Femtosecond spectroscopy of the primary charge separation in reaction centers of chloroflexus aurantiacus with selective excitation in the Q _y and soret bands

The primary charge separation and electron-transfer processes of photosynthesis occur in the reaction center (RC). Isolated RCs of the green filamentous anoxygenic phototrophic bacterium Chloroflexus aurantiacus were studied at room temperature by using femtosecond transient absorption spectroscopy with selective excitation. Upon excitation in the Q _Y absorbance band of the bacteriochlorophyll (BChl) dimer (P) at 865 nm, a 7.0 ± 0.5 ps kinetic component was observed in the 538 nm region (Q _X band of the bacteriopheophytin (BPheo)), 750 nm region (Q _Y band of the BPheo), and 920 nm region (stimulated emission of the excited-state of P), indicating that this lifetime represents electron transfer from P to BPheo. The same time constant was also observed upon 740 nm or 800 nm excitation. A longer lifetime (300 ± 30 ps), which was assigned to the time of reduction of the primary quinone, Q _A, was also observed. The transient absorption spectra and kinetics all indicate that only one electron-transfer branch is involved in primary charge separation under these excitation conditions. However, the transient absorption changes upon excitation in the Soret band at 390 nm reveal a more complex set of energy and electron-transfer processes. By comparison to studies on the RCs of the purple bacterium Rhodobacter sphaeroides, we discuss the possible mechanism of electron-transfer pathway dependence on excitation energy and propose a model of the Cf. aurantiacus RC that better explains the observed results.