Photoproduction of proton gradients with pi-stacked fluorophore scaffolds in lipid bilayers.
Rigid p-octiphenyl rods were used to create helical tetrameric pi-stacks of blue, red-fluorescent naphthalene diimides that can span lipid bilayer membranes. In lipid vesicles containing quinone as electron acceptors and surrounded by ethylenediaminetetraacetic acid as hole acceptors, transmembrane proton gradients arose through quinone reduction upon excitation with visible light. Quantitative ultrafast and relatively long-lived charge separation was confirmed as the origin of photosynthetic activity by femtosecond fluorescence and transient absorption spectroscopy. Supramolecular self-organization was essential in that photoactivity was lost upon rod shortening (from p-octiphenyl to biphenyl) and chromophore expansion (from naphthalene diimide to perylene diimide). Ligand intercalation transformed the photoactive scaffolds into ion channels.
Bhosale
Sheshanath
S
Department of Organic Chemistry, University of Geneva, Geneva, Switzerland.
Sisson
Adam L
AL
Talukdar
Pinaki
P
Fürstenberg
Alexandre
A
Banerji
Natalie
N
Vauthey
Eric
E
Bollot
Guillaume
G
Mareda
Jiri
J
Röger
Cornelia
C
Würthner
Frank
F
Sakai
Naomi
N
Matile
Stefan
S
D001555:Benzene Derivatives / Q000737:chemistry; D016227:Benzoquinones / Q000737:chemistry*; D004492:Edetic Acid; D004583:Electrons; D007094:Imides; D008024:Ligands; D008027:Light; D008051:Lipid Bilayers; D015394:Molecular Structure; D009281:Naphthalenes; D010084:Oxidation-Reduction; D010618:Phenanthrolines / Q000737:chemistry*; D010777:Photochemistry; D011522:Protons; D013696:Temperature; D013816:Thermodynamics
D001555:Benzene Derivatives; D016227:Benzoquinones; D007094:Imides; D008024:Ligands; D008051:Lipid Bilayers; D009281:Naphthalenes; D010618:Phenanthrolines; D011522:Protons; C542131:naphthalenediimide; C004532:quinone; D004492:Edetic Acid