Abstract
The correlation functions of the fluctuations of vibrational frequencies of azide ions and carbon monoxide in proteins are determined directly from stimulated photon echoes generated with femtosecond infrared pulses. The asymmetric stretching vibration of azide bound to carbonic anhydrase II exhibits a pronounced evolution of its vibrational frequency distribution on the time scale of a few picoseconds, which is attributed to modifications of the ligand structure through interactions with the nearby Thr-199. When azide is bound in hemoglobin, a more complex evolution of the protein structure is required to interchange the different ligand configurations, as evidenced by the much slower relaxation of the frequency distribution in this case. The time evolution of the distribution of frequencies of carbon monoxide bound in hemoglobin occurs on the ≈10-ps time scale and is very nonexponential. The correlation functions of the frequency fluctuations determine the evolution of the protein structure local to the probe and the extent to which the probe can navigate those parts of the energy landscape where the structural configurations are able to modify the local potential energy function of the probe.
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Dates
Type | When |
---|---|
Created | 23 years, 1 month ago (July 26, 2002, 10:35 a.m.) |
Deposited | 3 years, 4 months ago (April 13, 2022, 4:12 p.m.) |
Indexed | 1 week, 6 days ago (Aug. 21, 2025, 1:26 p.m.) |
Issued | 26 years, 8 months ago (Dec. 22, 1998) |
Published | 26 years, 8 months ago (Dec. 22, 1998) |
Published Online | 26 years, 8 months ago (Dec. 22, 1998) |
Published Print | 26 years, 8 months ago (Dec. 22, 1998) |
@article{Lim_1998, title={Protein fluctuations are sensed by stimulated infrared echoes of the vibrations of carbon monoxide and azide probes}, volume={95}, ISSN={1091-6490}, url={http://dx.doi.org/10.1073/pnas.95.26.15315}, DOI={10.1073/pnas.95.26.15315}, number={26}, journal={Proceedings of the National Academy of Sciences}, publisher={Proceedings of the National Academy of Sciences}, author={Lim, Manho and Hamm, Peter and Hochstrasser, Robin M.}, year={1998}, month=dec, pages={15315–15320} }