TY - JOUR
T1 - Templated Chromophore Assembly on Peptide Scaffolds
T2 - A Structural Evolution
AU - Rocard, Lou
AU - Wragg, Darren
AU - Jobbins, Samuel Alexander
AU - Luciani, Lorenzo
AU - Wouters, Johan
AU - Leoni, Stefano
AU - Bonifazi, Davide
N1 - Funding Information:
D.B. and L.R. gratefully acknowledge the EU through the ERC Starting Grant “COLORLANDS” and ITN-ETN “PHOTOTRAIN” projects, as well as Cardiff University for the financial support.
Funding Information:
The work has been performed using resources provided by the “Cambridge Service for Data Discovery” (CSD3, http://csd3. cam.ac.uk) system operated by the University of Cambridge Research Computing Service (http://www.hpc.cam.ac.uk) funded by EPSRC Tier-2 capital grant EP/P020259/1. We also thank A. De Leo for his contribution to the artwork.
Publisher Copyright:
© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
PY - 2018/10/26
Y1 - 2018/10/26
N2 - The use of a template that bears pre-programmed receptor sites for selectively accommodating chromophores at given positions is an attractive approach for engineering artificial-light-harvesting systems. Indulging this line of thought, this work tackles the creation of tailored antenna architectures with yellow, red and blue chromophores, exploiting three dynamic covalent reactions simultaneously, namely disulfide exchange, acyl hydrazone, and boronic ester formations. The effect of various structural modifications, such as the chromophores as well as their spatial organization (distance, orientation, order) on the energy transfer within the antennas was studied by means of steady-state UV/Vis absorption and fluorescence spectroscopies. This systematic study allowed for a significant improvement of the energy-transfer efficiencies to a noticeable 22 and 15 % for the yellow and red donors, respectively, across the chromophores to the blue acceptor. Metadynamics simulations suggested that the conformational properties of the antennas are driven by intramolecular chromophoric stacking interactions that, upon forcing the α-helix to fold on itself, annul any effects deriving from the programming of the spatial arrangement of the receptor sides in the peptide backbone.
AB - The use of a template that bears pre-programmed receptor sites for selectively accommodating chromophores at given positions is an attractive approach for engineering artificial-light-harvesting systems. Indulging this line of thought, this work tackles the creation of tailored antenna architectures with yellow, red and blue chromophores, exploiting three dynamic covalent reactions simultaneously, namely disulfide exchange, acyl hydrazone, and boronic ester formations. The effect of various structural modifications, such as the chromophores as well as their spatial organization (distance, orientation, order) on the energy transfer within the antennas was studied by means of steady-state UV/Vis absorption and fluorescence spectroscopies. This systematic study allowed for a significant improvement of the energy-transfer efficiencies to a noticeable 22 and 15 % for the yellow and red donors, respectively, across the chromophores to the blue acceptor. Metadynamics simulations suggested that the conformational properties of the antennas are driven by intramolecular chromophoric stacking interactions that, upon forcing the α-helix to fold on itself, annul any effects deriving from the programming of the spatial arrangement of the receptor sides in the peptide backbone.
KW - chromophores
KW - energy transfer
KW - metadynamics
KW - peptide
KW - self-assembly
U2 - 10.1002/chem.201803205
DO - 10.1002/chem.201803205
M3 - Article
C2 - 30133049
AN - SCOPUS:85054524995
SN - 0947-6539
VL - 24
SP - 16136
EP - 16148
JO - Chemistry - A European Journal
JF - Chemistry - A European Journal
IS - 60
M1 - 201803205
ER -