(Dibenzoylmethanato)boron difluoride derivatives containing triphenylamine moieties were synthesized as a new type of electron-donor/π-acceptor system. These new compounds exhibited long-wavelength absorptions in the UV/Vis spectra, and reversible oxidation and reduction waves in cyclic voltammetry experiments. Their amphoteric redox properties are based on their resonance hybrid forms, in which a positive charge is delocalized on the triphenylamine moieties and a negative charge is localized on the boron atoms. Molecular orbital (MO) calculations indicate that their HOMO and LUMO energies vary with the number of phenylene rings connected to the difluoroboron-chelating ring. This is useful for optimizing the HOMO and LUMO levels to an iodine redox (I(-)/I3(-)) potential and a titanium dioxide conduction band, respectively. Dye-sensitized solar cells fabricated by using these compounds as dye sensitizers exhibited solar-to-electric power conversion efficiencies of 2.7-4.4 % under AM 1.5 solar light.

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The proton transfer reaction belongs to one of the key triggers for the functional expression of membrane proteins. Rod and cone opsins are light-sensitive G-protein-coupled receptors (GPCRs) that undergo the cis–trans isomerization of the retinal chromophore in response to light. The isomerization event initiates a conformational change in the opsin protein moiety, which propagates the downstream effector signaling. The final step of receptor activation is the deprotonation of the retinal Schiff base, a proton transfer reaction which has been believed to be identical among the cone opsins. Here, we report an unexpected proton transfer reaction occurring in the early photoreaction process of primate blue-sensitive pigment (MB). By using low-temperature UV–visible spectroscopy, we found that the Lumi intermediate of MB formed in transition from the BL intermediate shows an absorption maximum in the UV region, indicating the deprotonation of the retinal Schiff base. Comparison of the light-induced difference FTIR spectra of Batho, BL, and Lumi showed significant α-helical backbone C=O stretching and protonated carboxylate C=O stretching vibrations only in the Lumi intermediate. The transition from BL to Lumi thus involves dramatic changes in protein environment with a proton transfer reaction between the Schiff base and the counterion resulting in an absorption maximum in the UV region.

Energy transfer from light-harvesting ketocarotenoids to light-driven proton pumps xanthorhodopsins has been previously demonstrated in two unique cases: an extreme halophilic bacterium and a terrestrial cyanobacterium. Attempts to find carotenoids that bind and transfer energy to rhodopsin proton pumps from the abundant marine and freshwater photoheterotrophs have thus far failed. Here, using functional metagenomics combined with chromophore extraction from the environment, we detected light energy transfer from the widespread hydroxylated carotenoids zeaxanthin and lutein to the retinal moiety of xanthorhodopsins and proteorhodopsins. The light-harvesting carotenoids transfer up to 42% of the harvested energy in the violet/blue-light range to the green-light absorbing retinal chromophore. Our data suggest that these antennas have a significant impact on rhodopsin phototrophy in the worlds lakes, seas and oceans.