Femtosecond primary charge separation in Synechocystis sp. PCC 6803 photosystem I

AbstractThe ultrafast (<100fs) conversion of delocalized exciton into charge-separated state between the primary donor P700 (bleaching at 705nm) and the primary acceptor A0 (bleaching at 690nm) in photosystem I (PS I) complexes from Synechocystis sp. PCC 6803 was observed. The data were obtained by application of pump–probe technique with 20-fs low-energy pump pulses centered at 720nm. The earliest absorbance changes (close to zero delay) with a bleaching at 690nm are similar to the product of the absorption spectrum of PS I complex and the laser pulse spectrum, which represents the efficiency spectrum of the light absorption by PS I upon femtosecond excitation centered at 720nm. During the first ∼60fs the energy transfer from the chlorophyll (Chl) species bleaching at 690nm to the Chl bleaching at 705nm occurs, resulting in almost equal bleaching of the two forms with the formation of delocalized exciton between 690-nm and 705-nm Chls. Within the next ∼40fs the formation of a new broad band centered at ∼660nm (attributed to the appearance of Chl anion radical) is observed. This band decays with time constant simultaneously with an electron transfer to A1 (phylloquinone). The subtraction of kinetic difference absorption spectra of the closed (state P700+A0A1) PS I reaction center (RC) from that of the open (state P700A0A1) RC reveals the pure spectrum of the P700+A0− ion–radical pair. The experimental data were analyzed using a simple kinetic scheme: An* →k1 [(PA0)*A1→<100fs P+A0−A1] →k2P+A0A1−, and a global fitting procedure based on the singular value decomposition analysis. The calculated kinetics of transitions between intermediate states and their spectra were similar to the kinetics recorded at 694 and 705nm and the experimental spectra obtained by subtraction of the spectra of closed RCs from the spectra of open RCs. As a result, we found that the main events in RCs of PS I under our experimental conditions include very fast (<100fs) charge separation with the formation of the P700+A0−A1 state in approximately one half of the RCs, the ∼5-ps energy transfer from antenna Chl* to P700A0A1 in the remaining RCs, and ∼25-ps formation of the secondary radical pair P700+A0A1−

FeOx-TiO2 Film with Different Microstructures Leading to Femtosecond Transients with Different Properties: Biological Implications under Visible Light

This study presents the first report addressing the effect of FeOx-TiO2 films microstructure on the transients detected by fast spectroscopy related to the long-range bacterial inactivation performance. The different fast kinetic femtosecond transient spectroscopy is reported for each FeOx+TiO2 microstructure. The lifetime of the short transient-species and the oxidative intermediate radicals generated under light were identified. Co-sputtered FeOx-TiO2 on polyethylene films presenting random distribution for both oxides were compared with sequentially sputtered FeOx/TiO2 films made up only by FeOx in the topmost layers. The ratio FeOx: TiO2 was optimized to attain the highest photo-conversion. By X-ray fluorescence, the Fe:Ti ration was found to be similar to 1.4 in the film bulk and by XPS-etching a ratio of 4: 1 was found on the photocatalyst top-most layers. For co-sputtered FeOx-TiO2-PE films, the FeOx-TiO2 heterojunction led to electron injection from the FeOx to lower-lying TiO2 trapping states. The film optical properties, particle size, roughness, hydrophobic-hydrophilic shift and temporal evolution of the transient redox states were characterized in detail. Films with different microstructure led to different antibacterial activity. This suggests that the FeOx-TiO2-PE microstructure and not the position of the potential energy level of the semiconductors FeOx and TiO2 control the charge transfer under light irradiation

Unprecedented Coordination-Induced Bright Red Emission from Group 12 Metal-Bound Triarylazoimidazoles

Arylazoimidazoles are important dyes which were intensively studied in the past. In contrast, triarylazoimidazoles (derivatives which carry aryl substituents at the imidazole core) received almost no attention in the scientific literature. Here, we report a new family of simple and easily accessible triarylazoimidazole-group 12 metal complexes, which feature highly efficient photo-luminescence emission (Φ up to  0.44). Novel compounds exhibit bright red emission in solution, which could be excited with a visible light

Role of hydrogen bond alternation and charge transfer states in photoactivation of the Orange Carotenoid Protein

Here, we propose a possible photoactivation mechanism of a 35-kDa blue light-triggered photoreceptor, the Orange Carotenoid Protein (OCP), suggesting that the reaction involves the transient formation of a protonated ketocarotenoid (oxocarbenium cation) state. Taking advantage of engineering an OCP variant carrying the Y201W mutation, which shows superior spectroscopic and structural properties, it is shown that the presence of Trp201 augments the impact of one critical H-bond between the ketocarotenoid and the protein. This confers an unprecedented homogeneity of the dark-adapted OCP state and substantially increases the yield of the excited photoproduct S*, which is important for the productive photocycle to proceed. A 1.37 Å crystal structure of OCP Y201W combined with femtosecond time-resolved absorption spectroscopy, kinetic analysis, and deconvolution of the spectral intermediates, as well as extensive quantum chemical calculations incorporating the effect of the local electric field, highlighted the role of charge-transfer states during OCP photoconversion

Role of hydrogen bond alternation and charge transfer states in photoactivation of the Orange Carotenoid Protein

Here, we propose a possible photoactivation mechanism of a 35-kDa blue light-triggered photoreceptor, the Orange Carotenoid Protein (OCP), suggesting that the reaction involves the transient formation of a protonated ketocarotenoid (oxocarbenium cation) state. Taking advantage of engineering an OCP variant carrying the Y201W mutation, which shows superior spectroscopic and structural properties, it is shown that the presence of Trp201 augments the impact of one critical H-bond between the ketocarotenoid and the protein. This confers an unprecedented homogeneity of the dark-adapted OCP state and substantially increases the yield of the excited photoproduct S*, which is important for the productive photocycle to proceed. A 1.37 Å crystal structure of OCP Y201W combined with femtosecond time-resolved absorption spectroscopy, kinetic analysis, and deconvolution of the spectral intermediates, as well as extensive quantum chemical calculations incorporating the effect of the local electric field, highlighted the role of charge-transfer states during OCP photoconversion