BIOINORGANIC COPPER COORDINATION CHEMISTRY

Summary

Principal Investigator: Kenneth D Karlin
Abstract: DESCRIPTION (provided by applicant): The goal of the proposed research is to further develop fundamental aspects of copper coordination chemistry relevant to its essential role in the biochemical processing of dioxygen (O2) and nitrogen oxides (NOx). Many questions remain concerning copper(I)/O2 interactions, dynamics &energetics of O2-adduct formation, as well as questions concerning structure, associated spectroscopy, O-O bond cleavage (i.e., O2-activation) and substrate oxidation chemistries. Copper-NOx interactions relate to the possible role of copper ion in nitrogen monoxide (NO) biology, then leading to oxidative and/or nitrative stress. The research divides into sub- projects, directed along various themes or chemical systems. These include: (1) dicopper chemistry studies, where recent advances have brought focus to very low coordinate Cu2 centers in particulate methane monooxygenase, of great biological and energy concerns. Attention will be paid to dicopper complexes with a single oxo ion bridge, as the possible reactive species toward methane. Also, mixed-valent bis-oxo dicopper complexes will be sought and investigations into the fundamentally important O-O cleavage process will be carried out, (2) the study of O2 and carbon monoxide (CO, as O2-surrogate) kinetics and thermodynamics of binding to tetradentate ligand CuI-chelates including with one thioether donor atom, that being biologically relevant. Previously unseen classes of copper-dioxygen complexes will also be studied employing tridentate ligand chelates. The very fast reactions involved call for application of time-resolved techniques. With new collaborators, additional state-of-the-art time-resolved methods will be applied, (3) comparative studies of copper peroxo and copper-superoxo species substrate reactivity will be carried out using ligands with synthetically placed internal substrates. In addition, we will explore the possibility that copper active-site chemistry involves methionine sulfur radical cation formation during O2-actvation and enzyme turnover, a new paradigm in the field, (4) direct in-depth reactivity studies with a series of stabilized copper-superoxo complexes. These will include oxidation of phenols, substrates with weak C-H bonds and electron-proton reduction to copper-hydroperoxo complexes. (5) advanced investigations into copper/O2/nitrogen-monoxide (nitric oxide) interactions, following a new paradigm concerning the possible role of copper ion in the biological formation of the reactive nitrogen species peroxynitrite (-OON=O). Peroxynitrite complexes with copper(II) ion will be generated and characterized in detail, and their reactions with especially phenolic or carbon dioxide substrates will be examined. Mechanistic inquiries will include their transformation to nitrite plus oxygen or to nitrate. Overall, the proposed studies contribute to a broader understanding of copper biochemistry, other metalloprotein (e.g., heme or non-heme iron) activation/reduction of O2 and NOx in biology, and associated disease states. Potential long-term applications of this basic research include development of enzyme inhibitors and relevant disease therapeutic strategies. PUBLIC HEALTH RELEVANCE: The proposed studies contribute to a broader understanding of copper biochemistry, other metalloprotein (e.g., heme or non-heme iron) activation/reduction of O2 and NOx in biology and associated disease states. Potential long-term applications of this basic research include development of enzyme inhibitors and relevant disease therapeutic strategies.
Funding Period: 1981-04-01 - 2015-03-31
more information: NIH RePORT

Top Publications

  1. pmc Mechanistic insights into the oxidation of substituted phenols via hydrogen atom abstraction by a cupric-superoxo complex
    Jung Yoon Lee
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 136:9925-37. 2014
  2. pmc Coordination chemistry and reactivity of a cupric hydroperoxide species featuring a proximal H-bonding substituent
    Sunghee Kim
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    Inorg Chem 51:12603-5. 2012
  3. pmc Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity
    Atsutoshi Yokoyama
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    J Am Chem Soc 134:15269-72. 2012
  4. pmc Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(II) complex
    Yusuke Yamada
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka 565 0871, Japan
    Phys Chem Chem Phys 14:9654-9. 2012
  5. pmc Geometric and electronic structure of [{Cu(MeAN)}2(μ-η2:η2(O2(2-)))]2+ with an unusually long O-O bond: O-O bond weakening vs activation for reductive cleavage
    Ga Young Park
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 134:8513-24. 2012
  6. pmc Formation of a long-lived electron-transfer state in mesoporous silica-alumina composites enhances photocatalytic oxygenation reactivity
    Shunichi Fukuzumi
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka, Japan
    Proc Natl Acad Sci U S A 109:15572-7. 2012
  7. pmc Dioxygen reactivity of new bispidine-copper complexes
    Peter Comba
    Anorganisch Chemisches Institut, Universitat Heidelberg, INF 270, D 69120 Heidelberg, Germany
    Inorg Chem 51:2841-51. 2012
  8. pmc Electron-transfer reduction of dinuclear copper peroxo and bis-μ-oxo complexes leading to the catalytic four-electron reduction of dioxygen to water
    Laleh Tahsini
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    Chemistry 18:1084-93. 2012
  9. pmc Homogeneous catalytic O2 reduction to water by a cytochrome c oxidase model with trapping of intermediates and mechanistic insights
    Zakaria Halime
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka 565 0871, Japan
    Proc Natl Acad Sci U S A 108:13990-4. 2011
  10. pmc Cupric superoxo-mediated intermolecular C-H activation chemistry
    Ryan L Peterson
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 133:1702-5. 2011

Detail Information

Publications54

  1. pmc Mechanistic insights into the oxidation of substituted phenols via hydrogen atom abstraction by a cupric-superoxo complex
    Jung Yoon Lee
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 136:9925-37. 2014
    ..By contrast, four-electron oxygenation (O-O cleavage) mainly occurs for p-R-DTBP which gives (18)O-labeled DTBQ and elimination of the R group...
  2. pmc Coordination chemistry and reactivity of a cupric hydroperoxide species featuring a proximal H-bonding substituent
    Sunghee Kim
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    Inorg Chem 51:12603-5. 2012
    ..Unlike a close analogue not possessing internal H-bonding, 2 affords no oxidative reactivity with internal or external substrates. However, 2 can be protonated to release H(2)O(2), but only with HClO(4), while 1 equiv Et(3)N restores 2...
  3. pmc Chromium(IV)-peroxo complex formation and its nitric oxide dioxygenase reactivity
    Atsutoshi Yokoyama
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    J Am Chem Soc 134:15269-72. 2012
    ..The latter is suggested to form via a Cr(III)-peroxynitrite intermediate. [Cr(II)(12-TMC)(NO)(Cl)](+) (4), a Cr(II)-nitrosyl complex derived from 1 and NO, could also be synthesized; however, it does not react with O(2)...
  4. pmc Improvement of durability of an organic photocatalyst in p-xylene oxygenation by addition of a Cu(II) complex
    Yusuke Yamada
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka 565 0871, Japan
    Phys Chem Chem Phys 14:9654-9. 2012
    ....
  5. pmc Geometric and electronic structure of [{Cu(MeAN)}2(μ-η2:η2(O2(2-)))]2+ with an unusually long O-O bond: O-O bond weakening vs activation for reductive cleavage
    Ga Young Park
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 134:8513-24. 2012
    ..These results highlight the necessity of understanding electronic structure changes associated with spectral changes for correlations to reactivity...
  6. pmc Formation of a long-lived electron-transfer state in mesoporous silica-alumina composites enhances photocatalytic oxygenation reactivity
    Shunichi Fukuzumi
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka, Japan
    Proc Natl Acad Sci U S A 109:15572-7. 2012
    ....
  7. pmc Dioxygen reactivity of new bispidine-copper complexes
    Peter Comba
    Anorganisch Chemisches Institut, Universitat Heidelberg, INF 270, D 69120 Heidelberg, Germany
    Inorg Chem 51:2841-51. 2012
    ..The mechanism of dioxygen binding as well as the preference of each of the three ligands for a particular dioxygen adduct is discussed on the basis of a computational (density functional theory) analysis...
  8. pmc Electron-transfer reduction of dinuclear copper peroxo and bis-μ-oxo complexes leading to the catalytic four-electron reduction of dioxygen to water
    Laleh Tahsini
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    Chemistry 18:1084-93. 2012
    ..The bis-μ-oxo species (4) is reduced by Fc* with a much faster rate than the η(2):η(2)-peroxo complex (3), but this also leads to the four-electron reduction of dioxygen to water...
  9. pmc Homogeneous catalytic O2 reduction to water by a cytochrome c oxidase model with trapping of intermediates and mechanistic insights
    Zakaria Halime
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, Osaka University, Suita, Osaka 565 0871, Japan
    Proc Natl Acad Sci U S A 108:13990-4. 2011
    ..Thus, the role of the Cu ion is to assist the heme and lead to faster O(2)-binding at RT. However, the proximate Cu ion has no effect on the O-O bond cleavage of the Fe(III)-OOH species at low temperature...
  10. pmc Cupric superoxo-mediated intermolecular C-H activation chemistry
    Ryan L Peterson
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 133:1702-5. 2011
    ..Kinetic studies indicated a first-order dependence on both the Cu complex and BNAH with a deuterium kinetic isotope effect (KIE) of 12.1, similar to that observed for certain copper monooxygenases...
  11. pmc Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand
    Yu Jin Choi
    Department of Chemistry and Nano Science, Ewha Womans University, Seoul, Korea
    Dalton Trans 40:2234-41. 2011
    ..These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions...
  12. pmc Temperature-independent catalytic two-electron reduction of dioxygen by ferrocenes with a copper(II) tris[2-(2-pyridyl)ethyl]amine catalyst in the presence of perchloric acid
    Dipanwita Das
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    J Am Chem Soc 135:2825-34. 2013
    ....
  13. pmc Acid-induced mechanism change and overpotential decrease in dioxygen reduction catalysis with a dinuclear copper complex
    Dipanwita Das
    Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    J Am Chem Soc 135:4018-26. 2013
    ....
  14. pmc Observation of a Cu(II)(2) (μ-1,2-peroxo)/Cu(III)(2) (μ-oxo)(2) equilibrium and its implications for copper-dioxygen reactivity
    Matthew T Kieber-Emmons
    Department of Chemistry, Stanford University, Stanford, CA 94305 USA
    Angew Chem Int Ed Engl 53:4935-9. 2014
    ..This study is the first report of the interconversion of an end-on peroxo to bis-μ-oxo species in transition metal-dioxygen chemistry. ..
  15. pmc Excitation wavelength dependent O2 release from copper(II)-superoxide compounds: laser flash-photolysis experiments and theoretical studies
    Claudio Saracini
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, United States
    J Am Chem Soc 136:1260-3. 2014
    ..TD-DFT studies, carried out for 1, support the experimental results confirming the dissociative character of the excited states formed upon blue- or red-light laser excitation. ..
  16. pmc An isoelectronic NO dioxygenase reaction using a nonheme iron(III)-peroxo complex and nitrosonium ion
    Atsutoshi Yokoyama
    Department of Chemistry and Nano Science, Department of Bioinspired Science, Ewha Womans University, Seoul 120 750, Korea
    Chem Commun (Camb) 50:1742-4. 2014
    ....
  17. pmc Peroxynitrite chemistry derived from nitric oxide reaction with a Cu(II)-OOH species and a copper mediated NO reductive coupling reaction
    Sunghee Kim
    Department of Chemistry, The Johns Hopkins University, 3400 N Charles Street, Baltimore, MD 21218, USA
    Chem Commun (Camb) 50:2844-6. 2014
    ..In characterizing the system, the ligand-Cu(i) complex was shown to effect a seldom observed ˙NO(g) reductive coupling reaction. Biological implications are discussed. ..
  18. pmc Correlation of the electronic and geometric structures in mononuclear copper(II) superoxide complexes
    Jake W Ginsbach
    Department of Chemistry, Stanford University, Stanford, California 94305, United States
    Inorg Chem 52:12872-4. 2013
    ....
  19. pmc L-edge X-ray absorption spectroscopy and DFT calculations on Cu2O2 species: direct electrophilic aromatic attack by side-on peroxo bridged dicopper(II) complexes
    Munzarin F Qayyum
    Department of Chemistry, Stanford University, Stanford, California 94305, United States
    J Am Chem Soc 135:17417-31. 2013
    ..Thus, species P is capable of direct hydroxylation of aromatic substrates without the intermediacy of an O-type species...
  20. pmc Reactions of a chromium(III)-superoxo complex and nitric oxide that lead to the formation of chromium(IV)-oxo and chromium(III)-nitrito complexes
    Atsutoshi Yokoyama
    Department of Bioinspired Science and Department of Chemistry and Nano Science, Ewha Womans University, Seoul 120 750, Korea
    J Am Chem Soc 135:14900-3. 2013
    ..The Cr(IV)-oxo and Cr(III)-nitrito complexes were also characterized spectroscopically and/or structurally. ..
  21. pmc Enhanced catalytic four-electron dioxygen (O2) and two-electron hydrogen peroxide (H2O2) reduction with a copper(II) complex possessing a pendant ligand pivalamido group
    Saya Kakuda
    Department of Material and Life Science, Division of Advanced Science and Biotechnology, Graduate School of Engineering, ALCA JST, Osaka University, Suita, Osaka 565 0871, Japan
    J Am Chem Soc 135:6513-22. 2013
    ..For both complexes, reaction rates are greater than for the overall four-electron O2-reduction to water, an important asset in the design of catalysts for the latter...
  22. pmc Spectroscopic and computational studies of an end-on bound superoxo-Cu(II) complex: geometric and electronic factors that determine the ground state
    Julia S Woertink
    Department of Chemistry, Stanford University, Stanford, California 94305, USA
    Inorg Chem 49:9450-9. 2010
    ....
  23. pmc Sulfur donor atom effects on copper(I)/O(2) chemistry with thioanisole containing tetradentate N(3)S ligand leading to μ-1,2-peroxo-dicopper(II) species
    Yunho Lee
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 49:8873-85. 2010
    ..A detailed discussion of the spectroscopic and structural characteristics of 1b(P), 2b(P), and 3b(O) is presented...
  24. ncbi Copper dioxygen adducts: formation of bis(mu-oxo)dicopper(III) versus (mu-1,2)Peroxodicopper(II) complexes with small changes in one pyridyl-ligand substituent
    Debabrata Maiti
    Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA
    Inorg Chem 47:3787-800. 2008
    ....
  25. ncbi Carbon monoxide coordination and reversible photodissociation in copper(I) pyridylalkylamine compounds
    H Christopher Fry
    The Johns Hopkins University, Department of Chemistry, Baltimore, MD 21218, USA
    Inorg Chem 47:241-56. 2008
    ..Comparisons to O2-binding data available for these copper complexes as well as to small molecule (O2, CO, NO) reactions with hemes and copper proteins are discussed...
  26. ncbi Reactions of a copper(II) superoxo complex lead to C-H and O-H substrate oxygenation: modeling copper-monooxygenase C-H hydroxylation
    Debabrata Maiti
    Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA
    Angew Chem Int Ed Engl 47:82-5. 2008
  27. ncbi Thiol-copper(I) and disulfide-dicopper(I) complex O2-reactivity leading to sulfonate-copper(II) complex or the formation of a cross-linked thioether-phenol product with phenol addition
    Yunho Lee
    Department of Chemistry, The Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218, USA
    J Inorg Biochem 101:1845-58. 2007
    ..Separately, complex [L(SPhO)Cu(II)(ClO(4))] (4), possessing the cross-linked L(SPhOH), was characterized by ESI mass spectrometry and X-ray crystallography...
  28. ncbi Copper(I)/S(8) reversible reactions leading to an end-on bound dicopper(II) disulfide complex: nucleophilic reactivity and analogies to copper-dioxygen chemistry
    Debabrata Maiti
    Department of Chemistry, Johns Hopkins University, Baltimore, Maryland 21218, USA
    J Am Chem Soc 129:8882-92. 2007
    ..The investigation thus reveals striking analogies of copper/sulfur and copper/dioxygen chemistries, with regard to structure type formation and specific substrate reactivity patterns...
  29. ncbi Copper(I) complex O(2)-reactivity with a N(3)S thioether ligand: a copper-dioxygen adduct including sulfur ligation, ligand oxygenation, and comparisons with all nitrogen ligand analogues
    Dong Heon Lee
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 46:6056-68. 2007
    ..Discussion of the relevance of the chemistry to copper enzyme O(2)-activation, and situations of biological stress involving methionine oxidation, is provided...
  30. ncbi Thioether sulfur oxygenation from O2 or H2O2 reactivity of copper complexes with tridentate N2Sthioether ligands
    Yunho Lee
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 45:10098-107. 2006
    ..These results may provide some insight into recent reports concerning protein methionine oxidation, showing the potential importance of copper-mediated oxidation processes in certain biological settings...
  31. ncbi Dioxygen reactivity of a copper(I) complex with a N3S thioether chelate; peroxo-dicopper(II) formation including sulfur-ligation
    Lanying Q Hatcher
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21212, USA
    Inorg Chem 45:10055-7. 2006
    ..Direct evidence for thioether ligation comes from EXAFS spectroscopy {Cu K-edge; Cu-S = 2.4 A}...
  32. ncbi Targeted guanine oxidation by a dinuclear copper(II) complex at single stranded/double stranded DNA junctions
    Lei Li
    Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, USA
    Inorg Chem 45:7144-59. 2006
    ..The Cu2-O2 intermediate responsible for guanine oxidation appears to be different from that responsible for direct-strand scission induced by other multinuclear copper complexes; the likely course of reaction is discussed...
  33. pmc Selective DNA strand scission with binuclear copper complexes: implications for an active Cu2-O2 species
    Sunita Thyagarajan
    Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA
    J Am Chem Soc 128:7003-8. 2006
    ..Spectroscopic and reactivity studies with [Cu(II)(2)(N4)(Y)(2)](2+) (2) and H(2)O(2) are consistent with DNA oxidation mediated by formation of a side-on peroxodicopper(II) (Cu(2)-O(2)) complex...
  34. ncbi Copper-dioxygen adducts and the side-on peroxo dicopper(II)/bis(mu-oxo) dicopper(III) equilibrium: Significant ligand electronic effects
    Lanying Q Hatcher
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 45:3004-13. 2006
    ..Observations concerning the reactivity of the dioxygen adducts 2H and 3(NMe2) toward external substrates are also presented...
  35. ncbi Hydrogen peroxide and dioxygen activation by dinuclear copper complexes in aqueous solution: hydroxyl radical production initiated by internal electron transfer
    Qing Zhu
    Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742, USA
    J Am Chem Soc 130:6304-5. 2008
    ..These results imply that DNA cleavage does not result from direct reaction with a metal-peroxo intermediate but instead arises from reaction with either OH radicals or ligand-based radicals...
  36. ncbi Reaction of a copper-dioxygen complex with nitrogen monoxide (*NO) leads to a copper(II)-peroxynitrite species
    Debabrata Maiti
    Departments of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    J Am Chem Soc 130:6700-1. 2008
    ..The results suggest the viability of biological CuI/O2/(*NO) peroxynitrite formation and chemistry, that is, not coming from free superoxide plus *NO reaction...
  37. pmc Copper-hydroperoxo-mediated N-debenzylation chemistry mimicking aspects of copper monooxygenases
    Debabrata Maiti
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 47:8736-47. 2008
    ....
  38. pmc CO and O2 binding to pseudo-tetradentate ligand-copper(I) complexes with a variable N-donor moiety: kinetic/thermodynamic investigation reveals ligand-induced changes in reaction mechanism
    Heather R Lucas
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    J Am Chem Soc 132:12927-40. 2010
    ..Results reported here are also compared to relevant copper and/or iron biological systems and analogous synthetic ligand-copper systems...
  39. pmc Bioinspired heme, heme/nonheme diiron, heme/copper, and inorganic NOx chemistry: *NO((g)) oxidation, peroxynitrite-metal chemistry, and *NO((g)) reductive coupling
    Mark P Schopfer
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 49:6267-82. 2010
    ....
  40. pmc Mononuclear copper complex-catalyzed four-electron reduction of oxygen
    Shunichi Fukuzumi
    Department of Material and Life Science, Graduate School of Engineering, Osaka University, Suita, Osaka 565 0871, Japan
    J Am Chem Soc 132:6874-5. 2010
    ..Its reduction by a ferrocene derivative (Fc*) and reaction with O(2) leads to the formation of a peroxodicopper(II) complex; this is subsequently reduced by Fc* in the presence of protons to regenerate the Cu(II) complex...
  41. pmc Thioether S-ligation in a side-on micro-eta2:eta2-peroxodicopperii complex
    Ga Young Park
    Department of Chemistry, The Johns Hopkins University, 3400 N Charles Street, Baltimore, MD 21218, USA
    Chem Commun (Camb) 46:91-3. 2010
    ..The finding is a rare occurrence and new for side-on O(2)(2-) binding...
  42. pmc Copper(I)/O2 chemistry with imidazole containing tripodal tetradentate ligands leading to mu-1,2-peroxo-dicopper(II) species
    Yunho Lee
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 48:11297-309. 2009
    ....
  43. pmc Molecular oxygen and sulfur reactivity of a cyclotriveratrylene derived trinuclear copper(I) complex
    Debabrata Maiti
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    Inorg Chem 48:8342-56. 2009
    ....
  44. pmc A peroxynitrite complex of copper: formation from a copper-nitrosyl complex, transformation to nitrite and exogenous phenol oxidative coupling or nitration
    Ga Young Park
    Department of Chemistry, Johns Hopkins University, Baltimore, MD 21218, USA
    J Biol Inorg Chem 14:1301-11. 2009
    ....
  45. pmc Copper-dioxygen complex mediated C-H bond oxygenation: relevance for particulate methane monooxygenase (pMMO)
    RICHARD A HIMES
    Department of Chemistry, The Johns Hopkins University, Baltimore, MD 21218, United States
    Curr Opin Chem Biol 13:119-31. 2009
    ..Herein the authors briefly review the current understanding of the pMMO metal sites and discuss advances in small molecule Cu-O(2) chemistry that may contribute to an understanding of copper-ion mediated hydrocarbon oxidation chemistry...
  46. pmc Toluene and ethylbenzene aliphatic C-H bond oxidations initiated by a dicopper(II)-mu-1,2-peroxo complex
    Heather R Lucas
    Department of Chemistry, The Johns Hopkins University, Baltimore, Maryland 21218, USA
    J Am Chem Soc 131:3230-45. 2009
    ..Using (L)Cu(I), CO-binding properties (i.e., nu(C-O) values) along with electrochemical property comparisons, the relative donor abilities of (O)L, (Bz)L, and (Py)L are assessed...
  47. ncbi A mu-eta2:eta2-disulfide dicopper(II) complex from reaction of S8 with a copper(I) precursor: reactivity of the bound disulfur moiety
    Matthew E Helton
    Department of Chemistry, Johns Hopkins University, 3400 North Charles Street, Baltimore, MD 21218, USA
    Angew Chem Int Ed Engl 45:1138-41. 2006

Research Grants30

  1. Synthetic Modeling of Copper Protein Active Sites
    William B Tolman; Fiscal Year: 2013
    ..In addition to aspiring to a deep understanding of copper enzyme structure/function relationships, the proposed work is aimed at developing novel copper chemistry of fundamental significance. ..
  2. Transient catalytic oxygen species in iron enzymes
    Denis A Proshlyakov; Fiscal Year: 2013
    ..We will investigate three representative enzymes: ribonucleotide reductase is involved in DNA replication and two bacterial oxygenases provide important models of analogous enzymes in mammals. ..
  3. Simultaneous Time-Resolved X-ray Spectroscopy and Crystallography: A Mechanistic
    Rosalie Tran; Fiscal Year: 2013
    ..abstract_text> ..
  4. Reactivity of Manganese and Iron Metalloenzyme Models
    David P Goldberg; Fiscal Year: 2013
    ..Fundamental information regarding the mechanisms of biomimetic HAT, OAT, ET and related reactions will be obtained. ..