Carsten Krebs

Summary

Affiliation: Pennsylvania State University
Country: USA

Publications

  1. ncbi request reprint AurF from Streptomyces thioluteus and a possible new family of manganese/iron oxygenases
    Carsten Krebs
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 46:10413-8. 2007
  2. pmc Non-heme Fe(IV)-oxo intermediates
    Carsten Krebs
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Acc Chem Res 40:484-92. 2007
  3. doi request reprint Freeze-quench (57)Fe-Mössbauer spectroscopy: trapping reactive intermediates
    Carsten Krebs
    Department of Chemistry, The Pennsylvania State University, University Park, 332 Chemistry Building, Pennsylvania, PA 16802, USA
    Photosynth Res 102:295-304. 2009
  4. ncbi request reprint Rapid freeze-quench 57Fe Mössbauer spectroscopy: monitoring changes of an iron-containing active site during a biochemical reaction
    Carsten Krebs
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Inorg Chem 44:742-57. 2005
  5. pmc Cyanobacterial alkane biosynthesis further expands the catalytic repertoire of the ferritin-like 'di-iron-carboxylate' proteins
    Carsten Krebs
    Department of Chemistry, Penn State University, 332 Chemistry Building, University Park, PA 16802, USA
    Curr Opin Chem Biol 15:291-303. 2011
  6. ncbi request reprint Oxygen activation by a mixed-valent, diiron(II/III) cluster in the glycol cleavage reaction catalyzed by myo-inositol oxygenase
    Gang Xing
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 45:5402-12. 2006
  7. pmc Substrate-triggered formation and remarkable stability of the C-H bond-cleaving chloroferryl intermediate in the aliphatic halogenase, SyrB2
    Megan L Matthews
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 48:4331-43. 2009
  8. pmc CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases
    Michael L Neidig
    Department of Chemistry, Stanford University, Stanford, California 94305, USA
    J Am Chem Soc 129:14224-31. 2007
  9. ncbi request reprint A coupled dinuclear iron cluster that is perturbed by substrate binding in myo-inositol oxygenase
    Gang Xing
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 45:5393-401. 2006
  10. pmc Branched activation- and catalysis-specific pathways for electron relay to the manganese/iron cofactor in ribonucleotide reductase from Chlamydia trachomatis
    Wei Jiang
    Department of Biochemistry and Molecular Biology and Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:8477-84. 2008

Research Grants

Collaborators

Detail Information

Publications80

  1. ncbi request reprint AurF from Streptomyces thioluteus and a possible new family of manganese/iron oxygenases
    Carsten Krebs
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 46:10413-8. 2007
    ..Hypothetical proteins encoded in the genomes of several other bacteria have similar sequences and may also be members of this nascent family of oxygen-activating Mn/Fe proteins...
  2. pmc Non-heme Fe(IV)-oxo intermediates
    Carsten Krebs
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Acc Chem Res 40:484-92. 2007
    ....
  3. doi request reprint Freeze-quench (57)Fe-Mössbauer spectroscopy: trapping reactive intermediates
    Carsten Krebs
    Department of Chemistry, The Pennsylvania State University, University Park, 332 Chemistry Building, Pennsylvania, PA 16802, USA
    Photosynth Res 102:295-304. 2009
    ..In this article, we summarize these findings and demonstrate the potential of the method...
  4. ncbi request reprint Rapid freeze-quench 57Fe Mössbauer spectroscopy: monitoring changes of an iron-containing active site during a biochemical reaction
    Carsten Krebs
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Inorg Chem 44:742-57. 2005
    ..By using the example of TauD, we show that comparison of experimental Mössbauer parameters with those obtained from calculations on model systems can be used to provide insight into the structure of a reaction intermediate...
  5. pmc Cyanobacterial alkane biosynthesis further expands the catalytic repertoire of the ferritin-like 'di-iron-carboxylate' proteins
    Carsten Krebs
    Department of Chemistry, Penn State University, 332 Chemistry Building, University Park, PA 16802, USA
    Curr Opin Chem Biol 15:291-303. 2011
    ....
  6. ncbi request reprint Oxygen activation by a mixed-valent, diiron(II/III) cluster in the glycol cleavage reaction catalyzed by myo-inositol oxygenase
    Gang Xing
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 45:5402-12. 2006
    ..The use of the mixed-valent, diiron(II/III) cluster by MIOX represents a significant departure from the mechanisms of other known diiron oxygenases, which all involve activation of O(2) from the II/II manifold...
  7. pmc Substrate-triggered formation and remarkable stability of the C-H bond-cleaving chloroferryl intermediate in the aliphatic halogenase, SyrB2
    Megan L Matthews
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 48:4331-43. 2009
    ....
  8. pmc CD and MCD of CytC3 and taurine dioxygenase: role of the facial triad in alpha-KG-dependent oxygenases
    Michael L Neidig
    Department of Chemistry, Stanford University, Stanford, California 94305, USA
    J Am Chem Soc 129:14224-31. 2007
    ..These studies provide initial insight into the active-site features that favor chlorination by CytC3 over the hydroxylation reactions occurring in related enzymes...
  9. ncbi request reprint A coupled dinuclear iron cluster that is perturbed by substrate binding in myo-inositol oxygenase
    Gang Xing
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 45:5393-401. 2006
    ....
  10. pmc Branched activation- and catalysis-specific pathways for electron relay to the manganese/iron cofactor in ribonucleotide reductase from Chlamydia trachomatis
    Wei Jiang
    Department of Biochemistry and Molecular Biology and Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:8477-84. 2008
    ..Thus, the presence of branched activation- and catalysis-specific electron relay pathways may be functionally important uniquely in the Mn/Fe-dependent class Ic R2s...
  11. pmc Biogenesis of iron-sulfur clusters in photosystem I: holo-NfuA from the cyanobacterium Synechococcus sp. PCC 7002 rapidly and efficiently transfers [4Fe-4S] clusters to apo-PsaC in vitro
    Zhao Jin
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Biol Chem 283:28426-35. 2008
    ..These results establish that cyanobacterial NfuA can act as a scaffolding protein for the insertion of [4Fe-4S] clusters into PsaC of PS I in vitro...
  12. ncbi request reprint A manganese(IV)/iron(III) cofactor in Chlamydia trachomatis ribonucleotide reductase
    Wei Jiang
    Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, PA 16802, USA
    Science 316:1188-91. 2007
    ..By enzyme activity measurements and spectroscopic methods, we show that this RNR actually uses a previously unknown stable manganese(IV)/iron(III) cofactor for radical initiation...
  13. ncbi request reprint Kinetic dissection of the catalytic mechanism of taurine:alpha-ketoglutarate dioxygenase (TauD) from Escherichia coli
    John C Price
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 44:8138-47. 2005
    ..g., temperature), protein mutagenesis, the use of substrate analogues, or some combination of these...
  14. doi request reprint Rapid and quantitative activation of Chlamydia trachomatis ribonucleotide reductase by hydrogen peroxide
    Wei Jiang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:4477-83. 2008
    ..Sjöberg, B.-M., Backes, G., Loehr, T., and Sanders-Loehr, J. (1990) Biochem. Biophys. Res. Commun. 167, 813-818]...
  15. pmc O(2)-evolving chlorite dismutase as a tool for studying O(2)-utilizing enzymes
    Laura M K Dassama
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    Biochemistry 51:1607-16. 2012
    ....
  16. pmc A manganese(IV)/iron(IV) intermediate in assembly of the manganese(IV)/iron(III) cofactor of Chlamydia trachomatis ribonucleotide reductase
    Wei Jiang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 46:8709-16. 2007
    ....
  17. ncbi request reprint Structural characterization of the peroxodiiron(III) intermediate generated during oxygen activation by the W48A/D84E variant of ribonucleotide reductase protein R2 from Escherichia coli
    Jeffrey Baldwin
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 42:13269-79. 2003
    ..4 A). Possible explanations for this difference in detected Fe-Fe distance include an O(2)-induced conformational change prior to covalent chemistry or differing O(2) reactivity among multiple diiron(II) forms of the cluster...
  18. pmc Direct spectroscopic detection of a C-H-cleaving high-spin Fe(IV) complex in a prolyl-4-hydroxylase
    Lee M Hoffart
    Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, PA 16802, USA
    Proc Natl Acad Sci U S A 103:14738-43. 2006
    ..The close correspondence of the accumulating states in the P4H and TauD reactions supports the hypothesis of a conserved mechanism for substrate hydroxylation by enzymes in this family...
  19. ncbi request reprint Use of a chemical trigger for electron transfer to characterize a precursor to cluster X in assembly of the iron-radical cofactor of Escherichia coli ribonucleotide reductase
    Lana Saleh
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 43:5953-64. 2004
    ....
  20. doi request reprint Further characterization of Cys-type and Ser-type anaerobic sulfatase maturating enzymes suggests a commonality in the mechanism of catalysis
    Tyler L Grove
    Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA
    Biochemistry 52:2874-87. 2013
    ..Lastly, we show that the electron generated during catalysis by AtsB and anSMEcpe can be utilized for multiple turnovers, albeit through a reduced flavodoxin-mediated pathway...
  21. pmc Formation and function of the Manganese(IV)/Iron(III) cofactor in Chlamydia trachomatis ribonucleotide reductase
    Wei Jiang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:13736-44. 2008
    ..In this review, we recount the discovery of the novel Mn/Fe redox cofactor in Ct RNR and summarize our current understanding of how it assembles and initiates nucleotide reduction...
  22. doi request reprint The manganese(IV)/iron(III) cofactor of Chlamydia trachomatis ribonucleotide reductase: structure, assembly, radical initiation, and evolution
    J Martin Bollinger
    Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA
    Curr Opin Struct Biol 18:650-7. 2008
    ....
  23. ncbi request reprint The first direct characterization of a high-valent iron intermediate in the reaction of an alpha-ketoglutarate-dependent dioxygenase: a high-spin FeIV complex in taurine/alpha-ketoglutarate dioxygenase (TauD) from Escherichia coli
    John C Price
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 42:7497-508. 2003
    ..The detection of this intermediate sets the stage for a more detailed dissection of the TauD reaction mechanism than has previously been reported for any other member of this important enzyme family...
  24. ncbi request reprint Evidence for hydrogen abstraction from C1 of taurine by the high-spin Fe(IV) intermediate detected during oxygen activation by taurine:alpha-ketoglutarate dioxygenase (TauD)
    John C Price
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, PA 16802, USA
    J Am Chem Soc 125:13008-9. 2003
    ....
  25. pmc Characterization of RimO, a new member of the methylthiotransferase subclass of the radical SAM superfamily
    Kyung Hoon Lee
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 48:10162-74. 2009
    ..We discuss the possible requirement for an assembled ribosome for fully active RimO in vitro. Our findings are consistent with those of other enzymes that catalyze sulfur insertion, such as biotin synthase, lipoyl synthase, and MiaB...
  26. pmc Two distinct mechanisms of inactivation of the class Ic ribonucleotide reductase from Chlamydia trachomatis by hydroxyurea: implications for the protein gating of intersubunit electron transfer
    Wei Jiang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 49:5340-9. 2010
    ....
  27. pmc Function of the diiron cluster of Escherichia coli class Ia ribonucleotide reductase in proton-coupled electron transfer
    Bigna Wörsdörfer
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 135:8585-93. 2013
    ..The results thus provide the first evidence that the diiron cluster of this prototypical class Ia RNR functions not only in its well-known role as generator of the enzyme's essential Y122(•), but also directly in catalysis...
  28. doi request reprint Radical-translocation intermediates and hurdling of pathway defects in "super-oxidized" (Mn(IV)/Fe(IV)) Chlamydia trachomatis ribonucleotide reductase
    Laura M K Dassama
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    J Am Chem Soc 134:20498-506. 2012
    ..Thus, the use of the more oxidized cofactor permits the accumulation of hopping intermediates and the "hurdling" of engineered defects in the RT pathway...
  29. doi request reprint Structural analysis of the Mn(IV)/Fe(III) cofactor of Chlamydia trachomatis ribonucleotide reductase by extended X-ray absorption fine structure spectroscopy and density functional theory calculations
    Jarod M Younker
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 130:15022-7. 2008
    ..The site-placement of the metal ions cannot be discerned from the available data...
  30. doi request reprint A radically different mechanism for S-adenosylmethionine-dependent methyltransferases
    Tyler L Grove
    Department of Chemistry, The Pennsylvania State University, University Park, PA 16802, USA
    Science 332:604-7. 2011
    ..In neither case is a methyl group transferred directly from SAM to the RNA; rather, both reactions proceed by a ping-pong mechanism involving intermediate methylation of a conserved cysteine residue...
  31. pmc Substrate positioning controls the partition between halogenation and hydroxylation in the aliphatic halogenase, SyrB2
    Megan L Matthews
    Department of Chemistry, Pennsylvania State University, University Park, PA 16802, USA
    Proc Natl Acad Sci U S A 106:17723-8. 2009
    ..Thus, substrate-intermediate disposition and the carboxylate --> halide ligand swap combine to specify the halogenation outcome...
  32. ncbi request reprint Functional mimic of dioxygen-activating centers in non-heme diiron enzymes: mechanistic implications of paramagnetic intermediates in the reactions between diiron(II) complexes and dioxygen
    Dongwhan Lee
    Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA
    J Am Chem Soc 124:3993-4007. 2002
    ..A mechanism for this reaction is proposed and compared with those of other synthetic and biological systems, in which electron transfer occurs from a low-valent starting material to putative high-valent dioxygen adduct(s)...
  33. pmc Structural basis for assembly of the Mn(IV)/Fe(III) cofactor in the class Ic ribonucleotide reductase from Chlamydia trachomatis
    Laura M K Dassama
    Department of Chemistry and Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    Biochemistry 52:6424-36. 2013
    ..2 Å) Mn(II)-Fe(II) interionic distance, promoting formation of the Mn(IV)/Fe(IV) activation intermediate. ..
  34. pmc Characterization of quinolinate synthases from Escherichia coli, Mycobacterium tuberculosis, and Pyrococcus horikoshii indicates that [4Fe-4S] clusters are common cofactors throughout this class of enzymes
    Allison H Saunders
    Department of Chemistry and Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:10999-1012. 2008
    ..does not accurately represent the active site of the protein, and that the "activity" reported does not correspond to quinolinate formation...
  35. doi request reprint RlmN and AtsB as models for the overproduction and characterization of radical SAM proteins
    Nicholas D Lanz
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania, USA
    Methods Enzymol 516:125-52. 2012
    ....
  36. doi request reprint Evidence for only oxygenative cleavage of aldehydes to alk(a/e)nes and formate by cyanobacterial aldehyde decarbonylases
    Ning Li
    Department of Biochemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 51:7908-16. 2012
    ....
  37. pmc Cfr and RlmN contain a single [4Fe-4S] cluster, which directs two distinct reactivities for S-adenosylmethionine: methyl transfer by SN2 displacement and radical generation
    Tyler L Grove
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 133:19586-9. 2011
    ..It serves to methylate C355 of RlmN (C338 of Cfr), or to generate the 5'-deoxyadenosyl 5'-radical, required for substrate-dependent methyl synthase activity...
  38. ncbi request reprint Escherichia coli L-serine deaminase requires a [4Fe-4S] cluster in catalysis
    Robert M Cicchillo
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, 16802, USA
    J Biol Chem 279:32418-25. 2004
    ..03 in the EPR spectrum of the protein, and a dramatic loss in signal intensity, suggesting that the amino acid interacts directly with the cluster...
  39. ncbi request reprint Enzymatic C-H activation by metal-superoxo intermediates
    J Martin Bollinger
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, PA 16802, USA
    Curr Opin Chem Biol 11:151-8. 2007
    ....
  40. ncbi request reprint Further insights into the spectroscopic properties, electronic structure, and kinetics of formation of the heme-peroxo-copper complex [(F8TPP)FeIII-(O2(2-)-CuII(TMPA)]+
    Reza A Ghiladi
    Department of Chemistry, The Johns Hopkins University, Charles and 34th Streets, Baltimore, Maryland 21218, USA
    Inorg Chem 46:3889-902. 2007
    ..5 mol O2 per mol 3. Characterization of the reaction 1a/1b + O2 --> 2 --> 3 --> 4, presented here, advances our understanding and provides new insights to heme/Cu dioxygen-binding and reduction...
  41. pmc A long-lived, substrate-hydroxylating peroxodiiron(III/III) intermediate in the amine oxygenase, AurF, from Streptomyces thioluteus
    Victoria Korneeva Korboukh
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 131:13608-9. 2009
    ..The nearly quantitative conversion of pABA to pNBA by solutions containing an excess of the intermediate suggests that it may also be competent for the two subsequent two-electron oxidations leading to the product...
  42. pmc Organophosphonate-degrading PhnZ reveals an emerging family of HD domain mixed-valent diiron oxygenases
    Bigna Wörsdörfer
    Departments of Chemistry, and Biochemistry and Molecular Biology, and Huck Institutes of the Life Sciences, The Pennsylvania State University, University Park, PA 16802
    Proc Natl Acad Sci U S A 110:18874-9. 2013
    ..The results demonstrate that the catalytic repertoire of the HD superfamily extends well beyond phosphohydrolysis and suggest that the mechanism used by MIOX and PhnZ may be a common strategy for oxidative C-X bond cleavage. ..
  43. pmc In vitro characterization of AtsB, a radical SAM formylglycine-generating enzyme that contains three [4Fe-4S] clusters
    Tyler L Grove
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 47:7523-38. 2008
    ..Use of a peptide substrate in which the target serine is changed to cysteine also gives rise to turnover, supporting approximately 4-fold the activity of that observed with the natural substrate...
  44. pmc A consensus mechanism for Radical SAM-dependent dehydrogenation? BtrN contains two [4Fe-4S] clusters
    Tyler L Grove
    Department of Chemistry, Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 49:3783-5. 2010
    ..In this work, we show that BtrN contains an additional [4Fe-4S] cluster, thought to bind in contact with the substrate to facilitate loss of the second electron in the two-electron oxidation...
  45. ncbi request reprint Stalking intermediates in oxygen activation by iron enzymes: motivation and method
    J Martin Bollinger
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, 306 South Frear Building, University Park, PA 16802, USA
    J Inorg Biochem 100:586-605. 2006
    ..That work elegantly illustrated that, although it may be impossible to develop a true algorithm for the process, a synthesis of guidelines and general principles can be of considerable value...
  46. pmc Active site threonine facilitates proton transfer during dioxygen activation at the diiron center of toluene/o-xylene monooxygenase hydroxylase
    Woon Ju Song
    Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA
    J Am Chem Soc 132:13582-5. 2010
    ..A mechanism is postulated for dioxygen activation, and possible structures of oxygenated intermediates are discussed...
  47. ncbi request reprint Escherichia coli quinolinate synthetase does indeed harbor a [4Fe-4S] cluster
    Robert M Cicchillo
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, 16802, USA
    J Am Chem Soc 127:7310-1. 2005
    ..coli contains one [4Fe-4S] cluster per polypeptide. The protein is active, catalyzing the formation of quinolinic acid with a Vmax [ET]-1 of 0.01 s-1...
  48. ncbi request reprint Two interconverting Fe(IV) intermediates in aliphatic chlorination by the halogenase CytC3
    DANICA P GALONIC
    Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, 240 Longwood Ave, Boston, Massachusetts 02115, USA
    Nat Chem Biol 3:113-6. 2007
    ..The demonstration that chlorination proceeds through an Fe(IV) intermediate that cleaves a C-H bond reveals the mechanistic similarity of aliphatic halogenases to the iron- and alphaKG-dependent hydroxylases...
  49. ncbi request reprint Evidence for basic ferryls in cytochromes P450
    Rachel K Behan
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 128:11471-4. 2006
    ..16 mm/s; P450cam, DeltaE(Q) = 2.06 mm/s) are in good agreement with the values calculated for the protonated forms of the enzymes. Our results suggest that basic ferryls are a natural consequence of thiolate-ligated hemes...
  50. pmc The active form of Chlamydia trachomatis ribonucleotide reductase R2 protein contains a heterodinuclear Mn(IV)/Fe(III) cluster with S = 1 ground state
    Wei Jiang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 129:7504-5. 2007
  51. pmc Four-electron oxidation of p-hydroxylaminobenzoate to p-nitrobenzoate by a peroxodiferric complex in AurF from Streptomyces thioluteus
    Ning Li
    Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, 16802, USA
    Proc Natl Acad Sci U S A 107:15722-7. 2010
    ..This novel type of four-electron N-oxidation is likely also to occur in the reaction sequences of nitro-installing di-iron amine oxygenases in the biosyntheses of other natural products...
  52. pmc Conversion of fatty aldehydes to alka(e)nes and formate by a cyanobacterial aldehyde decarbonylase: cryptic redox by an unusual dimetal oxygenase
    Ning Li
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 133:6158-61. 2011
    ....
  53. ncbi request reprint Demonstration by 2H ENDOR spectroscopy that myo-inositol binds via an alkoxide bridge to the mixed-valent diiron center of myo-inositol oxygenase
    Sun Hee Kim
    Department of Chemistry, Northwestern University, Evanston, Illinois 60208 3113, USA
    J Am Chem Soc 128:10374-5. 2006
    ..Analysis shows that MI adopts a symmetrical geometry in which the O-C-2H plane of the bridge is approximately orthogonal to the Fe-O-Fe plane...
  54. pmc Substrate-triggered addition of dioxygen to the diferrous cofactor of aldehyde-deformylating oxygenase to form a diferric-peroxide intermediate
    Maria E Pandelia
    Departments of Chemistry and Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    J Am Chem Soc 135:15801-12. 2013
    ....
  55. doi request reprint Evidence that the fosfomycin-producing epoxidase, HppE, is a non-heme-iron peroxidase
    Chen Wang
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, PA, USA
    Science 342:991-5. 2013
    ..The ability of catalase to suppress the HppE activity previously attributed to its direct utilization of O2 implies that reduction of O2 and utilization of the resultant H2O2 were actually operant. ..
  56. pmc Evidence that the β subunit of Chlamydia trachomatis ribonucleotide reductase is active with the manganese ion of its manganese(IV)/iron(III) cofactor in site 1
    Laura M K Dassama
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 134:2520-3. 2012
    ....
  57. ncbi request reprint Escherichia coli lipoyl synthase binds two distinct [4Fe-4S] clusters per polypeptide
    Robert M Cicchillo
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 43:11770-81. 2004
    ....
  58. pmc Importance of the maintenance pathway in the regulation of the activity of Escherichia coli ribonucleotide reductase
    Daniela Hristova
    Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA
    Biochemistry 47:3989-99. 2008
    ..Whole cell Mössbauer analysis on cells induced with 0.5 mM arabinose supports high iron loading in beta. These results suggest that modulation of the level of Y (*) in vivo in E. coli is a mechanism of regulating RNR activity...
  59. pmc Direct spectroscopic evidence for a high-spin Fe(IV) intermediate in tyrosine hydroxylase
    Bekir E Eser
    Department of Chemistry, Texas A and M University, College Station, Texas 77843, USA
    J Am Chem Soc 129:11334-5. 2007
  60. pmc Detection of formate, rather than carbon monoxide, as the stoichiometric coproduct in conversion of fatty aldehydes to alkanes by a cyanobacterial aldehyde decarbonylase
    Douglas M Warui
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, United States
    J Am Chem Soc 133:3316-9. 2011
    ..Two possible resolutions to this conundrum are suggested...
  61. ncbi request reprint Demonstration of peroxodiferric intermediate in M-ferritin ferroxidase reaction using rapid freeze-quench Mössbauer, resonance Raman, and XAS spectroscopies
    Carsten Krebs
    Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Methods Enzymol 354:436-54. 2002
  62. pmc Evidence for C-H cleavage by an iron-superoxide complex in the glycol cleavage reaction catalyzed by myo-inositol oxygenase
    Gang Xing
    Department of Biochemistry, Pennsylvania State University, University Park, PA 16802, USA
    Proc Natl Acad Sci U S A 103:6130-5. 2006
    ..This step is associated with a kinetic isotope effect of > or =5, showing that the superoxide-level complex does indeed cleave a C-H(D) bond of MI...
  63. ncbi request reprint Reaction of cytochrome P450BM3 and peroxynitrite yields nitrosyl complex
    Rachel K Behan
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 129:5855-9. 2007
    ..We present density functional calculations as well as Mössbauer and stopped-flow spectroscopic characterizations of the peroxynitrite-generated intermediate in P450BM3...
  64. doi request reprint Elucidation of the Fe(IV)=O intermediate in the catalytic cycle of the halogenase SyrB2
    Shaun D Wong
    Department of Chemistry, Stanford University, Stanford, California 94305, USA
    Nature 499:320-3. 2013
    ....
  65. ncbi request reprint Evidence for two ferryl species in chloroperoxidase compound II
    Kari L Stone
    Department of Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    J Am Chem Soc 128:6147-53. 2006
    ..The unchanging ratio of component concentrations is in agreement with CPO-II's visible absorption spectrum, which shows no change over the enzyme's range of pH stability...
  66. ncbi request reprint A role for iron in an ancient carbonic anhydrase
    Brian C Tripp
    Department of Biochemistry and Molecular Biology, Eberly College of Science, The Pennsylvania State University, University Park, Pennsylvania 16802 4500, USA
    J Biol Chem 279:6683-7. 2004
    ..The results identify a previously unrecognized biological function for iron...
  67. ncbi request reprint Ability of tetrahydrobiopterin analogues to support catalysis by inducible nitric oxide synthase: formation of a pterin radical is required for enzyme activity
    Amy R Hurshman
    Department of Medicinal Chemistry, University of Michigan, Ann Arbor, Michigan 48109 0606, USA
    Biochemistry 42:13287-303. 2003
    ..Although binding of H(4)B also stabilizes the NOS structure and active site, the most critical role of the pterin cofactor in NOS appears to be in electron transfer...
  68. ncbi request reprint Spectroscopic evidence for a high-spin Br-Fe(IV)-oxo intermediate in the alpha-ketoglutarate-dependent halogenase CytC3 from Streptomyces
    Danica Galonic Fujimori
    Department of Biological Chemistry and Molecular Pharmacology, Harvard Medical School, Cambridge, MA 02115, USA
    J Am Chem Soc 129:13408-9. 2007
  69. ncbi request reprint Spectroscopic and computational evaluation of the structure of the high-spin Fe(IV)-oxo intermediates in taurine: alpha-ketoglutarate dioxygenase from Escherichia coli and its His99Ala ligand variant
    Sebastian Sinnecker
    Max Planck Institut fur Bioanorganische Chemie, D 45470 Mulheim an der Ruhr, Germany
    J Am Chem Soc 129:6168-79. 2007
    ..This work lends credence to the idea that the combination of Mössbauer spectroscopy and DFT calculations can provide detailed structural information for reactive intermediates in the catalytic cycles of iron enzymes...
  70. ncbi request reprint SufR coordinates two [4Fe-4S]2+, 1+ clusters and functions as a transcriptional repressor of the sufBCDS operon and an autoregulator of sufR in cyanobacteria
    Gaozhong Shen
    Departments of Biochemistry and Molecular Biology and Chemistry, The Pennsylvania State University, University Park, Pennsylvania 16802
    J Biol Chem 282:31909-19. 2007
    ..The Fe/S protein SufR thus functions both as a transcriptional repressor of the sufBCDS operon and as an autoregulator of sufR...
  71. ncbi request reprint Identification of FX in the heliobacterial reaction center as a [4Fe-4S] cluster with an S = 3/2 ground spin state
    Mark Heinnickel
    Department of Biochemistry and Molecular Biology, The Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 45:6756-64. 2006
    ....
  72. ncbi request reprint Facile electron transfer during formation of cluster X and kinetic competence of X for tyrosyl radical production in protein R2 of ribonucleotide reductase from mouse
    Danny Yun
    Department of Biochemistry and Molecular Biology, Pennsylvania State University, University Park, Pennsylvania 16802, USA
    Biochemistry 41:981-90. 2002
    ..The conclusions that cluster X is an intermediate in Y177 radical formation and that transfer of the reducing equivalent is relatively facile imply that the mouse R2 and E. coli R2 reactions are mechanistically similar...
  73. pmc A catalytic di-heme bis-Fe(IV) intermediate, alternative to an Fe(IV)=O porphyrin radical
    Xianghui Li
    Department of Biochemistry, University of Mississippi Medical Center, 2500 North State Street, Jackson, MS 39216, USA
    Proc Natl Acad Sci U S A 105:8597-600. 2008
    ..These findings broaden our views of how proteins can stabilize a highly reactive oxidizing species and the scope of enzyme-catalyzed posttranslational modifications...
  74. ncbi request reprint Stoichiometric production of hydrogen peroxide and parallel formation of ferric multimers through decay of the diferric-peroxo complex, the first detectable intermediate in ferritin mineralization
    Guy N L Jameson
    Department of Physics, Emory University, Atlanta, Georgia 30322, USA
    Biochemistry 41:13435-43. 2002
    ....
  75. ncbi request reprint Exchange coupling constant J of peroxodiferric reaction intermediates determined by Mössbauer spectroscopy
    Carsten Krebs
    Department of Physics, Emory University, Atlanta, GA 30322, USA
    J Biol Inorg Chem 7:863-9. 2002
    ..This work demonstrates the capability of Mössbauer spectroscopy to determine exchange coupling constants of diiron complexes, including reaction intermediates. The approach and its limitations are described...
  76. ncbi request reprint Coordination of adenosylmethionine to a unique iron site of the [4Fe-4S] of pyruvate formate-lyase activating enzyme: a Mössbauer spectroscopic study
    Carsten Krebs
    Department of Physics, Emory University, Atlanta, Georgia 30322, USA
    J Am Chem Soc 124:912-3. 2002
    ..This observation indicates that AdoMet coordination is a necessary prerequisite to adenosyl radical generation...
  77. ncbi request reprint EXAFS spectroscopic evidence for an Fe=O unit in the Fe(IV) intermediate observed during oxygen activation by taurine:alpha-ketoglutarate dioxygenase
    Pamela J Riggs-Gelasco
    Department of Chemistry and Biochemistry, College of Charleston, Charleston, SC 29424, USA
    J Am Chem Soc 126:8108-9. 2004
    ..The detection of this interaction strongly corroborates the hypothesis that the intermediate contains an Fe=O structural motif...
  78. ncbi request reprint YfaE, a ferredoxin involved in diferric-tyrosyl radical maintenance in Escherichia coli ribonucleotide reductase
    Chia Hung Wu
    Departments of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139, USA
    Biochemistry 46:11577-88. 2007
    ..The titrations and kinetic studies provide the first evidence for a protein involved in the maintenance pathway and likely the biosynthetic pathway...
  79. ncbi request reprint Characterization of the cofactor composition of Escherichia coli biotin synthase
    Michele Mader Cosper
    Department of Chemistry and Center for Metalloenzyme Studies, University of Georgia, Athens, Georgia 30602, USA
    Biochemistry 43:2007-21. 2004
    ..In addition, they provide a firm foundation for assessing cluster transformations that occur during turnover and the catalytic competence of the [2Fe-2S](2+) cluster as the immediate S-donor for biotin biosynthesis...
  80. ncbi request reprint NifS-mediated assembly of [4Fe-4S] clusters in the N- and C-terminal domains of the NifU scaffold protein
    Archer D Smith
    Department of Chemistry and Center for Metalloenzyme Studies, University of Georgia, Athens, Georgia 30602, USA
    Biochemistry 44:12955-69. 2005
    ..The assembly and transfer of clusters on NifU are compared with results reported for U- and Nfu-type scaffold proteins, and the need for two functional Fe-S cluster scaffolding domains on NifU is discussed...

Research Grants5

  1. Mechanism of taurine: alpha-ketoglutarate dioxygenase
    Carsten Krebs; Fiscal Year: 2007
    ..Achievement of these goals will provide new and unprecedented insight into the molecular details of the catalytic mechanism of TauD and, more importantly, of the Fe(ll)/a-ketoglutarate-dependent dioxygenases in general. ..