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Implications for the catalytic mechanism of the vanadium-containing enzyme chloroperoxidase from the fungus Curvularia inaequalis by X-ray structures of the native and peroxide form.

Implications for the catalytic mechanism of the vanadium-containing chloroperoxidase from the fungus Curvularia inaequalis have been obtained from the crystal structures of the native and peroxide forms of the enzyme. The X-ray structures have been solved by difference Fourier techniques using the atomic model of the azide chloroperoxidase complex. The 2.03 A crystal structure (R = 19.7%) of the native enzyme reveals the geometry of the intact catalytic vanadium center. The vanadium is coordinated by four non-protein oxygen atoms and one nitrogen (NE2) atom from histidine 496 in a trigonal bipyramidal fashion. Three oxygens are in the equatorial plane and the fourth oxygen and the nitrogen are at the apexes of the bipyramid. In the 2.24 A crystal structure (R = 17.7%) of the peroxide derivate the peroxide is bound to the vanadium in an eta2-fashion after the release of the apical oxygen ligand. The vanadium is coordinated also by 4 non-protein oxygen atoms and one nitrogen (NE2) from histidine 496. The coordination geometry around the vanadium is that of a distorted tetragonal pyramid with the two peroxide oxygens, one oxygen and the nitrogen in the basal plane and one oxygen in the apical position. A mechanism for the catalytic cycle has been proposed based on these X-ray structures and kinetic data.

Binding Sites↗

PubMedDate not supplied

Re-entrainment of circadian rhythms after phase-shifts of the Zeitgeber.

To describe anabrupt shift of the Zeitgeber sufficiently, it is necessary to indicate whether the phase has been advanced or delayed, for how many hours it has been shifted, and what part of the Zeitgeber has been lengthened or shortened respectively. The entrained circadian system usually follows a shift of the Zeitgeber in the same direction and by an equal amount. However, there can be exceptions to both of these rules: a) an instantaneous 12-h shift of a (symmertric) Zeitgeber always represents a delya (= doubling of one-half of its period). In contrast to this, the gradual re-entrainment of the circadian system can be accompalished by either advances or by delays (Fig. 2), it can occur in both dirctions simultaneously by splitting the rhythmic variable (Fig. 1),or it can represent an apparent advance not distinghushable from a delay ( Fig. 6); b) after complietion of re-entraiment, the phase-angle difference psi between organism and Zeitgeber an differ systematically from the pre-shift psi-value...

Activity Cycles↗