PMID- 30872581
OWN - NLM
STAT- MEDLINE
DCOM- 20190405
LR  - 20210109
IS  - 2041-1723 (Electronic)
IS  - 2041-1723 (Linking)
VI  - 10
IP  - 1
DP  - 2019 Mar 14
TI  - Intrinsic photoisomerization dynamics of protonated Schiff-base retinal.
PG  - 1210
LID - 10.1038/s41467-019-09225-7 [doi]
LID - 1210
AB  - The retinal protonated Schiff-base (RPSB) in its all-trans form is found in 
      bacterial rhodopsins, whereas visual rhodopsin proteins host 11-cis RPSB. In both 
      cases, photoexcitation initiates fast isomerization of the retinal chromophore, 
      leading to proton transport, storage of chemical energy or signaling. It is an 
      unsolved problem, to which degree this is due to protein interactions or 
      intrinsic RPSB quantum properties. Here, we report on time-resolved 
      action-spectroscopy studies, which show, that upon photoexcitation, cis isomers 
      of RPSB have an almost barrierless fast 400 fs decay, whereas all-trans isomers 
      exhibit a barrier-controlled slow 3 ps decay. Moreover, formation of the 11-cis 
      isomer is greatly favored for all-trans RPSB when isolated. The very fast 
      photoresponse of visual photoreceptors is thus directly related to intrinsic 
      retinal properties, whereas bacterial rhodopsins tune the excited state 
      potential-energy surface to lower the barrier for particular double-bond 
      isomerization, thus changing both the timescale and specificity of the 
      photoisomerization.
FAU - Kiefer, Hjalte V
AU  - Kiefer HV
AUID- ORCID: 0000-0002-7540-3627
AD  - Department of Physics and Astronomy, Aarhus University, 8000, Aarhus C, Denmark.
FAU - Gruber, Elisabeth
AU  - Gruber E
AUID- ORCID: 0000-0002-1195-3638
AD  - Department of Physics and Astronomy, Aarhus University, 8000, Aarhus C, Denmark.
FAU - Langeland, Jeppe
AU  - Langeland J
AD  - Department of Physics and Astronomy, Aarhus University, 8000, Aarhus C, Denmark.
FAU - Kusochek, Pavel A
AU  - Kusochek PA
AD  - Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, Russia.
FAU - Bochenkova, Anastasia V
AU  - Bochenkova AV
AUID- ORCID: 0000-0003-4101-3564
AD  - Chemistry Department, Lomonosov Moscow State University, 119991, Moscow, Russia.
FAU - Andersen, Lars H
AU  - Andersen LH
AUID- ORCID: 0000-0002-0996-3968
AD  - Department of Physics and Astronomy, Aarhus University, 8000, Aarhus C, Denmark. 
      lha@phys.au.dk.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20190314
PL  - England
TA  - Nat Commun
JT  - Nature communications
JID - 101528555
RN  - 0 (Protons)
RN  - 0 (Schiff Bases)
RN  - 53026-44-1 (Bacteriorhodopsins)
RN  - 9009-81-8 (Rhodopsin)
RN  - RR725D715M (Retinaldehyde)
SB  - IM
MH  - Bacteriorhodopsins/chemistry/*radiation effects
MH  - Computer Simulation
MH  - Isomerism
MH  - Light
MH  - *Models, Biological
MH  - *Protons
MH  - Retinaldehyde/*chemistry/radiation effects
MH  - Rhodopsin/chemistry/*radiation effects
MH  - Schiff Bases/chemistry
PMC - PMC6418104
COIS- The authors declare no competing interests.
EDAT- 2019/03/16 06:00
MHDA- 2019/04/06 06:00
PMCR- 2019/03/14
CRDT- 2019/03/16 06:00
PHST- 2018/08/31 00:00 [received]
PHST- 2019/02/27 00:00 [accepted]
PHST- 2019/03/16 06:00 [entrez]
PHST- 2019/03/16 06:00 [pubmed]
PHST- 2019/04/06 06:00 [medline]
PHST- 2019/03/14 00:00 [pmc-release]
AID - 10.1038/s41467-019-09225-7 [pii]
AID - 9225 [pii]
AID - 10.1038/s41467-019-09225-7 [doi]
PST - epublish
SO  - Nat Commun. 2019 Mar 14;10(1):1210. doi: 10.1038/s41467-019-09225-7.