Temperature dependence and electronic transition energies in the magnetic circular dichroism spectrum of horeseradish peroxidase compound I

Browett, William R.; Gasyna, Zbigniew; Stillman, Martin J.

doi:10.1021/ja00219a044

Cited by 44 publications

(40 citation statements)

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“…spectrum that best reflects the differences in the ground states of these two n-cation radical species. In previous work (Browett and Stillman, 198 la;Browett et al, 1988), we have noted that the m.c.d. spectra of neither catalase I nor HRP I are represented closely by either the TPP(-1) or OEP(-1) radical cation models.…”

Section: Discussionmentioning

confidence: 72%

“…We have most recently concluded that the 2A2u and 2ALu states must lie close in energy so that a greater component of either 2A2u for HRP I or 2A1U for catalase I is actually seen in the optical spectrum (Browett et al, 1988). A scheme explaining the proposed energies of these two states is shown in Figure 1.…”

Section: Introductionmentioning

confidence: 95%

“…While the m.c.d. data for different ring-oxidized porphyrins easily allow characterization of either a 2Alu or 2A2u ground state (Gasyna and Stillman, 1990), the differences observed for HRP I and catalase I are not nearly as well marked (Browett et al, 1988).…”

Section: Introductionmentioning

confidence: 98%

“…The spectral properties of these species have been studied extensively in order to interpret the role of the electronic structure of the iron and the porphyrin ring in the observed enzymatic chemistry (Strickland et al, 1968;Fajer et al, 1973;Stillman et al, 1975Dunford and Stillman, 1976;Morishima and Ogawa, 1978;Browett and Stillman, 1979, 1981aDolphin, 1981;Hanson et al, 1981;Teraoka et al, 1982;Browett et al, 1983a,b;Sievers et al, 1983;Fujita et al, 1983;Ohlsson et al, 1984;Oertling and Babcock, 1985;van Wart and Zimmer, 1985;Penner-Hahn et al, 1986;Foote et al, 1987;Oertling et al, 1987;Ogura and Kitagawa, 1987;Browett et al, 1988;Gasyna et al, 1988a;Dawson et al, 1991;Loew et al, 1991;Du et al, 1991;Du and Loew, 1992). The absorption spectra of HRP I and catalase I have long puzzled spectroscopists, as these spectra are quite unique.…”

Section: Introductionmentioning

confidence: 99%

“…Slight differences in the absorption spectra between HRP I and catalase I were interpreted (Dolphin et al, 1971) in terms of differences in the orbital ordering for the n-cation radicals that comprise electronic configurations of the compound I haem groups. Dolphin's (1971) assignment of the electronic structure of compound I of HRP and catalase involves oxidation of both the ring and the metal to a species that can be written as [Fe(IV)P(-1)]3+ (using current nomenclature) to describe the porphyrin charge, where P( -2) is the dianion and P ( -1) of a number of model compounds with those of the enzyme intermediates (Browett and Stillman, 1980, 198 lb;Browett et al, 1988 (Browett and Stillman, 1980 (Dolphin, 1971;Browett and Stillman, 1981a). While the m.c.d.…”

Section: Introductionmentioning

confidence: 99%

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Analysis of the optical absorption and magnetic-circular-dichroism spectra of peanut peroxidase: electronic structure of a peroxidase with biochemical properties similar to those of horseradish peroxidase

Marañón

Mercier

Huystee

et al. 1994

Biochemical Journal

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The electronic structures of the cationic isoenzyme of peanut peroxidase, horseradish peroxidase (isoenzyme C) and bovine liver catalase are compared through analysis of their optical absorption and magnetic c.d. (m.c.d.) spectral properties. The spectral data for the native resting states and compounds I and II of peanut peroxidase (PeP) are reported. The absorption and m.c.d. data for the native PeP exhibit bands characteristic of the high-spin ferric haem. The absorption spectrum of PeP compound I closely resembles that observed for the HRP compound I species. The m.c.d. data for PeP I clearly identifies that ring oxidation has occurred. One-electron reduction forms the PeP compound II species. The absorption and m.c.d. spectra recorded for PeP II exhibit the well-resolved spectral characteristics previously observed for both HRP compound II and catalase compound II. The spectral data of PeP with HRP and catalase are compared. The data clearly indicate that the m.c.d. spectral patterns of both plant peroxidases (PeP and HRP) are very similar and, therefore, the electronic structures of their resting states, and as well their primary and secondary compounds, must be similar. The m.c.d. data suggest that, while the compound I species of PeP and HRP belong to one electronic class, catalase compound I belongs to a different class. These data emphasize how the ground states of these two classes of oxidized haem, may be characterized as predominantly 2A2u (PeP I and HRP I) or 2A1u (catalase I). Peanut peroxidase is the second plant peroxidase for which the electronic structure of the compound I intermediate has been studied using the m.c.d. technique. The similarities with horseradish peroxidase allow us to suggest that plant peroxidases may operate by the same general mechanism, in spite of the low degree of sequence similarity between their polypeptide chains.

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Section: Discussionmentioning

confidence: 72%

Section: Introductionmentioning

confidence: 95%

Section: Introductionmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Analysis of the optical absorption and magnetic-circular-dichroism spectra of peanut peroxidase: electronic structure of a peroxidase with biochemical properties similar to those of horseradish peroxidase

Marañón

Mercier

Huystee

et al. 1994

Biochemical Journal

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Effect of Substitution on the ESR Spectra and Electronic Ground State of ZnTPP Cation Radicals

Dave

Srinivas

2000

Eur. J. Inorg. Chem.

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Synthesis, Optical Properties, Structures and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines and Related Compounds

Kobayashi

1999

J. Porphyrins Phthalocyanines

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The synthesis of and spectroscopic data on subazaporphyrins, subphthalocyanines, subnaphthalocyanines and their related compounds reported to date are summarized, together with the results of molecular orbital (MO) calculations from our laboratory. Thus the problems and key points in the synthesis of these subazamacrocycles and their electronic absorption and magnetic circular dichroism (MCD) spectra are discussed, together with those of the monosubstituted-type low-symmetrical phthalocyanines obtained by their ring expansion reaction. The Q bands of these subazamacrocycles are orbitally doubly degenerate, and in the Soret band region, three transitions to the orbitally degenerate state are found. The MO calculations suggest that the HOMO levels destabilize considerably while the LUMO levels change slightly with increasing size of the π system. In addition, the electronic adsorption data are reproduced by the calculation only when the two pyrrole hydrogens in the monosubstituted-type phthalocyanines are assumed to be linked to the two pyrrole nitrogens along the short axis.

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Temperature dependence and electronic transition energies in the magnetic circular dichroism spectrum of horeseradish peroxidase compound I

Cited by 44 publications

References 4 publications

Analysis of the optical absorption and magnetic-circular-dichroism spectra of peanut peroxidase: electronic structure of a peroxidase with biochemical properties similar to those of horseradish peroxidase

Analysis of the optical absorption and magnetic-circular-dichroism spectra of peanut peroxidase: electronic structure of a peroxidase with biochemical properties similar to those of horseradish peroxidase

Effect of Substitution on the ESR Spectra and Electronic Ground State of ZnTPP Cation Radicals

Synthesis, Optical Properties, Structures and Molecular Orbital Calculations of Subazaporphyrins, Subphthalocyanines, Subnaphthalocyanines and Related Compounds

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