PMID- 23140223 OWN - NLM STAT- MEDLINE DCOM- 20131204 LR - 20130426 IS - 1520-5207 (Electronic) IS - 1520-5207 (Linking) VI - 117 IP - 16 DP - 2013 Apr 25 TI - Probing ultrafast photochemistry of retinal proteins in the near-IR: bacteriorhodopsin and anabaena sensory rhodopsin vs retinal protonated Schiff base in solution. PG - 4670-9 LID - 10.1021/jp309189y [doi] AB - Photochemistry of bacteriorhodopsin (bR), anabaena sensory rhodopsin (ASR), and all-trans retinal protonated Schiff base (RPSB) in ethanol is followed with femtosecond pump-hyperspectral near-IR (NIR) probe spectroscopy. This is the first systematic probing of retinal protein photochemistry in this spectral range. Stimulated emission of the proteins is demonstrated to extend deep into the NIR, and to decay on the same characteristic time scales previously determined by visible probing. No signs of a transient NIR absorption band above lambdapr > 1.3 mum, which was recently reported and is verified here for the RPSB in solution, is observed in either protein. This discrepancy demonstrates that the protein surroundings change photochemical traits of the chromophore significantly, inducing changes either in the energies or couplings of photochemically relevant electronic excited states. In addition, low-frequency and heavily damped spectral modulations are observed in the NIR signals of all three systems up to 1.4 mum. By background subtraction and Fourier analysis they are shown to resemble wave packet signatures in the visible, stemming from multiple vibrational modes and by analogy are assigned to torsional wave packets in the excited state of the retinal chromophore. Differences in the vibrational frequencies between the three samples and the said discrepancy in transient spectra are discussed in terms of opsin effects on the RPSB electronic structure. FAU - Wand, Amir AU - Wand A AD - Institute of Chemistry and the Farkas Center for Light-Induced Processes, The Hebrew University of Jerusalem, Edmond J. Safra Campus, Givat Ram, Jerusalem 91904, Israel. FAU - Loevsky, Boris AU - Loevsky B FAU - Friedman, Noga AU - Friedman N FAU - Sheves, Mordechai AU - Sheves M FAU - Ruhman, Sanford AU - Ruhman S LA - eng PT - Journal Article PT - Research Support, Non-U.S. Gov't PT - Research Support, U.S. Gov't, Non-P.H.S. DEP - 20121126 PL - United States TA - J Phys Chem B JT - The journal of physical chemistry. B JID - 101157530 RN - 0 (Eye Proteins) RN - 0 (Protons) RN - 0 (Schiff Bases) RN - 0 (Sensory Rhodopsins) RN - 0 (Solutions) RN - 53026-44-1 (Bacteriorhodopsins) SB - IM MH - Anabaena/*metabolism MH - Bacteriorhodopsins/*chemistry/metabolism MH - Eye Proteins/*chemistry/metabolism MH - Fourier Analysis MH - Isomerism MH - Protons MH - Schiff Bases/*chemistry MH - Sensory Rhodopsins/*chemistry/metabolism MH - Solutions/chemistry MH - Spectroscopy, Near-Infrared EDAT- 2012/11/13 06:00 MHDA- 2013/12/16 06:00 CRDT- 2012/11/13 06:00 PHST- 2012/11/13 06:00 [entrez] PHST- 2012/11/13 06:00 [pubmed] PHST- 2013/12/16 06:00 [medline] AID - 10.1021/jp309189y [doi] PST - ppublish SO - J Phys Chem B. 2013 Apr 25;117(16):4670-9. doi: 10.1021/jp309189y. Epub 2012 Nov 26.