PMID- 32374610
OWN - NLM
STAT- MEDLINE
DCOM- 20201023
LR  - 20220716
IS  - 1948-7185 (Electronic)
IS  - 1948-7185 (Linking)
VI  - 11
IP  - 11
DP  - 2020 Jun 4
TI  - Computational and Spectroscopic Characterization of the Photocycle of an 
      Artificial Rhodopsin.
PG  - 4245-4252
LID - 10.1021/acs.jpclett.0c00751 [doi]
AB  - The photocycle of a reversible photoisomerizing rhodopsin mimic (M2) is 
      investigated. This system, based on the cellular retinoic acid binding protein, 
      is structurally different from natural rhodopsin systems, but exhibits a similar 
      isomerization upon light irradiation. More specifically, M2 displays a 15-cis to 
      all-trans conversion of retinal protonated Schiff base (rPSB) and all-trans to 
      15-cis isomerization of unprotonated Schiff base (rUSB). Here we use hybrid 
      quantum mechanics/molecular mechanics (QM/MM) tools coupled with transient 
      absorption and cryokinetic UV-vis spectroscopies to investigate these 
      isomerization processes. The results suggest that primary rPSB photoisomerization 
      of M2 occurs around the C13 horizontal lineC14 double bond within 2 ps following an 
      aborted-bicycle pedal (ABP) isomerization mechanism similar to natural microbial 
      rhodopsins. The rUSB isomerization is much slower and occurs within 48 ps around 
      the C15 horizontal lineN double bond. Our findings reveal the possibility to engineer naturally 
      occurring mechanistic features into artificial rhodopsins and also constitute a 
      step toward understanding the photoisomerization of UV pigments. We conclude by 
      reinforcing the idea that the presence of the retinal chromophore inside a tight 
      protein cavity is not mandatory to exhibit ABP mechanism.
FAU - Manathunga, Madushanka
AU  - Manathunga M
AUID- ORCID: 0000-0002-3594-8112
AD  - Department of Chemistry, Bowling Green State University, Bowling Green, Ohio 
      43403, United States.
FAU - Jenkins, Adam J
AU  - Jenkins AJ
AD  - Department of Chemistry, University of California, Davis, One Shields Avenue, 
      Davis, California 95616, United States.
FAU - Orozco-Gonzalez, Yoelvis
AU  - Orozco-Gonzalez Y
AUID- ORCID: 0000-0001-7225-2424
AD  - Department of Chemistry, Bowling Green State University, Bowling Green, Ohio 
      43403, United States.
FAU - Ghanbarpour, Alireza
AU  - Ghanbarpour A
AUID- ORCID: 0000-0002-7485-029X
AD  - Department of Chemistry, Michigan State University, Lansing, Michigan 48824, 
      United States.
FAU - Borhan, Babak
AU  - Borhan B
AUID- ORCID: 0000-0002-3193-0732
AD  - Department of Chemistry, Michigan State University, Lansing, Michigan 48824, 
      United States.
FAU - Geiger, James H
AU  - Geiger JH
AD  - Department of Chemistry, Michigan State University, Lansing, Michigan 48824, 
      United States.
FAU - Larsen, Delmar S
AU  - Larsen DS
AUID- ORCID: 0000-0003-4522-2689
AD  - Department of Chemistry, University of California, Davis, One Shields Avenue, 
      Davis, California 95616, United States.
FAU - Olivucci, Massimo
AU  - Olivucci M
AUID- ORCID: 0000-0002-8247-209X
AD  - Department of Chemistry, Bowling Green State University, Bowling Green, Ohio 
      43403, United States.
AD  - Dipartimento di Biotecnologie, Chimica e Farmacia, Universita di Siena, via A. 
      Moro 2, I-53100 Siena, Italy.
AD  - Institut de Physique et Chimie des Materiaux de Strasbourg, UMR 7504 Universite 
      de Strasbourg-CNRS, F-67034 Strasbourg, France.
LA  - eng
GR  - R15 GM126627/GM/NIGMS NIH HHS/United States
PT  - Journal Article
DEP - 20200513
PL  - United States
TA  - J Phys Chem Lett
JT  - The journal of physical chemistry letters
JID - 101526034
RN  - 0 (Receptors, Retinoic Acid)
RN  - 0 (Schiff Bases)
RN  - 9009-81-8 (Rhodopsin)
SB  - IM
MH  - Isomerism
MH  - Light
MH  - Quantum Theory
MH  - Receptors, Retinoic Acid
MH  - Rhodopsin/*chemistry/*radiation effects
MH  - Schiff Bases/chemistry
MH  - Spectrum Analysis/methods
PMC - PMC9272672
MID - NIHMS1810314
COIS- The authors declare no competing financial interest.
EDAT- 2020/05/07 06:00
MHDA- 2020/10/24 06:00
PMCR- 2022/07/11
CRDT- 2020/05/07 06:00
PHST- 2020/05/07 06:00 [pubmed]
PHST- 2020/10/24 06:00 [medline]
PHST- 2020/05/07 06:00 [entrez]
PHST- 2022/07/11 00:00 [pmc-release]
AID - 10.1021/acs.jpclett.0c00751 [doi]
PST - ppublish
SO  - J Phys Chem Lett. 2020 Jun 4;11(11):4245-4252. doi: 10.1021/acs.jpclett.0c00751. 
      Epub 2020 May 13.