Redistribution Of Excitation Energy Research Articles

Identification of Exciton–Exciton Annihilation in Hematite Thin Films

Hematite, a common type of iron oxide, is a promising material for solar technologies because of its small band gap that allows for solar radiation absorption in the visible region, low toxicity in aqueous solutions, easy synthesis, and natural abundance. However, fast electron–hole recombination has been hampering full applicability of hematite in solar technologies. In this study, we used visible femtosecond transient absorption spectroscopy to investigate the excited-state decay and electron–hole recombination dynamics of nanostructured hematite thin films. By varying the pump excitation fluence and performing global and target data analysis, we identified the presence of nonlinear decay processes during the initial picosecond after photoexcitation, which have a non-negligible contribution at pump fluences of >∼1 mJ/(pulse·cm2). Calculations show exciton–exciton annihilation to be the dominant nonlinear process, with an average rate constant of 7.09 × 10–9 cm3 s–1. Annihilation calculations also allowed us to estimate the annihilation radius to be 2.3 nm, thus explaining the rapid exciton–exciton annihilation in the immediate aftermath of photoexcitation. Probe wavelength-dependent decay dynamics points to excitation energy redistribution and involvement of traps in the recombination dynamics. We finally present a kinetic model, verified by performing target data analysis, showing the rates and channels of the dominant processes involved with electron–hole recombination upon relatively high excitation rates. The extremely fast electron–hole recombination process in hematite is one of the main reasons hindering the full applicability of the material in solar water splitting. Measures to limit these ultrafast recombination processes should, therefore, be incorporated into device fabrication and preparation to further improve the material.

Multilevel regulation of non-photochemical quenching andstate transitions by chloroplast NADPH-dependent thioredoxin reductase.

In natural growth habitats, plants face constant, unpredictable changes in light conditions. To avoid damage to the photosynthetic apparatus on thylakoid membranes in chloroplasts, and to avoid wasteful reactions, it is crucial to maintain a redox balance both within the components of photosynthetic electron transfer chain and between the light reactions and stromal carbon metabolism under fluctuating light conditions. This requires coordinated function of the photoprotective and regulatory mechanisms, such as non‐photochemical quenching (NPQ) and reversible redistribution of excitation energy between photosystem II (PSII) and photosystem I (PSI). In this paper, we show that the NADPH‐dependent chloroplast thioredoxin system (NTRC) is involved in the control of the activation of these mechanisms. In plants with altered NTRC content, the strict correlation between lumenal pH and NPQ is partially lost. We propose that NTRC contributes to downregulation of a slow‐relaxing constituent of NPQ, whose induction is independent of lumenal acidification. Additionally, overexpression of NTRC enhances the ability to adjust the excitation balance between PSII and PSI, and improves the ability to oxidize the electron transfer chain during changes in light conditions. Thiol regulation allows coupling of the electron transfer chain to the stromal redox state during these changes.

Ultrafast photoactivation of C─H bonds inside water-soluble nanocages.

Light energy absorbed by molecules can be harnessed to activate chemical bonds with extraordinary speed. However, excitation energy redistribution within various molecular degrees of freedom prohibits bond-selective chemistry. Inspired by enzymes, we devised a new photocatalytic scheme that preorganizes and polarizes target chemical bonds inside water-soluble cationic nanocavities to engineer selective functionalization. Specifically, we present a route to photoactivate weakly polarized sp3 C─H bonds in water via host-guest charge transfer and control its reactivity with aerial O2. Electron-rich aromatic hydrocarbons self-organize inside redox complementary supramolecular cavities to form photoactivatable host-guest charge transfer complexes in water. An ultrafast C─H bond cleavage within ~10 to 400 ps is triggered by visible-light excitation, through a cage-assisted and solvent water-assisted proton-coupled electron transfer reaction. The confinement prolongs the lifetime of the carbon-centered radical to enable a facile yet selective reaction with molecular O2 leading to photocatalytic turnover of oxidized products in water.

Effect of Gd3+ doping on structural and optical properties of ZnO nanocrystals

To investigate the effect of rare earth ions on the excitation energy redistribution between the UV and visible photoluminescence, the Gd3+ doped ZnO nanocrystals prepared through Sol-Gel method were studied. Different structural characterizations and spectroscopic studies were carried out to establish a correlation between the structural effect and the photoluminescence. Our study indicates that the incorporation of Gd3+ in ZnO nanocrystals prepared through this synthesis takes place predominantly on the surface up to 0.18 mole fraction of Gd3+. This is manifested by the observed lattice contraction due to the presence of Gd3+ on the surface. This structural defect introduces various defects that modifies the photoluminescence properties. For these modifications in crystal system, the A1 symmetry phonon modes of wurtzite structure are found to be gradually more Raman active than the other modes as the Gd3+ concentration is increased while the E modes are suppressed. These doping induced modification of phonon spectrum strongly influences the exciton phonon coupling and thereby the photophysical properties. Resulting crystal imperfections strongly enhance the defect band luminescence. It is shown that energy transfer from selectively excited Gd3+ centers to surface states can be effectively exploited for the sensitization of defect band luminescence in various fields such as bio imaging, light emitting devices etc.

The High Efficiency of Photosystem I in the Green Alga Chlamydomonas reinhardtii Is Maintained after the Antenna Size Is Substantially Increased by the Association of Light-harvesting Complexes II

Photosystems (PS) I and II activities depend on their light-harvesting capacity and trapping efficiency, which vary in different environmental conditions. For optimal functioning, these activities need to be balanced. This is achieved by redistribution of excitation energy between the two photosystems via the association and disassociation of light-harvesting complexes (LHC) II, in a process known as state transitions. Here we study the effect of LHCII binding to PSI on its absorption properties and trapping efficiency by comparing time-resolved fluorescence kinetics of PSI-LHCI and PSI-LHCI-LHCII complexes of Chlamydomonas reinhardtii. PSI-LHCI-LHCII of C. reinhardtii is the largest PSI supercomplex isolated so far and contains seven Lhcbs, in addition to the PSI core and the nine Lhcas that compose PSI-LHCI, together binding ∼ 320 chlorophylls. The average decay time for PSI-LHCI-LHCII is ∼ 65 ps upon 400 nm excitation (15 ps slower than PSI-LHCI) and ∼ 78 ps upon 475 nm excitation (27 ps slower). The transfer of excitation energy from LHCII to PSI-LHCI occurs in ∼ 60 ps. This relatively slow transfer, as compared with that from LHCI to the PSI core, suggests loose connectivity between LHCII and PSI-LHCI. Despite the relatively slow transfer, the overall decay time of PSI-LHCI-LHCII remains fast enough to assure a 96% trapping efficiency, which is only 1.4% lower than that of PSI-LHCI, concomitant with an increase of the absorption cross section of 47%. This indicates that, at variance with PSII, the design of PSI allows for a large increase of its light-harvesting capacities.

The fluorescent indices of bean leaves treated with sodium fluoride

It is shown that the treatment of bean leaves with NaF in concentration of 10(-2) M resulted in the alteration of fluorescent indices registered by the method of pulse fluorimetry. Fluorescent parameters F(0) and F(m) decreased, but the ratio F(v)/F(m) = (F(m) - F(0))/F(m), characterizing the maximal photochemical activity of photosystem II remained invariable. Photochemical fluorescence quenching (qP) was higher than in control during the first minutes of illumination with the actinic light, and it markedly decreased with the following illumination. Nonphotochemical quenching (qN), in contrary, decreased at the beginning of illumination, and then increased. Photosynthetic activity as characterizing by the ratio (F(M) - F(T))/F(T) reduced after the leaf treatment with NaF. Results obtained are interpreted proceeding, on the one hand, from the influence of NaF on redistribution of excitation energy between photosystem II and photosystem I and its inhibitory effect on the ATPase complex and Kalvin-Benson cycle, on the other.

The slow S to M rise of chlorophyll a fluorescence reflects transition from state 2 to state 1 in the green alga Chlamydomonas reinhardtii.

The green alga Chlamydomonas (C.) reinhardtii is a model organism for photosynthesis research. State transitions regulate redistribution of excitation energy between photosystem I (PS I) and photosystem II (PS II) to provide balanced photosynthesis. Chlorophyll (Chl) a fluorescence induction (the so-called OJIPSMT transient) is a signature of several photosynthetic reactions. Here, we show that the slow (seconds to minutes) S to M fluorescence rise is reduced or absent in the stt7 mutant (which is locked in state 1) in C. reinhardtii. This suggests that the SM rise in wild type C. reinhardtii may be due to state 2 (low fluorescence state; larger antenna in PS I) to state 1 (high fluorescence state; larger antenna in PS II) transition, and thus, it can be used as an efficient and quick method to monitor state transitions in algae, as has already been shown in cyanobacteria (Papageorgiou et al. 1999, 2007; Kaňa et al. 2012). We also discuss our results on the effects of (1) 3-(3,4-dichlorophenyl)-1,4-dimethyl urea, an inhibitor of electron transport; (2) n-propyl gallate, an inhibitor of alternative oxidase (AOX) in mitochondria and of plastid terminal oxidase in chloroplasts; (3) salicylhydroxamic acid, an inhibitor of AOX in mitochondria; and (4) carbonyl cyanide p-trifluoromethoxyphenylhydrazone, an uncoupler of phosphorylation, which dissipates proton gradient across membranes. Based on the data presented in this paper, we conclude that the slow PSMT fluorescence transient in C. reinhardtii is due to the superimposition of, at least, two phenomena: qE dependent non-photochemical quenching of the excited state of Chl, and state transitions.

UV-B induced alteration of oxygen evolving reactions in pea thylakoid membranes as affected by scavengers of reactive oxygen species

The effect of UV-B irradiation at temperatures of 22 and 4 °C on flash induced oxygen yields, photochemical activity, and energy transfer in pea thylakoid membranes in the absence and presence of scavengers of reactive oxygen species (ROS) was studied. Three different scavengers were used: dimethyl sulfoxide (DMSO), histidine (His), and n-propyl gallate (nPG). As result of the UV-B treatment of isolated membranes, the flash oxygen yields were considerably affected — the amplitudes decreased and the oscillation pattern was lost. The analysis of the flash oxygen yields and initial oxygen burst showed alterations of a number of oxygen evolving centers in the S0 state as well as changes of decay kinetics of the oxygen burst under continuous irradiation. ROS scavengers exhibited more or less expressed protective effects, nPG being the most effective against UV-B induced damages of the flash oxygen yields. At both the temperatures, photosystem II (PS II) mediated electron transport was more sensitive to the UV-B treatment in comparison with photosystem I (PS I). The analysis of 77 K fluorescence spectra showed that the fluorescence ratio F735/F685 increased by the UV-B treatment probably due to a redistribution of excitation energy between both photosystems most likely caused by partial unstacking and due to a decrease of PS II fluorescence resulting from reaction center-type quenching. The nPG was the most powerful scavenger which protected the oxygen evolution capacity of PS II in the absence and presence of an exogenous electron acceptor to the highest extent.

Transient absorption spectra of excitation energy transfer in supramolecular complexes: A mixed quantum-classical description of pheophorbide-a systems

A mixed quantum-classical methodology is utilized to compute transient optical spectra reflecting excitation energy transfer in large pheophorbide-a complexes dissolved in ethanol. Room-temperature molecular dynamics simulations are used to describe the nuclear dynamics of the whole solvent–solute complex. The electronic excitation energy dynamics is accounted for by solving the time-dependent electronic Schrödinger equation. All computations are carried out in the framework of the ground-state classical path approximation and in the presence of optical excitations to determine the nonlinear response. A specification to a pump–probe scheme allows to determine spectra of transient anisotropy which offer signatures of a 10ps excitation energy redistribution already found in earlier studies (Chem. Phys. Chem. 12, (2011) 645).

Fast side-chain losses in keV ion-induced dissociation of protonated peptides

In this paper, we compare ionization and dissociation of a series of singly and doubly protonated peptides, namely leucine enkephalin, bradykinin, LHRH and substance P as induced by collisions with keV H +, He + and He 2+. For all peptides under study, the fragmentation pattern depends strongly on the electronic structure of the projectile ions. Immonium ions, side-chains and their fragments dominate the spectrum whereas fragments due to peptide backbone cleavage are weak or even almost absent for He +. Here, resonant electron capture from the peptide is ruled out and only interaction channels accompanied by much higher excitation contribute. Cleavage of the side-chain linkage appears to be a process alternative to backbone fragmentation occurring after internal vibrational redistribution of excitation energy. Depending on the peptide, this process can lead to the loss of a side-chain cation (leucine enkephalin, LHRH) or a neutral side-chain (substance P).

Acclimation of photosynthesis to nitrogen deficiency in Phaseolus vulgaris

Nitrogen deficiency diminishes consumption of photosynthates in anabolic metabolism. We studied adjustments of the photosynthetic machinery in nitrogen-deficient bean plants and found four phenomena. First, the number of chloroplasts per cell decreased. Chloroplasts of nitrogen starved leaves contained less pigments than those of control leaves, but the in vitro activities of light reactions did not change when measured on chlorophyll basis. Second, nitrogen deficiency induced cyclic electron transfer. The amounts of Rubisco and ferredoxin-NADP(+) reductase decreased in nitrogen starved plants. Low activities of these enzymes are expected to lead to increase in reduction of oxygen by photosystem I. However, diaminobenzidine staining did not reveal hydrogen peroxide production in nitrogen starved plants. Measurements of far-red-light-induced redox changes of the primary donor of photosystem I suggested that instead of producing oxygen radicals, nitrogen starved plants develop a high activity of cyclic electron transport that competes with oxygen for electrons. Nitrogen starvation led to decrease in photochemical quenching and increase in non-photochemical quenching, indicating that cyclic electron transport reduces the plastoquinone pool and acidifies the lumen. A third effect is redistribution of excitation energy between the photosystems in favor of photosystem I. Thus, thylakoids of nitrogen starved plants appeared to be locked in state 2, which further protects photosystem II by decreasing its absorption cross-section. As a fourth response, the proportion of non-Q(B)-reducing photosystem II reaction centers increased and the redox potential of the Q(B)/Q(B)(-) pair decreased by 25 mV in a fraction of photosystem II centers of nitrogen starved plants.

Role of Plastid Protein Phosphatase TAP38 in LHCII Dephosphorylation and Thylakoid Electron Flow

Author SummaryPlants are able to adapt photosynthesis to changes in light levels by adjusting the activities of their two photosystems, the structures responsible for light energy capture. During a process called state transitions, a part of the photosynthetic complex responsible for light harvesting (the photosynthetic antennae) becomes reversibly phosphorylated and migrates between the photosystems to redistribute light-derived energy. The protein kinase responsible for phosphorylating photosynthetic antenna proteins was identified recently. However, despite extensive biochemical efforts to isolate the enzyme that catalyzes the corresponding dephosphorylation reaction, the identity of this protein phosphatase has remained unknown. In this study, we identified and characterized the thylakoid-associated phosphatase TAP38. We first demonstrate by spectroscopic measurements that the redistribution of excitation energy between photosystems that are characteristic of state transitions do not take place in plants without a functional TAP38 protein. We then show that the phosphorylation of photosynthetic antenna proteins is markedly increased in plants without TAP38, but decreased in plants that express more TAP38 protein than wild-type plants. This, together with the observation that addition of recombinant TAP38 decreases the level of antenna protein phosphorylation in an in vitro assay, suggests that TAP38 directly acts on the photosynthetic antenna proteins as the critical phosphatase regulating state transitions. Moreover, in plants without TAP38, photosynthetic electron flow is enhanced, resulting in more rapid growth under constant low-light regimes, thus providing the first instance of a mutant plant with improved photosynthesis.

Time and frequency resolved spontaneous emission from supramolecular pheophorbide- a complexes: A mixed quantum classical computation

A mixed quantum classical methodology is utilized to compute the time and frequency resolved emission spectrum of a chromophore complex dissolved in ethanol. The single complex is formed by a butanediamine dendrimer to which pheophorbide- a molecules are covalently linked. The electronic excitations are described in a Frenkel-exciton model treated quantum mechanically and all nuclear coordinates are described classically by carrying out room-temperature MD simulations. Starting with the full quantum formula for the emission spectrum, it is translated to the mixed quantum classical case and used to compute time resolved spectra up to 2 ns. To account for radiative decay the chromophore complex excited-state dynamics have to be described in a density matrix theory. While the full emission spectrum only reflects excited-state decay the introduction of partial spectra allows to uncover details of excitation energy redistribution among the chromophores.

Photosystem II core phosphorylation and photosynthetic acclimation require two different protein kinases

Illumination changes elicit modifications of thylakoid proteins and reorganization of the photosynthetic machinery. This involves, in the short term, phosphorylation of photosystem II (PSII) and light-harvesting (LHCII) proteins. PSII phosphorylation is thought to be relevant for PSII turnover, whereas LHCII phosphorylation is associated with the relocation of LHCII and the redistribution of excitation energy (state transitions) between photosystems. In the long term, imbalances in energy distribution between photosystems are counteracted by adjusting photosystem stoichiometry. In the green alga Chlamydomonas and the plant Arabidopsis, state transitions require the orthologous protein kinases STT7 and STN7, respectively. Here we show that in Arabidopsis a second protein kinase, STN8, is required for the quantitative phosphorylation of PSII core proteins. However, PSII activity under high-intensity light is affected only slightly in stn8 mutants, and D1 turnover is indistinguishable from the wild type, implying that reversible protein phosphorylation is not essential for PSII repair. Acclimation to changes in light quality is defective in stn7 but not in stn8 mutants, indicating that short-term and long-term photosynthetic adaptations are coupled. Therefore the phosphorylation of LHCII, or of an unknown substrate of STN7, is also crucial for the control of photosynthetic gene expression.

Influence of State-2 transition on the proton motive force across the thylakoid membrane in spinach chloroplasts

The proton motive force (pmf) across the thylakoid membrane is composed of the proton gradient and the membrane potential, which promotes millisecond-delayed light emission (ms-DLE). In this study, the time courses of LHC II phosphorylation and ms-DLE were investigated in spinach chloroplast during State-2 transition. Red light illumination resulted in an exponential rise in LHC II phosphorylation and a biphasic time course of ms-DLE. The phospho-LHC II appeared upon approximately 1 min illumination. The phosphorylation level increased exponentially when illumination was elongated to 20 min. The t((1/2) )of saturated LHC II phosphorylation was estimated 4-5 min under present illumination. During this process, the amplitudes of ms-DLE increased transiently to a maximal amplitude within 0.5 min illumination, and the reached maximum of the fast phase of ms-DLE was approximately 140% of the dark control. Then, ms-DLE decreased from the maximum. After > or =3 min illumination, ms-DLE decreased to a lower level than the dark control. In the presence of uncouplers and inhibitors, the transient increase in the biphasic time course of ms-DLE was removed by nigericin and DCMU, and the sequential decrease was delayed by DCCD. The time course was not affected significantly by valinomycin and DBMIB. Moreover, the level of LHC II phosphorylation was enhanced by nigericin, valinomycin and DCCD, and was inhibited completely by DCMU and partially by DBMIB. Taken together, we proposed that the PS II photochemical activity remained unaffected even with a higher level of LHC II phosphorylation, which was reflected by the effect of DCCD on the time course of ms-DLE. Probably, the evidence of LHC II phosphorylation is the rearrangement of LHC II-PS II complex and the thylakoid, a feedback to light-exposure, rather than the redistribution of excitation energy from PS II to PS I.

Theoretical analysis of inductive effects in higher plant photosynthesis

The proposed mathematical model of the light stages of photosynthesis in higher plants takes into account the regulatory process of excitation energy redistribution between photosystems depending on the redox state of electron carriers. Nonmonotonic changes in the intensity of pigment fluorescence upon switching on the excitation light (delayed fluorescence induction) are described. The time required for fluorescence to reach its peak intensity and the degree of fluorescence quenching depending on light intensity are analyzed. Th kinetics of light-induced changes in EPR I signal upon switching from the far-red to white light is simulated.

Regulation of the distribution of chlorophyll and phycobilin-absorbed excitation energy in cyanobacteria. A structure-based model for the light state transition.

The light state transition regulates the distribution of absorbed excitation energy between the two photosystems (PSs) of photosynthesis under varying environmental conditions and/or metabolic demands. In cyanobacteria, there is evidence for the redistribution of energy absorbed by both chlorophyll (Chl) and by phycobilin pigments, and proposed mechanisms differ in the relative involvement of the two pigment types. We assayed changes in the distribution of excitation energy with 77K fluorescence emission spectroscopy determined for excitation of Chl and phycobilin pigments, in both wild-type and state transition-impaired mutant strains of Synechococcus sp. PCC 7002 and Synechocystis sp. PCC 6803. Action spectra for the redistribution of both Chl and phycobilin pigments were very similar in both wild-type cyanobacteria. Both state transition-impaired mutants showed no redistribution of phycobilin-absorbed excitation energy, but retained changes in Chl-absorbed excitation. Action spectra for the Chl-absorbed changes in excitation in the two mutants were similar to each other and to those observed in the two wild types. Our data show that the redistribution of excitation energy absorbed by Chl is independent of the redistribution of excitation energy absorbed by phycobilin pigments and that both changes are triggered by the same environmental light conditions. We present a model for the state transition in cyanobacteria based on the x-ray structures of PSII, PSI, and allophycocyanin consistent with these results.

Analysis of chlorophyll–protein complexes from the cyanobacterium Cyanothece sp. ATCC 51142 by non-denaturing gel electrophoresis

The unicellular diazotrophic cyanobacterium, Cyanothece sp. ATCC 51142 temporally separates N 2 fixation from photosynthesis. We are analyzing the mechanism by which photosynthesis is down-regulated so that O 2 evolution is minimized during N 2 fixation. Previous results suggested changes in photosynthesis that are mediated through the redox poise of the plastoquinone pool (a process involving state transitions, in which the redistribution of excitation energy between the two photosystems helps to optimize photosynthetic yield) and the oligomerization state of the photosystems. Our working hypothesis was that the regulation of photosynthesis involved changes in the oligomerization of the photosystems. To analyze this hypothesis, we utilized a low-ionic strength, non-denaturing gel electrophoresis system to study the Chl–protein complexes. We determined that PSI is mostly trimeric, whereas PSII appears mainly as monomers. We demonstrated that most of the Chl–protein complexes in Cyanothece sp. remained constant throughout the diurnal cycle, except for the transient accumulation of a Chl–protein complex (band C) which appeared only during the late light period. Based on the size of this complex, band C represents either an interaction of PSI and PSII or a PSII dimer. These results provide support for the dynamic nature of the photosystems with respect to the diurnal cycle.

Observation of energy-distribution-dependent homogeneousupconversion in erbium-doped silica glass fibres

It has been demonstrated experimentally that the rate of homogeneous upconversion in erbium-doped fibres increases with increasing pump and signal power, even if the same degree of excitation is maintained. This is due to an increased redistribution of excitation energy among erbium ions by absorption and stimulated emission. A signal of 8.6 mW could more than double the upconversion rate in a densely doped fibre.

Comparison of state 1-state 2 transitions in the green alga Chlamydomonas reinhardtii and in the red alga Rhodella violacea: effect of kinase and phosphatase inhibitors

In the green alga Chlamydomonas reinhardtii, state transitions occur upon phosphorylation of the light-harvesting complex. The protein kinase inhibitor staurosporine, and the phosphoprotein phosphatase inhibitor NaF, suppress state 2 and state 1 transitions, respectively. By contrast, in the red alga Rhodella violacea none of these inhibitors has any effect, suggesting that, in red algae, the mechanisms of redistribution of excitation energy are independent of protein phosphorylation.