A fast photoswitch for minimally perturbed peptides: investigation of the trans-->cis photoisomerization of N-methylthioacetamide

Journal of the American Chemical Society
Jan HelbingMassimo Olivucci

Abstract

Thio amino acids can be integrated into the backbone of peptides without significantly perturbing their structure. In this contribution we use ultrafast infrared and visible spectroscopy as well as state-of-the-art ab initio computations to investigate the photoisomerization of the trans form of N-methylthioacetamide (NMTAA) as a model conformational photoswitch. Following the S2 excitation of trans-NMTAA in water, the return of the molecule into the trans ground state and the formation of the cis isomer is observed on a dual time scale, with a fast component of 8-9 ps and a slow time constant of approximately 250 ps. On both time scales the probability of isomerization to the cis form is found to be 30-40%, independently of excitation wavelength. Ab initio CASPT2//CASSCF photochemical reaction path calculations indicate that, in vacuo, the trans-->cis isomerization event takes place on the S1 and/or T1 triplet potential energy surfaces and is controlled by very small energy barriers, in agreement with the experimentally observed picosecond time scale. Furthermore, the calculations identify one S2/S1 and four nearly isoenergetic S1/S0 conical intersection decay channels. In line with the observed isomerization probability, only...Continue Reading

References

Jun 1, 1967·The Journal of Physical Chemistry·E B Nielsen, J A Schellman
Apr 13, 2000·Proceedings of the National Academy of Sciences of the United States of America·J R KumitaG A Woolley
Aug 16, 2000·Proceedings of the National Academy of Sciences of the United States of America·R González-LuqueM Olivucci
Apr 11, 2002·Journal of the American Chemical Society·Luca De VicoMassimo Olivucci
Dec 20, 2002·Organic Letters·Julia H MiwaKatherine E Lee
Dec 4, 2003·Chemical Communications : Chem Comm·Jianzhang ZhaoCordelia Schiene-Fischer
Dec 11, 2007·Optics Letters·P HammJ Stenger

❮ Previous
Next ❯

Citations

Oct 5, 2010·Journal of the American Chemical Society·Jacob M GoldbergE James Petersson
Nov 14, 2008·Proceedings of the National Academy of Sciences of the United States of America·Adalgisa SinicropiMassimo Olivucci
Nov 9, 2007·Annual Review of Physical Chemistry·Peter HammJens Bredenbeck
Oct 5, 2013·The Journal of Chemical Physics·Martin Gruebele, D Thirumalai
Jun 5, 2008·Journal of Peptide Science : an Official Publication of the European Peptide Society·Yun HuangShouliang Dong
Oct 21, 2016·Journal of Peptide Science : an Official Publication of the European Peptide Society·Somnath Mukherjee, Jayanta Chatterjee
Aug 21, 2015·Organic & Biomolecular Chemistry·Shah Md Abdur RaufBahareh Honarparvar
Aug 20, 2016·Chemical Communications : Chem Comm·Robert J Mart, Rudolf K Allemann
Jul 5, 2011·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Frank ScholzJosef Wachtveitl
Apr 28, 2006·Chembiochem : a European Journal of Chemical Biology·Christian Renner, Luis Moroder
Oct 4, 2012·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Rachel Crespo-OteroWolfram Sander
Sep 30, 2006·Angewandte Chemie·Ulrike KusebauchChristian Renner
Jul 7, 2007·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Jens BredenbeckPeter Hamm
Aug 19, 2007·Chemistry : a European Journal·Valentina CervettoJan Helbing
Jan 13, 2009·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Lars DworakJosef Wachtveitl
Jul 14, 2011·Chembiochem : a European Journal of Chemical Biology·Amit Choudhary, Ronald T Raines
Dec 18, 2013·Organic & Biomolecular Chemistry·Matteo De Poli, Jonathan Clayden
Sep 12, 2012·Journal of Physics. Condensed Matter : an Institute of Physics Journal·Lars DworakJosef Wachtveitl
Oct 30, 2004·Chemistry : a European Journal·Jianzhang ZhaoCordelia Schiene-Fischer
Jul 16, 2014·Physical Chemistry Chemical Physics : PCCP·Mauro TorselloAntonino Polimeno
May 9, 2012·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Shengxue YangJian Gong
Jun 24, 2008·The Journal of Physical Chemistry. B·Valentina CervettoJan Helbing
Jun 3, 2008·Journal of the American Chemical Society·Andreas ReinerThomas Kiefhaber
May 21, 2010·Journal of the American Chemical Society·Yun HuangGunter Fischer
Sep 4, 2007·The Journal of Physical Chemistry. B·Christoph KolanoPeter Hamm
Jul 8, 2021·The Journal of Physical Chemistry. B·Jasmin SpekowiusJan Helbing
Mar 12, 2013·Journal of Chemical Theory and Computation·Sergi Ruiz-BarraganLluís Blancafort
Mar 29, 2019·Journal of the American Chemical Society·Chidambar KulkarniE W Meijer
Jan 31, 2019·ACS Chemical Biology·Nilkamal MahantaDouglas A Mitchell
May 7, 2019·The Journal of Physical Chemistry Letters·Malte OppermannJan Helbing
Apr 3, 2007·Journal of the American Chemical Society·Dirk WildemannGunter Fischer
Sep 1, 2005·Journal of Chemical Theory and Computation·Luca De VicoRoland Lindh
Jul 21, 2006·The Journal of Physical Chemistry. B·H SatzgerG Fischer
Feb 26, 2008·The Journal of Physical Chemistry. B·Valentina CervettoJan Helbing
Apr 21, 2006·The Journal of Physical Chemistry. B·V V MatylitskyJ Wachtveitl

❮ Previous
Next ❯

Related Concepts

Related Feeds

Autoimmune Diseases

Autoimmune diseases occur as a result of an attack by the immune system on the body’s own tissues resulting in damage and dysfunction. There are different types of autoimmune diseases, in which there is a complex and unknown interaction between genetics and the environment. Discover the latest research on autoimmune diseases here.

Related Papers

Proceedings of the National Academy of Sciences of the United States of America
S SpörleinJ Wachtveitl
Proceedings of the National Academy of Sciences of the United States of America
Jens BredenbeckPeter Hamm
Proceedings of the National Academy of Sciences of the United States of America
J R KumitaG A Woolley
© 2022 Meta ULC. All rights reserved