Dassama, L.M.K.,  Krebs C., Bollinger Jr. J. M , Silakov A.
Direct Measurement of the Radical Translocation Distance in the Class I Ribonucleotide Reductase from Chlamydia trachomatis.
J. Phys.Chem. B, 2015, 119 (43): 13777–13784

Krest, C.M., Silakov, A., Rittle J., Yosca T.H., Onderko E.L., Green M.T
Significantly shorter Fe–S bond in cytochrome P450-I is consistent with greater reactivity relative to chloroperoxidase. Nature Chem. 2015, 7:696 - 702

Martinie, R.J., Livada, J., Chang W.C., Green M.T., Krebs, C., Bollinger J.M., Silakov A.
Experimental Correlation of Substrate Position with Reaction Outcome in the Aliphatic Halogenase, SyrB2. J. Am. Chem. Soc. 2015, 137(21): 6912-6919.
* featured in JACS Spotlights: Perkel J.M., J. Am. Chem. Soc. 2015, 137, 6973−6974

Lanz, N.D., Rectenwald J.M., Wang B., Kakar E.S.,  Laremore T.N., Booker, S.J., Silakov, A.
Characterization of a Radical Intermediate in Lipoyl Cofactor Biosyn-thesis
J. Am. Chem. Soc. 2015, 137(41):13216-13219

Silakov, A.; Radle M.I.; Grove T.L.; Bauerle M.R.; Green M.T.;  Rosenzweig A.R.; Boal A.K.; Booker S.J. Observation and Characterization of a Cross-linked Protein–Nucleic Acid Substrate Radical in the Reaction Catalyzed by RlmN. J. Am. Chem. Soc. 2014, 136(23): 8221-8228

Yosca T.H.; Rittle J.; Krest C.M.; Calixto J.C.; Silakov A.; Onderko E.L.; R.K. Behan, and Green M.T.
Understanding C-H Bond Activation in Cytochrome P450: The ferryl pKa and the role of thiolate ligation. Science 2013, 342 (6160): 825-829.

Grove T.L.; Livada J.; Schwalm E.L.; Green M.T.; Booker S.J.; Silakov A.
"A substrate radical intermediate in catalysis by the antibiotic resistance protein Cfr."
Nat. Chem. Biol. 2013, 9(7) 422-427

Silakov, A.; Olsen, M.T.; Sproules, S .; Reijerse, E.J.; Rauchfuss, T.B.; Lubitz, W.; 
"EPR/ENDOR, Mossbauer, and Quantum-Chemical Investigations of Diiron Complexes Mimicking the Active Oxidized State of [FeFe]Hydrogenase" Inorg.Chem. 2012, 51(15)  8617-8628

Silakov, A.; Reijerse, E.; Lubitz, W. "Unraveling the electronic properties of the photo-induced states of the H-cluster in [FeFe] hydrogenase from Desulfovibrio desulfuricans." Eur J Inorg Chem 2011, 2011 (7): 1056–1066