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The predischarge chromophore in bacteriorhodopsin: A 15N solid-state NMR study of the L photointermediate

The predischarge chromophore in bacteriorhodopsin: A 15N solid-state NMR study of the L photointermediate

Biochemistry 36(31): 9316-9322

ISSN/ISBN: 0006-2960

PMID: 9235973

DOI: 10.1021/bi970416y

The L-550 intermediate in the bacteriorhodopsin (bR) photocycle has drawn much attention with respect to the mechanism of light-driven proton transport because it selectively releases the Schiff base (SB) proton to the extracellular proton channel in the L fwdarw M transition. Here we extend our solid-state NMR studies of bR photocycle intermediates to the L state. Under conditions that stabilize L-550, a new SB signal is detected in the 15N NMR spectrum which disappears upon thermal relaxation. This signal is in the range for a protonated SB, but downfield from the SB signals of bR-568 and N-520. Since steric interactions would have the opposite effect on shielding, the data argue against a 13,14-dicis chromophore in L-550. Comparison with the 15N chemical shifts of halide salts of protonated Schiff bases (pSB's) of retinal suggests that the interaction of the SB with its counterion is significantly stronger in L-550 than in N-520 (which in turn is stronger than in bR-568). This is consistent with models of the early photocycle in which the electrostatic interaction between the SB and its counterion constitutes an important constraint. Although the L counterion interaction is comparable to that of a 6-s-trans,13-cis chloride salt, the visible spectrum is strongly red-shifted from the lambda-max = 491 nm of the chloride. This suggests some double bond strain in L-550, particularly about the C dbd N bond. This strain is apparently gone in the N intermediate, which has a normal relationship between the 15N chemical shift and lambda-max. Such a relaxed chromophore is consistent with orientation of the SB proton toward the cytoplasmic surface in the N intermediate.

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