Effect of Dehydrated Trehalose Matrix on the Kinetics of Forward Electron Transfer Reactions in Photosystem I

The effect of dehydration on the kinetics of forward electron transfer (ET) has been studied in cyanobacterial photosystem I (PS I) complexes in a trehalose glassy matrix by time-resolved optical and EPR spectroscopies in the 100 fs to 1 ms time domain. The kinetics of the flash-induced absorption changes in the subnanosecond time domain due to primary and secondary charge separation steps were monitored by pump–probe laser spectroscopy with 20-fs low-energy pump pulses centered at 720 nm. The back-reaction kinetics of P700 were measured by high-field time-resolved EPR spectroscopy and the forward kinetics of A∙−1A/A∙−1B→FX by time-resolved optical spectroscopy at 480 nm. The kinetics of the primary ET reactions to form the primary P∙+700A∙−0 and the secondary P∙+700A∙−1 ion radical pairs were not affected by dehydration in the trehalose matrix, while the yield of the P∙+700A∙−1 was decreased by ~20%. Forward ET from the phylloquinone molecules in the A∙−1A and A∙−1B sites to the iron–sulfur cluster FX slowed from ~220 ns and ~20 ns in solution to ~13 μs and ~80 ns, respectively. However, as shown by EPR spectroscopy, the ~15 μs kinetic phase also contains a small contribution from the recombination between A∙−1B and P∙+700. These data reveal that the initial ET reactions from P700 to secondary phylloquinone acceptors in the A- and B-branches of cofactors (A1A and A1B) remain unaffected whereas ET beyond A1A and A1B is slowed or prevented by constrained protein dynamics due to the dry trehalose glass matrix

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

Ultrafast Quenching of Excitons in the ZnxCd1−xS/ZnS Quantum Dots Doped with Mn2+ through Charge Transfer Intermediates Results in Manganese Luminescence

For the first time, a specific time-delayed peak was registered in the femtosecond transient absorption (TA) spectra of ZnxCd1−xS/ZnS (x~0.5) alloy quantum dots (QDs) doped with Mn2+, which was interpreted as the electrochromic Stark shift of the band-edge exciton. The time-delayed rise and decay kinetics of the Stark peak in the manganese-doped QDs significantly distinguish it from the kinetics of the Stark peak caused by exciton–exciton interaction in the undoped QDs. The Stark shift in the Mn2+-doped QDs developed at a 1 ps time delay in contrast to the instantaneous appearance of the Stark shift in the undoped QDs. Simultaneously with the development of the Stark peak in the Mn2+-doped QDs, stimulated emission corresponding to 4T1-6A1 Mn2+ transition was detected in the subpicosecond time domain. The time-delayed Stark peak in the Mn2+-doped QDs, associated with the development of an electric field in QDs, indicates the appearance of charge transfer intermediates in the process of exciton quenching by manganese ions, leading to the ultrafast Mn2+ excitation. The usually considered mechanism of the nonradiative energy transfer from an exciton to Mn2+ does not imply the development of an electric field in a QD. Femtosecond TA data were analyzed using a combination of empirical and computational methods. A kinetic scheme of charge transfer processes is proposed to explain the excitation of Mn2+. The kinetic scheme includes the reduction of Mn2+ by a 1Se electron and the subsequent oxidation of Mn1+ with a hole, leading to the formation of an excited state of manganese

Ultrafast Spectroscopy of Fano-Like Resonance between Optical Phonon and Excitons in CdSe Quantum Dots: Dependence of Coherent Vibrational Wave-Packet Dynamics on Pump Fluence

The main goal of the present work is to study the coherent phonon in strongly confined CdSe quantum dots (QDs) under varied pump fluences. The main characteristics of coherent phonons (amplitude, frequency, phase, spectrogram) of CdSe QDs under the red-edge pump of the excitonic band [1S(e)-1S3/2(h)] are reported. We demonstrate for the first time that the amplitude of the coherent optical longitudinal-optical (LO) phonon at 6.16 THz excited in CdSe nanoparticles by a femtosecond unchirped pulse shows a non-monotone dependence on the pump fluence. This dependence exhibits the maximum at pump fluence ~0.8 mJ/cm2. At the same time, the amplitudes of the longitudinal acoustic (LA) phonon mode at 0.55 THz and of the coherent wave packet of toluene at 15.6, 23.6 THz show a monotonic rise with the increase of pump fluence. The time frequency representation of an oscillating signal corresponding to LO phonons revealed by continuous wavelet transform (CWT) shows a profound destructive quantum interference close to the origin of distinct (optical phonon) and continuum-like (exciton) quasiparticles. The CWT spectrogram demonstrates a nonlinear chirp at short time delays, where the chirp sign depends on the pump pulse fluence. The CWT spectrogram reveals an anharmonic coupling between optical and acoustic phonons

Donor&ndash;Acceptor Complexes of (5,10,15,20-Tetra(4-methylphenyl)porphyrinato)cobalt(II) with Fullerenes C60: Self-Assembly, Spectral, Electrochemical and Photophysical Properties

The noncovalent interactions of (5,10,15,20-tetra(4-methylphenyl)porphinato)cobalt(II) (CoTTP) with C60 and 1-N-methyl-2-(pyridin-4-yl)-3,4-fullero[60]pyrrolidine (PyC60) were studied in toluene using absorption and fluorescence titration methods. The self-assembly in the 2:1 complexes (the triads) (C60)2CoTTP and (PyC60)2CoTTP was established. The bonding constants for (C60)2CoTTP and (PyC60)2CoTTP are defined to be (3.47 &plusmn; 0.69) &times; 109 and (1.47 &plusmn; 0.28) &times; 1010 M&minus;2, respectively. 1H NMR, IR spectroscopy, thermogravimetric analysis and cyclic voltammetry data have provided very good support in favor of efficient complex formation in the ground state between fullerenes and CoTTP. PyC60/C60 fluorescence quenching in the PyC60/C60&ndash;CoTTP systems was studied and the fluorescence lifetime with various CoTTP additions was determined. The singlet oxygen quantum yield was determined for PyC60 and the intensity decrease in the 1O2 phosphorescence for C60 and PyC60 with the CoTTP addition leading to the low efficiency of intercombination conversion for the formation of the 3C60* triplet excited state was found. Using femtosecond transient absorption measurements in toluene, the photoinduced electron transfer from the CoTTP in the excited singlet state to fullerene moiety was established. Quantum chemical calculations were used for the determination of molecular structure, stability and the HOMO/LUMO energy levels of the triads as well as to predict the localization of frontier orbitals in the triads