Switching sides—Reengineered primary charge separation in the bacterial photosynthetic reaction center

We report 90% yield of electron transfer (ET) from the singlet excited state P* of the primary electron-donor P (a bacteriochlorophyll dimer) to the B-side bacteriopheophytin (HB) in the bacterial photosynthetic reaction center (RC). Starting from a platform Rhodobacter sphaeroides RC bearing several amino acid changes, an Arg in place of the native Leu at L185—positioned over one face of HB and only ∼4 Å from the 4 central nitrogens of the HB macrocycle—is the key additional mutation providing 90% yield of P+HB−. This all but matches the near-unity yield of A-side P+HA− charge separation in the native RC. The 90% yield of ET to HB derives from (minimally) 3 P* populations with distinct means of P* decay. In an ∼40% population, P* decays in ∼4 ps via a 2-step process involving a short-lived P+BB− intermediate, analogous to initial charge separation on the A side of wild-type RCs. In an ∼50% population, P* → P+HB− conversion takes place in ∼20 ps by a superexchange mechanism mediated by BB. An ∼10% population of P* decays in ∼150 ps largely by internal conversion. These results address the long-standing dichotomy of A- versus B-side initial charge separation in native RCs and have implications for the mechanism(s) and timescale of initial ET that are required to achieve a near-quantitative yield of unidirectional charge separation.

Synthesis of two cyanine dyes as potential artificial antennas for the bacterial photosynthetic Reaction Center

ABSTRACT:Particular attention has been recently devoted to the development of biohybrid photoconverters based on the bacterial Reaction Center (RC) of Rhodobacter sphaeroides. This highly efficient photoenzyme has a conversion yield close to unit that makes it extremely appealing in the field of artificial photosynthesis. Isolated RCs suffer of a limited absorption cross-section in the visible spectral region that limits their applicative employment. Here we report the synthesis of two heptamethine cyanine molecules, whose photophysical properties make them potentially suitable as light harvesting antennas for the RC.

A heptamethine cyanine dye suitable as antenna in biohybrids based on bacterial photosynthetic reaction center

ABSTRACT:Sunlight is the most environmental friendly energy source available on Earth; many efforts devoted to design artificial photoconversion systems are ongoing, nevertheless they are still expensive and poorly efficient. Photoconversion devices made with organic-biological hybrids, or biohybrids, based on the photosynthetic reaction center (RC) have been introduced. In these systems, the photoenzyme is garnished with artificial antennas to enhance the photoactivity of the RC. Here we present a newly synthesized heptamethine cyanine dye that fulfills requisites to act as efficient RC light harvesting antenna.

Basic and Combination Cross-Features in X- and Q-band HYSCORE of the 15N Labeled Bacteriochlorophyll a Cation Radical

Chlorophylls are an essential class of cofactors found in all photosynthetic organisms. Upon absorbing a photon, the excited state energy of the chlorophyll can either be transferred to another acceptor molecule, or be used to drive electron transfer. When acting as the primary donor in the bacterial photosynthetic reaction center, light-induced charge separation results in the formation of a cationic bacteriochlorophyll dimer. The hyperfine interactions between the unpaired electron of the