Unraveling the Intrinsic Color of Chlorophyll†
Corresponding Author
Dr. Bruce F. Milne
Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Centre for Computational Physics, Department of Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)
Bruce F. Milne, Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Steen Brøndsted Nielsen, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Search for more papers by this authorDr. Yoni Toker
Institute of Nanotechnology and Advanced Materials, Bar-Ilan University, Ramat-Gan 5290002 (Israel)
Search for more papers by this authorProf. Angel Rubio
Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg 22761 (Germany)
Search for more papers by this authorCorresponding Author
Prof. Steen Brøndsted Nielsen
Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Bruce F. Milne, Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Steen Brøndsted Nielsen, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Search for more papers by this authorCorresponding Author
Dr. Bruce F. Milne
Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Centre for Computational Physics, Department of Physics, University of Coimbra, Rua Larga, 3004-516 Coimbra (Portugal)
Bruce F. Milne, Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Steen Brøndsted Nielsen, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Search for more papers by this authorDr. Yoni Toker
Institute of Nanotechnology and Advanced Materials, Bar-Ilan University, Ramat-Gan 5290002 (Israel)
Search for more papers by this authorProf. Angel Rubio
Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Max Planck Institute for the Structure and Dynamics of Matter, Hamburg 22761 (Germany)
Search for more papers by this authorCorresponding Author
Prof. Steen Brøndsted Nielsen
Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Bruce F. Milne, Nano-Bio Spectroscopy group and ETSF Scientific Development Centre, Department of Materials Physics, University of the Basque Country, CFM CSIC-UPV/EHU-MPC and DIPC, Avenida de Tolosa 72, E-20018 Donostia (Spain)
Steen Brøndsted Nielsen, Department of Physics and Astronomy, Aarhus University, Ny Munkegade, DK-8000 Aarhus C (Denmark)
Search for more papers by this authorB.F.M. thanks DIPC and CFM (UPV/EHU) and the Laboratory for Advanced Computation (University of Coimbra) for support. S.B.N. acknowledges support from Lundbeckfonden. A.R. acknowledges support from ERC Advanced Grant DYNamo (ERC-2010-AdG-267374), Spanish Grant (FIS2013-46159-C3-1-P), Grupos Consolidados UPV/EHU del Gobierno Vasco (IT578-13), and EC FP7 CRONOS (Grant 280879-2).
Abstract
The exact color of light absorbed by chlorophyll (Chl) pigments, the light-harvesters in photosynthesis, is tuned by the protein microenvironment, but without knowledge of the intrinsic color of Chl it remains unclear how large this effect is. Experimental first absorption energies of Chl a and b isolated in vacuo and tagged with quaternary ammonium cations are reported. The energies are largely insensitive to details of the tag structure, a finding supported by first-principles calculations using time-dependent density functional theory. Absorption is significantly blue-shifted compared to that of Chl-containing proteins (by 30–70 nm). A single red-shifting perturbation, such as axial ligation or the protein medium, is insufficient to account even for the smallest shift; the largest requires pigment–pigment interactions.
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