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Spectroscopy and Photochemistry; General Theory
Point Mutation of Anabaena Sensory Rhodopsin Enhances Ground State Hydrogen-out-of-plane-wag Raman Activity Partha Pratim Roy, Rei Abe-Yoshizumi, Hideki Kandori, and Tiago Buckup J. Phys. Chem. Lett., Just Accepted Manuscript • DOI: 10.1021/acs.jpclett.8b03805 • Publication Date (Web): 11 Feb 2019 Downloaded from http://pubs.acs.org on February 12, 2019
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The Journal of Physical Chemistry Letters
Point Mutation of Anabaena Sensory Rhodopsin Enhances Ground State Hydrogen-out-of-plane-wag Raman Activity Partha Pratim Roy, Rei Abe-Yoshizumi, Hideki Kandori, Tiago Buckup* Physikalisch-Chemisches Institut, Ruprecht-Karls Universität Heidelberg, D-69120, Heidelberg, Germany. Department of Life Science and Applied Chemistry, Nagoya Institute of Technology, Showa-ku, Nagoya 466-8555, Japan. OptoBioTechnology Research Center, Nagoya Institute of Technology, Showa-ku, Nagoya 4668555, Japan. AUTHOR INFORMATION Corresponding Author *
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ABSTRACT. The interaction between the retinal protonated Schiff base (RPSB) and surrounding protein residues inside the retinal pocket is believed to play a major role in the ultrafast isomerization of the former. Coherent time-resolved vibrational spectroscopic techniques are applied to unveil the effect of changes in the protein architecture by point mutations (V112N and L83Q) close to the RPSB in Anabaena Sensory Rhodopsin (ASR). Our study reveals that such point mutations have a minor effect on the low frequency (V112N (230 fs) > L83Q (120 fs), whereas it affects much less the 13C-isomer: V112N (290 fs) > L83Q (200 fs) > WT (170 fs).
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Figure 2. The transients obtained by TA measurements of (a) AT and (b) 13C-isomers of RPSB in WT (black), V112N (red) and L83Q (blue) mutants of ASR detected at 620, 600 and 585 nm, respectively. Each transient was normalized to the maximum signal beyond 100 fs. The oscillatory residuals obtained after subtraction of population kinetics by a bi-exponential fit (see Fig. S3 in SI) of the transients are shown in the inset. (c-h) The respective spectra obtained by a fast Fourier transformation of the residuals.
On top of the exponential decay of the non-oscillatory (population) signal in the TA signal (Figure 2), an oscillatory feature (see residual in the inset of Figure 2(a) and (b)) can be observed for each ASR sample. The residuals, obtained after a bi-exponential fit (Fig. S3), exhibit damped periodic modulations (~2 mOD), which are well beyond the noise level (
