Design, Synthesis, and Dynamics of a Green Fluorescent Protein Fluorophore Mimic with an Ultrafast Switching Function.
While rotary molecular switches based on neutral and cationic organic π-systems have been reported, structurally homologous anionic switches providing complementary properties have not been prepared so far. Here we report the design and preparation of a molecular switch mimicking the anionic p-HBDI chromophore of the green fluorescent protein. The investigation of the mechanism and dynamics of the E/Z switching function is carried out both computationally and experimentally. The data consistently support axial rotary motion occurring on a sub-picosecond time scale. Transient spectroscopy and trajectory simulations show that the nonadiabatic decay process occurs in the vicinity of a conical intersection (CInt) between a charge transfer state and a covalent/diradical state. Comparison of our anionic p-HBDI-like switch with the previously reported cationic N-alkyl indanylidene pyrrolinium switch mimicking visual pigments reveals that these similar systems translocate, upon vertical excitation, a similar net charge in the same axial direction.
Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.
Marco
M
Paolino
Institut de Physique et Chimie des Matériaux de Strasbourg & Labex NIE, Université de Strasbourg, CNRS UMR 7504 , Strasbourg, France.
Moussa
M
Gueye
Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.
Elisa
E
Pieri
Chemistry Department, Bowling Green State University , Bowling Green, Ohio, United States.
Madushanka
M
Manathunga
Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.
Stefania
S
Fusi
Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.
Andrea
A
Cappelli
Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , Via Elce di Sotto, 8, 06123 Perugia, Italy.
Loredana
L
Latterini
Dipartimento di Chimica, Biologia e Biotecnologie, Università di Perugia , Via Elce di Sotto, 8, 06123 Perugia, Italy.
Danilo
D
Pannacci
Department of Chemistry, School of Natural Sciences, Ulsan National Institute of Science and Technology (UNIST) , Ulsan 689-798, Korea.
Michael
M
Filatov
Institut de Physique et Chimie des Matériaux de Strasbourg & Labex NIE, Université de Strasbourg, CNRS UMR 7504 , Strasbourg, France.
Jérémie
J
Léonard
Dipartimento di Biotecnologie, Chimica e Farmacia, Università di Siena , Via A. Moro 2, 53100 Siena, Italy.|Chemistry Department, Bowling Green State University , Bowling Green, Ohio, United States.|University of Strasbourg Institute for Advanced Studies , 5, allée du Général Rouvillois F-67083 Strasbourg, France.
Massimo
M
Olivucci
D000838:Anions; D002412:Cations; D000431:Ethanol / Q000737:chemistry; D049452:Green Fluorescent Proteins / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D000432:Methanol / Q000737:chemistry; D009038:Motion; D010777:Photochemistry; D010858:Pigmentation; D012984:Software; D012997:Solvents / Q000737:chemistry; D013050:Spectrometry, Fluorescence; D013053:Spectrophotometry
D000838:Anions; D002412:Cations; D012997:Solvents; D049452:Green Fluorescent Proteins; D000431:Ethanol; D000432:Methanol