PMID- 26376448
OWN - NLM
STAT- MEDLINE
DCOM- 20160420
LR  - 20151007
IS  - 1520-5126 (Electronic)
IS  - 0002-7863 (Linking)
VI  - 137
IP  - 39
DP  - 2015 Oct 7
TI  - Barrierless Photoisomerization of 11-cis Retinal Protonated Schiff Base in 
      Solution.
PG  - 12434-7
LID - 10.1021/jacs.5b06492 [doi]
AB  - A hallmark of the primary visual event is the barrierless, ultrafast, and 
      efficient 11-cis to all-trans photoisomerization of the retinal protonated Schiff 
      base (RPSB) chromophore. The remarkable reactivity of RPSB in the visual pigment 
      rhodopsin has been attributed to potential energy surface modifications enabled 
      by evolution-optimized chromophore-protein interactions. Here, we use a combined 
      synthetic and ultrafast spectroscopic approach to show that barrierless 
      photoisomerization is an intrinsic property of 11-cis RPSB, suggesting that the 
      protein may merely adjust the ratio between fast reactive and slow unreactive 
      decay channels. These results call for a re-evaluation of our understanding and 
      theoretical description of RPSB photochemistry.
FAU - Bassolino, Giovanni
AU  - Bassolino G
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
FAU - Sovdat, Tina
AU  - Sovdat T
AD  - Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 
      Mansfield Road, Oxford OX1 3TA, U.K.
FAU - Soares Duarte, Alex
AU  - Soares Duarte A
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
FAU - Lim, Jong Min
AU  - Lim JM
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
FAU - Schnedermann, Christoph
AU  - Schnedermann C
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
FAU - Liebel, Matz
AU  - Liebel M
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
FAU - Odell, Barbara
AU  - Odell B
AD  - Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 
      Mansfield Road, Oxford OX1 3TA, U.K.
FAU - Claridge, Timothy D W
AU  - Claridge TD
AD  - Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 
      Mansfield Road, Oxford OX1 3TA, U.K.
FAU - Fletcher, Stephen P
AU  - Fletcher SP
AD  - Department of Chemistry, Chemistry Research Laboratory, University of Oxford , 
      Mansfield Road, Oxford OX1 3TA, U.K.
FAU - Kukura, Philipp
AU  - Kukura P
AD  - Department of Chemistry, Physical and Theoretical Chemistry Laboratory, 
      University of Oxford , South Parks Road, Oxford OX1 3QZ, U.K.
LA  - eng
PT  - Journal Article
PT  - Research Support, Non-U.S. Gov't
DEP - 20150924
PL  - United States
TA  - J Am Chem Soc
JT  - Journal of the American Chemical Society
JID - 7503056
RN  - 0 (Schiff Bases)
RN  - 0 (Solutions)
RN  - RR725D715M (Retinaldehyde)
SB  - IM
MH  - Isomerism
MH  - Molecular Structure
MH  - *Photochemistry
MH  - Retinaldehyde/*chemistry/*metabolism
MH  - Schiff Bases/*chemistry
MH  - Solutions
EDAT- 2015/09/17 06:00
MHDA- 2016/04/21 06:00
CRDT- 2015/09/17 06:00
PHST- 2015/09/17 06:00 [entrez]
PHST- 2015/09/17 06:00 [pubmed]
PHST- 2016/04/21 06:00 [medline]
AID - 10.1021/jacs.5b06492 [doi]
PST - ppublish
SO  - J Am Chem Soc. 2015 Oct 7;137(39):12434-7. doi: 10.1021/jacs.5b06492. Epub 2015 
      Sep 24.