Resonance Raman spectroscopic characterization of compound III of lignin peroxidase
- Oregon Graduate Institute of Science and Technology, Beaverton (USA)
Resonance Raman (RR) spectra of several compounds III of lignin peroxidase (LiP) have been measured at 90 K with Soret and visible excitation wavelengths. The samples include LiPIIIa (or oxyLiP) prepared by oxygenation of the ferrous enzyme, LiPIIIb generated by reaction of the native ferric enzyme with superoxide, LiPIIIc prepared from native LiP plus H{sub 2}O{sub 2} followed by removal of excess peroxide with catalase, and LiPIII made by addition of excess H{sub 2}O{sub 2} to the native enzyme. The RR spectra of these four products appear to be similar and, thus, indicate that the environments of these hexacoordinate, low-spin ferriheme species must also be very similar. Nonetheless, the Soret absorption band of LiPIII is red-shifted by 5 nm from the 414-nm maximum common to LiPIIIa, -b, and -c. Analysis of the iron-porphyrin vibrational frequencies indicates that the electronic structures for the various compounds III are consistent with an Fe{sup III}O{sub 2}{sup {center dot}-}formulation. The spectral changes observed between the oxygenated complex and the ferrous heme of lignin peroxidase are similar to those between oxymyoglobin and deoxymyoglobin. The contraction in the core sizes in compound III relative to the native peroxidase is analyzed and compared with that of other heme systems. The Fe-O{sub 2} stretching vibration of the oxygenated peroxidase is observed at 563 cm{sup {minus}1} and shifts of 538 cm{sup {minus}1} with {sup 18}O isotope. The Fe-histidine stretching vibration is observed at 245 cm{sup {minus}1} in ferrous peroxidase and appears to shift to 276 cm{sup {minus}1} in the oxygenated complex.
- DOE Contract Number:
- FG06-87ER13715
- OSTI ID:
- 5674637
- Journal Information:
- Biochemistry; (USA), Vol. 29:41; ISSN 0006-2960
- Country of Publication:
- United States
- Language:
- English
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PEROXIDASES
RAMAN SPECTROSCOPY
PORPHYRINS
ELECTRONIC STRUCTURE
ABSORPTION SPECTRA
GEOMETRY
GLYCOPROTEINS
LIGNIN
MYOGLOBIN
OXYGEN 18
PHANEROCHAETE
RAMAN SPECTRA
ULTRAVIOLET SPECTROMETERS
VIBRATIONAL STATES
CARBOHYDRATES
CARBOXYLIC ACIDS
ENERGY LEVELS
ENZYMES
EUMYCOTA
EVEN-EVEN NUCLEI
EXCITED STATES
FUNGI
GLOBINS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
ISOTOPES
LASER SPECTROSCOPY
LIGHT NUCLEI
MATHEMATICS
MEASURING INSTRUMENTS
NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
OXIDOREDUCTASES
OXYGEN ISOTOPES
PIGMENTS
PLANTS
POLYSACCHARIDES
PROTEINS
SACCHARIDES
SPECTRA
SPECTROMETERS
SPECTROSCOPY
STABLE ISOTOPES
550201* - Biochemistry- Tracer Techniques