Magnetic and structural characterization of transition metal porphyrin complexes and the heme sites of heme peroxidases
Four studies of heme and heme model systems are described. The first study involves low temperature solution structural characterization of high-valent porphinatomanganese complexes via {sup 2}H- and {sup 13}C-NMR, and ESR spectroscopies. The reactive species were generated by low temperature reaction with chlorine (0) and chlorine(I) reagents. The implications of these species are discussed in terms of the relative reactivity of other +4 first row transition metal complexes and in terms of the catalytic effectiveness of porphinatomanganese (III) complexes in oxo-transfer reactions. The second study involved the analysis of isotropic {sup 2}H-NMR shifts observed for specifically deuterated chloro-N-methylporphinatomanganese(II) complexes. An ESR spectroscopic study of several ferrous heme peroxidase/NO complexes is presented. The {sup 14}N and {sup 15}N hyperfine splitting patterns and coupling constants in the ESR spectra clearly demonstrate the presence of a nitrogen-bound proximal ligand in lactoperoxidase. Finally, a catalytic autoxidation system involving cyclohexene and/or propanal as substrates is described. This reaction is catalyzed by high spin tetraarylporphinatoiron (III) complexes and evolves CO{sub 2}.
- Research Organization:
- Iowa State Univ. of Science and Technology, Ames, IA (USA)
- OSTI ID:
- 6948656
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
59 BASIC BIOLOGICAL SCIENCES
CARBON 13
CARBON ISOTOPES
CARBOXYLIC ACIDS
CHEMICAL SHIFT
COMPLEXES
DEUTERIUM
ELECTRON SPIN RESONANCE
ELEMENTS
ENZYMES
EVEN-ODD NUCLEI
HEME
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
HYDROGEN ISOTOPES
ISOTOPE APPLICATIONS
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MANGANESE
METALS
MOLECULAR STRUCTURE
NITROGEN 14
NITROGEN 15
NITROGEN ISOTOPES
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUCLEI
ODD-EVEN NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDOREDUCTASES
PEROXIDASES
PIGMENTS
PORPHYRINS
REAGENTS
RESONANCE
SPECTRA
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
TRACER TECHNIQUES
TRANSITION ELEMENTS