BIOMAT Database Logo BIOMAT Database Logo

Vibrational assignments of six-coordinate ferrous heme nitrosyls: new insight from nuclear resonance vibrational spectroscopy. 2008

Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Department of Chemistry, The University of Michigan, 930 N. University, Ann Arbor, Michigan 48109-1055, USA.

This Communication addresses a long-standing problem: the exact vibrational assignments of the low-energy modes of the Fe-N-O subunit in six-coordinate ferrous heme nitrosyl model complexes. This problem is addressed using nuclear resonance vibrational spectroscopy (NRVS) coupled to (15)N(18)O isotope labeling and detailed simulations of the obtained data. Two isotope-sensitive features are identified at 437 and 563 cm(-1). Normal coordinate analysis shows that the 437 cm(-1) mode corresponds to the Fe-NO stretch, whereas the 563 cm(-1) band is identified with the Fe-N-O bend. The relative NRVS intensities of these features determine the degree of vibrational mixing between the stretch and the bend. The implications of these results are discussed with respect to the trans effect of imidazole on the bound NO. In addition, a comparison to myoglobin-NO (Mb-NO) is made to determine the effect of the Mb active site pocket on the bound NO.

UI MeSH Term Description Entries
D007700 Kinetics The rate dynamics in chemical or physical systems.
D008958 Models, Molecular Models used experimentally or theoretically to study molecular shape, electronic properties, or interactions; includes analogous molecules, computer-generated graphics, and mechanical structures. Molecular Models,Model, Molecular,Molecular Model
D008968 Molecular Conformation The characteristic three-dimensional shape of a molecule. Molecular Configuration,3D Molecular Structure,Configuration, Molecular,Molecular Structure, Three Dimensional,Three Dimensional Molecular Structure,3D Molecular Structures,Configurations, Molecular,Conformation, Molecular,Conformations, Molecular,Molecular Configurations,Molecular Conformations,Molecular Structure, 3D,Molecular Structures, 3D,Structure, 3D Molecular,Structures, 3D Molecular
D009587 Nitrogen Isotopes Stable nitrogen atoms that have the same atomic number as the element nitrogen but differ in atomic weight. N-15 is a stable nitrogen isotope. Nitrogen Isotope,Isotope, Nitrogen,Isotopes, Nitrogen
D009589 Nitrogen Oxides Inorganic oxides that contain nitrogen. Nitrogen Oxide,Oxide, Nitrogen,Oxides, Nitrogen
D010103 Oxygen Isotopes Stable oxygen atoms that have the same atomic number as the element oxygen, but differ in atomic weight. O-17 and 18 are stable oxygen isotopes. Oxygen Isotope,Isotope, Oxygen,Isotopes, Oxygen
D004578 Electron Spin Resonance Spectroscopy A technique applicable to the wide variety of substances which exhibit paramagnetism because of the magnetic moments of unpaired electrons. The spectra are useful for detection and identification, for determination of electron structure, for study of interactions between molecules, and for measurement of nuclear spins and moments. (From McGraw-Hill Encyclopedia of Science and Technology, 7th edition) Electron nuclear double resonance (ENDOR) spectroscopy is a variant of the technique which can give enhanced resolution. Electron spin resonance analysis can now be used in vivo, including imaging applications such as MAGNETIC RESONANCE IMAGING. ENDOR,Electron Nuclear Double Resonance,Electron Paramagnetic Resonance,Paramagnetic Resonance,Electron Spin Resonance,Paramagnetic Resonance, Electron,Resonance, Electron Paramagnetic,Resonance, Electron Spin,Resonance, Paramagnetic
D006418 Heme The color-furnishing portion of hemoglobin. It is found free in tissues and as the prosthetic group in many hemeproteins. Ferroprotoporphyrin,Protoheme,Haem,Heme b,Protoheme IX
D013057 Spectrum Analysis The measurement of the amplitude of the components of a complex waveform throughout the frequency range of the waveform. (McGraw-Hill Dictionary of Scientific and Technical Terms, 6th ed) Spectroscopy,Analysis, Spectrum,Spectrometry
D013816 Thermodynamics A rigorously mathematical analysis of energy relationships (heat, work, temperature, and equilibrium). It describes systems whose states are determined by thermal parameters, such as temperature, in addition to mechanical and electromagnetic parameters. (From Hawley's Condensed Chemical Dictionary, 12th ed) Thermodynamic

Related Publications

Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Nuclear resonance vibrational spectroscopy applied to [Fe(OEP)(NO)]: the vibrational assignments of five-coordinate ferrous heme-nitrosyls and implications for electronic structure.
May 2010, Inorganic chemistry,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Interplay of structure and vibrational dynamics in six-coordinate heme nitrosyls.
February 2007, Journal of the American Chemical Society,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Ultrafast Dynamics and Vibrational Relaxation in Six-Coordinate Heme Proteins Revealed by Femtosecond Stimulated Raman Spectroscopy.
February 2020, Journal of the American Chemical Society,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Nuclear resonance vibrational spectroscopy--NRVS.
January 2005, Journal of inorganic biochemistry,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
The ferrous verdoheme-heme oxygenase complex is six-coordinate and low-spin.
December 2005, Journal of the American Chemical Society,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Probing vibrational anisotropy with nuclear resonance vibrational spectroscopy.
June 2010, Angewandte Chemie (International ed. in English),
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Axial ligand effects on vibrational dynamics of iron in heme carbonyl studied by nuclear resonance vibrational spectroscopy.
November 2012, The journal of physical chemistry. B,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
3D Motions of Iron in Six-Coordinate {FeNO}(7) Hemes by Nuclear Resonance Vibration Spectroscopy.
April 2016, Chemistry (Weinheim an der Bergstrasse, Germany),
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
What Can Be Learned from Nuclear Resonance Vibrational Spectroscopy: Vibrational Dynamics and Hemes.
October 2017, Chemical reviews,
Florian Paulat, and Timothy C Berto, and Serena DeBeer George, and Lauren Goodrich, and V K K Praneeth, and Corinne D Sulok, and Nicolai Lehnert
Nuclear resonance vibrational spectroscopy and DFT study of peroxo-bridged biferric complexes: structural insight into peroxo intermediates of binuclear non-heme iron enzymes.
January 2013, Angewandte Chemie (International ed. in English),
Copied contents to your clipboard!