Probing hydrogen bonding to bound dioxygen in synthetic models for heme proteins: the importance of precise geometry.

Distal hydrogen bonding in natural dioxygen binding proteins is crucial for the discrimination between different potential ligands such as O(2) or CO. In the present study, we probe the chemical requirements for proper distal hydrogen bonding in a series of synthetic model compounds for dioxygen-binding heme proteins. The model compounds 1-Co to 7-Co bear different distal residues. The hydrogen bonding in their corresponding dioxygen adducts is directly measured by pulse EPR spectroscopy. The geometrical requirements for this interaction to take place were found to be narrow and very specific. Only two model complexes, 1-Co and 7-Co, form a hydrogen bond to bound dioxygen, which was characterized in terms of geometry and nature of the bond. The geometry and dipolar nature of this interaction in 1-Co-O(2) is more similar to the one in natural cobalt myoglobin (Co-Mb), making 1-Co the best model compound in the entire series.

[1]  Gunnar Jeschke,et al.  Direkter Nachweis einer Wasserstoffbrücke zu gebundenem Disauerstoff in einem Modellkomplex für Myoglobin/Hämoglobin und in Cobalt‐Myoglobin durch Puls‐EPR , 2008 .

[2]  F. Diederich,et al.  Direct evidence for a hydrogen bond to bound dioxygen in a myoglobin/hemoglobin model system and in cobalt myoglobin by pulse-EPR spectroscopy. , 2008, Angewandte Chemie.

[3]  S. Stoll,et al.  5- and 6-pulse electron spin echo envelope modulation (ESEEM) of multi-nuclear spin systems. , 2008, Journal of magnetic resonance.

[4]  K. Shikama,et al.  Nature of the FeO2 bonding in myoglobin and hemoglobin: A new molecular paradigm. , 2006, Progress in biophysics and molecular biology.

[5]  Arthur Schweiger,et al.  EasySpin, a comprehensive software package for spectral simulation and analysis in EPR. , 2006, Journal of magnetic resonance.

[6]  S. Stoll,et al.  Peak suppression in ESEEM spectra of multinuclear spin systems. , 2005, Journal of magnetic resonance.

[7]  F. Diederich,et al.  Synthesis of Dendritic Metalloporphyrins with Distal H-Bond Donors as Model Systems for Hemoglobin , 2005 .

[8]  François Diederich,et al.  Wechselwirkungen mit aromatischen Ringen in chemischen und biologischen Erkennungsprozessen , 2003 .

[9]  F. Diederich,et al.  Dendritic metalloporphyrins with a distal H-bond donor as mimics of haemoglobin. , 2003, Organic & biomolecular chemistry.

[10]  F. Diederich,et al.  Interactions with aromatic rings in chemical and biological recognition. , 2003, Angewandte Chemie.

[11]  F. Diederich,et al.  Dendritic Iron Porphyrins with a Tethered Axial Ligand as New Model Compounds for Heme Monooxygenases , 2002 .

[12]  B. Kräutler,et al.  A Continuous Wave and Pulse EPR and ENDOR Investigation of Oxygenated Co(II) Corrin Complexes , 2001 .

[13]  I. V. Still,et al.  An efficient route to 5-iodo-1-methylimidazole: synthesis of xestomanzamine A , 2001 .

[14]  A. Schweiger,et al.  A Q-band pulse EPR/ENDOR spectrometer and the implementation of advanced one- and two-dimensional pulse EPR methodology. , 2001, Journal of magnetic resonance.

[15]  B. Vallone,et al.  The structures of deoxy human haemoglobin and the mutant Hb Tyrα42His at 120 K , 2000 .

[16]  Chen-zhong Li,et al.  Electrochemical and spectroelectrochemical studies on cobalt myoglobin , 2000 .

[17]  L. Moens,et al.  Modulation of the oxygen affinity of cobalt‐porphyrin by globin , 2000, FEBS letters.

[18]  2-Bromo-5-hydroxy­benz­aldehyde , 2000 .

[19]  Emma Lloyd Raven,et al.  Chemical reactivity of the active site of myoglobin , 2000 .

[20]  Mark A Miller,et al.  Refined Synthesis of 5-Substituted Dipyrromethanes , 1999 .

[21]  Christopher A. Hunter,et al.  Hydrogen-bond recognition of cyclic dipeptides in water , 1998 .

[22]  F. Diederich,et al.  Dendrimers with Porphyrin Cores: Synthetic Models for Globular Heme Proteins , 1997 .

[23]  S. Kojima,et al.  A CONCISE SYNTHESIS OF 7-SUBSTITUTED INDOLES , 1996 .

[24]  C. Hunter,et al.  How strong is a π-facial hydrogen bond? , 1996 .

[25]  B. Hoffman,et al.  Quantitative studies of davies pulsed ENDOR , 1992 .

[26]  C. Avendaño,et al.  Reactivity of 4(7)-aminobenzimidazole as a bidentate nucleophile. , 1991 .

[27]  Benno P. Schoenborn,et al.  Neutron diffraction reveals oxygen–histidine hydrogen bond in oxymyoglobin , 1981, Nature.

[28]  J. Chien,et al.  Electron paramagnetic resonance crystallography of 17O-enriched oxycobaltomyoglobin: stereoelectronic structure of the cobalt dioxygen system. , 1980, Proceedings of the National Academy of Sciences of the United States of America.

[29]  E. R. Davies,et al.  A new pulse endor technique , 1974 .

[30]  M. Joullié,et al.  Notes- Preparation of 5(6)-Iodobenzimidazole and 4(7)-Iodobenzimidazole. , 1961 .