Quantum Yield Of Electron Transfer Research Articles

Effects of Simulated Acid Rain on Photosynthesis in Pinus massoniana and Cunninghamia lanceolata in Terms of Prompt Fluorescence, Delayed Fluorescence, and Modulated Reflection at 820 nm.

The effects of simulated acid rain (SAR) on the photosynthetic performance of subtropical coniferous species have not been thoroughly investigated. In this study, we treated two coniferous species, Pinus massoniana (PM) and Cunninghamia lanceolata (CL), with four gradients of SAR and then analyzed their photosynthetic activities through measurements of gas exchange, prompt fluorescence (PF), delayed fluorescence (DF), and modulated reflection at 820 nm (MR820). Gas exchange analysis indicated that the decrease in the net photosynthetic rate (Pn) in PM and CL was unrelated to stomatal factors. For the PF transients, SAR induced positive K-band and L-band, a significant reduction in photosynthetic performance index (PIABS), the quantum yield of electron transfer per unit cross-section (ETO/CSm), and maximal photochemical efficiency of photosystem II (Fv/Fm). Analysis of the MR820 kinetics showed that the re-reduction kinetics of PSI reaction center (P700+) and plastocyanin (PC+) became slower and occurred at later times under SAR treatment. For the DF signals, a decrease in the amplitude of the DF induction curve reduced the maximum value of DF (I1). These results suggested that SAR obstructed photosystem II (PSII) donor-side and acceptor-side electron transfer capacity, impaired the connectivity between PSII and PSI, and destroyed the oxygen-evolving complex (OEC). However, PM was better able to withstand SAR stress than CL, likely because of the activation of a protective mechanism.

Long term co-application of biochar and fertilizer could increase soybean yield under continuous cropping: insights from photosynthetic physiology.

Photosynthesis is the key to crop yield. The effect of biochar on photosynthetic physiology and soybean yield under continuous cropping is unclear. We conducted a long-term field experiment to investigate the effects of co-application of biochar and fertilizer (BCAF) on these parameters. Five treatments were established: F2 (fertilizer), B1F1 (3 t hm-2 biochar plus fertilizer), B1F2 (3 t hm-2 biochar plus reduced fertilizer), B2F1 (6 t hm-2 biochar plus fertilizer), and B2F2 (6 t hm-2 biochar plus reduced fertilizer). BCAF increased chlorophyll and leaf area, enhancing soybean photosynthesis. The net photosynthetic rate (Pn ), transpiration rate (Tr ), stomatal conductance (Gs ), water use efficiency (WUE) and intercellular carbon dioxide (CO2 ) concentration (Ci ) were enhanced by BCAF. In addition, BCAF improved soybean photosystem II (PSII) photosynthetic performance, driving force, potential photochemical efficiency (Fv /F0 ), and quantum yield of electron transfer (φE0 ). Furthermore, BCAF enhanced the accumulation of photosynthetic products, such as soluble proteins, soluble sugars and sucrose content, resulting in higher leaf dry weight. Consequently, BCAF increased the soybean yield, with the highest increase of 41.54% in B2F1. The correlation analysis revealed positive relationships between soybean yield and chlorophyll, leaf area, maximal quantum yield of PSII (Fv /Fm ), electron transport flux per cross-section at t = 0 (ET0 /CS0 ), trapped energy flux per cross-section at t = 0 (TR0 /CS0 ), composite blade driving force (DFTotal ), and leaf dry weight. We demonstrated that long-term BCAF enhances soybean photosynthesis under continuous planting, reduces fertilizer use and increases yield. This study reveals a novel way and theory to sustainably increase soybean productivity. © 2023 Society of Chemical Industry.

Alleviation effect of GR24, a strigolactone analogue, on low-nitrogen stress in Malus baccata seedlings.

To investigate the efficacy of foliar application of GR24, a strigolactone analogue, in alleviating low-nitrogen stress in Malus baccata, we applied GR24 with different concentrations (0, 1, 5, 10, and 20 μmol·L-1) to leaves of plants under low nitrogen stress. We evaluated the changes in photosynthetic characteristics of leaves, reactive oxygen metabolism, and nitrogen assimilation in roots. The results showed that shoot biomass of seedling significantly decreased and root-shoot ratio increased under low-nitrogen stress. The chlorophyll contents decreased, the carotenoid content increased, and the photosynthetic activity decreased. The activities of superoxide dismutase and catalase enzymes in roots changed little, while the activities of peroxidase and ascorbic acid peroxidase enzymes, along with the levels of soluble sugar, free proline, and reactive oxygen species showed a significant increase, and the soluble protein content decreased. The NO3- content in roots decreased, the NH4+ content increased, while activities of nitrate reductase and glutamine synthase decreased. Compared to the control group without GR24 application, foliar sprays of 10 and 20 μmol·L-1 GR24 under both normal and low-nitrogen increased biomass and root-shoot ratio to varying degrees. Additionally, GR24 application increased chlorophyll content, photosynthesis indices (net photosynthetic rate, transpiration rate and stomatal conductance), and fluorescence (maximum photochemical efficiency of PSⅡ and quantum yield of electron transfer per unit area) performance parameters, as well as the contents of osmotic regulation substances (soluble protein, soluble sugar, and free proline) and glutamine synthase activity. Application of 10 and 20 μmol·L-1 GR24 under low-nitrogen stress decreased carotenoid, reactive oxygen species, and NH4+ contents, while increased the activities of antioxidases and key enzymes in nitrogen metabolism (nitrate reductase and glutamine synthase) and NO3- content. The 10 μmol·L-1 GR24 treatment was the most effective in alleviating low nitrogen stress, which has potential for application in apple orchards with low nitrogen soil.

Photoinduced electron transfer across the polymer-capped CsPbBr3 interface in a polar medium.

In-situ polymer capping of cesium lead bromide (CsPbBr3) nanocrystals with polymethyl acrylate is an effective approach to improve the colloidal stability in the polar medium and thus extends their use in photocatalysis. The photoinduced electron transfer properties of polymethyl acrylate (PMA)-capped CsPbBr3 nanocrystals have been probed using surface-bound viologen molecules with different alkyl chains as electron acceptors. The apparent association constant (Kapp) obtained for the binding of viologen molecules with PMA-capped CsPbBr3 was 2.3 × 107 M-1, which is an order of magnitude greater than that obtained with oleic acid/oleylamine-capped CsPbBr3. Although the length of the alkyl chain of the viologen molecule did not show any impact on the electron transfer rate constant, it influenced the charge separation efficiency and net electron transfer quantum yield. Viologen moieties with a shorter alkyl chain length exhibited a charge separation efficiency of 72% compared with 50% for the longer chain alkyl chain length viologens. Implications of polymer-capped CsPbBr3 perovskite nanocrystals for carrying out photocatalytic reduction in the polar medium are discussed.

Response of Fluorescence and Chlorophyll Physiological Characteristics of Typical Urban Trees to Ozone Stress

In this study, four typical urban landscaping tree species were selected, three open top air chambers with different ozone concentrations were set, and the responses of chlorophyll fluorescence, chlorophyll content and relative conductivity of the trees to ozone stress were studied. The results showed that with the increase in ozone concentration, the maximum photochemical efficiency, electron transfer quantum yield, electron transfer rate (ETR) and chlorophyll content of the different tree species decreased significantly, while the relative conductivity of the different tree species increased significantly. Compared with the ozone concentration of NF, under an ozone concentration of nf40 and nf80, the decline in the rate of Fv/Fm of Koelreuteria paniculata and Ginkgo biloba was 2.47 and 2.28 times that of Pinus bungeana and Platycladus orientalis, respectively, and the increase in the rate of relative conductivity of K. paniculata and G. biloba was 2.11 and 1.28 times that of P. bungeana and P. orientalis, respectively. Under different ozone concentrations, the photochemical efficiency, electron transfer rate, chlorophyll content and relative conductivity of P. bungeana and P. orientalis were higher than those of Ginkgo biloba and K. paniculata, indicating that K. paniculata and G. biloba were more sensitive to ozone. This study is of great significance for improving urban environmental quality and ozone control and also provides a basis for selecting tree species with strong ozone tolerance.

Intra-supramolecular electron transfer of the light harvesting porphyrin—phthalocyanine complex in aqueous medium

Report of the construction of the supramolecular light harvesting composed of zinc(II) phthalocyanine tetrasulfonic acid (ZnPcS[Formula: see text], as electron donor, and meso-tetra([Formula: see text]-methyl-4-pyridyl)porphyrin toluene sulfonate (TMPP), as electron acceptor. The steady-state absorption and fluorescence spectra of TMPP in MeOH showed the formation of monomer form ([Formula: see text] = 426 nm and [Formula: see text] = 654 and 715 nm). In water, different spectral features were recorded, suggesting the formation of aggregated forms. The formation of aggregated form in water was confirmed by recording the remarkable decrease of the fluorescence intensities of the singlet excited TMPP with increasing the concentrations of TMPP. In cationic micelle CTAB, both the absorption and fluorescence spectra were significantly decreased with increasing the concentrations of CTAB with a break at critical micelle concentration (CMC) at 6.00 × 10[Formula: see text] M. In an anionic micelle (SDS), the CMC value was found to be 1.00 × 10[Formula: see text] M. Upon interacting with ZnPcS4 in water, the steady state absorption measurement showed clear evidence for the formation of light harvesting porphyrin-phthalocyanine supramolecular complex through [Formula: see text]–[Formula: see text] and ionic interactions. The emission intensity of the singlet TMPP was found to significantly decrease in the presence of ZnPcS4 suggesting the intra-supramolecular electron transfer process from the electron donating ZnPcS4 to the electron deficient TMPP. From the fluorescence lifetime measurements, the rate and quantum yield of electron transfer were found to be 7.67 × 108 s[Formula: see text] and 0.81, respectively. The finding of the examined light-harvesting supramolecular complex ZnPcS4-TMPP shows the ability to absorb the light in a wide range of the solar spectrum (UV-vis-NIR), in addition to the efficient electron transfer process in an aqueous medium, rendering it as a simple model of the artificial photosynthetic reaction center.

Ozone responses in Arabidopsis: beyond stomatal conductance.

Tropospheric ozone (O3) is a major air pollutant that decreases yield of important crops worldwide. Despite long-lasting research of its negative effects on plants, there are many gaps in our knowledge on how plants respond to O3. In this study, we used natural variation in the model plant Arabidopsis (Arabidopsis thaliana) to characterize molecular and physiological mechanisms underlying O3 sensitivity. A key parameter in models for O3 damage is stomatal uptake. Here we show that the extent of O3 damage in the sensitive Arabidopsis accession Shahdara (Sha) does not correspond with O3 uptake, pointing toward stomata-independent mechanisms for the development of O3 damage. We compared tolerant (Col-0) versus sensitive accessions (Sha, Cvi-0) in assays related to photosynthesis, cell death, antioxidants, and transcriptional regulation. Acute O3 exposure increased cell death, development of lesions in the leaves, and decreased photosynthesis in sensitive accessions. In both Sha and Cvi-0, O3-induced lesions were associated with decreased maximal chlorophyll fluorescence and low quantum yield of electron transfer from Photosystem II to plastoquinone. However, O3-induced repression of photosynthesis in these two O3-sensitive accessions developed in different ways. We demonstrate that O3 sensitivity in Arabidopsis is influenced by genetic diversity given that Sha and Cvi-0 developed accession-specific transcriptional responses to O3. Our findings advance the understanding of plant responses to O3 and set a framework for future studies to characterize molecular and physiological mechanisms allowing plants to respond to high O3 levels in the atmosphere as a result of high air pollution and climate change.

Interaction of pretilachlor with PS-II activity of the cyanobacterium Desmonostoc muscorum PUPCCC 405.10.

Interaction of pretilachlor with photosystem (PS)-II of the cyanobacterium Desmonostoc muscorum PUPCCC 405.10 has been studied in this paper. Pretilachlor negatively affected growth, chlorophyll a (Chl a), photosynthesis, and carbon dissimilation in a dose-dependent manner. Effects were also observed in PSs, especially PS-II (an 11-35% decrease), as well as the whole photosynthetic electron transport activity. The fluorescence emission spectrum of Chl a revealed a dose-dependent effect of pretilachlor on both the antenna and the core complex of PSs, with more severe effect on the former. Data of O-J-I-P fluorescence transient of Chl a revealed that pretilachlor interfered with electron flow between QA and QB sites of PS-II. It was further observed that pretilachlor decreased maximum fluorescence, variable and relative variable fluorescence, maximum quantum yield, quantum yield of electron transport, the rate of trapped exciton movement, quantum yield of electron transfer, and performance index of primary photochemistry; however, there was a progressive increase in the net rate of PS-II closure, quantum yield of energy dissipation, and effective antenna size per active reaction center. A decrease in photosynthetic activity leads to a decrease in carbon dissimilation, as evidenced by low activity of glucose-6-phosphate dehydrogenase and pyruvate kinase. Thus, pretilachlor, which is otherwise known to kill weeds by interfering with cell division, affected the growth of the cyanobacteria by interacting with PS-II.

Effects of directional planting on light environment and leaf photosynthesis of summer maize population

To improve light environment, photosynthetic capacity, and thus the yield of maize, the effects of directional planting on light distribution in canopy and photosynthetic characteristics of ear leaves, as well as the performance of PSII that closely related with photosynthetic characteristics and reflected by the rapid chlorophyll fluorescence kinetic curves were examined in Zhengdan 958 maize variety. The results showed that the orientation of leaves remarkably affected photosynthetically active radiation (PAR) interception of ear leaves, with PAR interception of ear leaves in southward treatment being 271.8% higher than that under northward treatment. The orientation of leaves affec-ted photosynthetic light use efficiency of ear leaves under high and low light conditions. The southward treatment increased net photosynthetic rate (Pn) under saturated light in ear leaves, indicating that the use efficiency to high light was enhanced in leaves of southward treatment. In contrast, the northward treatment increased the apparent quantum yield (α) of ear leaves, indicating leaves in southward treatment adapted the light-limited environment. During the early stage after anthesis, the performance of PSII electron donor side and electron acceptor side was significantly improved, and thus enhanced the performance of PSII reaction center (PIABS) and fluorescence photochemical quenching coefficient (Ψo) in ear leaves of southward treatment. The increase of quantum yield of electron transfer (φEo) indicated the enhancement of transfer performance of electrons from photosystem 2 (PSII) to photosystem 1 (PSI) in leaves of southward treatment. The photosynthetic performance of ear leaves showed a trend of southward > eastward > westward > northward during the early stage after anthesis. Forty days after anthesis, the use efficiency to high light decreased in ear leaves of southward treatment, but the ear leaves of southward treatment showed high use efficiency to low light, which changed the trend of photosynthetic performance of ear leaves to northward > westward > eastward > southward. In summary, northward and eastward treatments improved the light distribution in canopy, the PAR interception of ear leaves, the capacity of photosynthesis and dry matter production, and consequently increased the yield of summer maize.

Triplet-State Photochemistry of Dissolved Organic Matter: Triplet-State Energy Distribution and Surface Electric Charge Conditions.

Excited triplet states of chromophoric dissolved organic matter (3CDOM*) are highly reactive species in sunlit surface waters and play a critical role in reactive oxygen species (ROS) formation and pollutant attenuation. In the present study, a series of chemical probes, including sorbic acid, sorbic alcohol, sorbic amine, trimethylphenol, and furfuryl alcohol, were employed to quantitatively determine 3CDOM* and 1O2 in various organic matters. Using a high concentration of sorbic alcohol as high-energy triplet states quencher, 3CDOM* can be first distinguished as high-energy triplet states (>250 kJ mol-1) and low-energy triplet states (<250 kJ mol-1). The terrestrial-origin natural organic matter (NOM) was found to mainly consist of low-energy triplet states, while high-energy triplet states were predominant in autochthonous-origin NOM and effluent/wastewater organic matter (EfOM/WWOM). The 1O2 quantum yields and electron transfer quantum yield coefficients ( fTMP) generated from low-energy triplet states remained constant in all tested organic matters. External phenolic compound showed quenching effects on triplet-state formation and tended to have a higher quenching efficiency for aromatic ketone triplet states, which are the main high-energy triplet states. In comparison with terrestrial-origin NOM, autochthonous-origin NOM and EfOM/WWOM presented lower reaction rate constants for sorbic amines and higher reaction rate constants for sorbic acid, and these differences are likely due to dissimilar surface electric charge conditions. Understanding the triplet-state photochemistry of CDOM is essential for providing useful insights into their photochemical effects in aquatic systems.

Effects of Antimony Stress on Photosynthesis and Growth of Acorus calamus.

This study was aimed to explore that effects of Sb on physiological parameters of Acorus calamus and the possibility of using A. calamus as a remediation plant. A. calamus potted experiments were conducted using different concentrations (0, 250, 500, 1000, and 2000 mg/kg) of antimony potassium tartrate (Sb3+) (marked as CK, T1, T2, T3, and T4, respectively) and potassium pyroantimonate (Sb5+) (marked as CK, T′1, T′2, T′3, and T′4, respectively). The effects of Sb stress (Sb3+ and Sb5+) on leaf photosynthetic pigments, biomass, photosynthetic characteristics and chlorophyll fluorescence parameters of potted A. calamus were studied. With the rise of Sb3+ concentration from T1 to T4, the leaf pigment contents (chlorophyll a, b, carotenoid), plant height, dry weight, net photosynthetic rate (Pn), stomatal conductance (Gs), evaporation rate (E), PSII maximum photochemical efficiency (Fv/Fm), and PSII electron transfer quantum yield rate (ΦPSII) of A. calamus all reduced, while intercellular CO2 concentration (Ci) significantly increased. The reduction of Pn was mainly induced by non-stomatal limitation. Chlorophyll a/b ratio increased significantly versus the control, while carotenoid/chlorophyll ratio (Car/Chl) first decreased and then increased. The leaf Chl a, Chl b, Car, plant height, dry weight, Pn, Gs, E, Fv/Fm, and ΦPSII all maximized in T′1 (250 mg/kg), but were not significantly different from the control. As the Sb5+ concentration increased from T′2 to T′4, the above indices all decreased and were significantly different from the control. Moreover, intercellular CO2 concentration (Ci) decreased significantly. The reduction of Pn was caused by non-stomatal limitation, indicating the mesophyll cells were damaged. The Car/Chl ratio was stable within 0–500 mg/kg Sb, but decreased in T3 and T4, and rose in T′3 and T′4. After Sb3+ and Sb5+ treatments, translocation factor varied 19.44–27.8 and 19.44–24.86%, respectively. In conclusion, different form Sb3+ treatment, Sb5+ treatment showed a Hormesi effect, as low-concentration treatment promoted A. calamus growth, but high-concentration treatment inhibited its growth. The two forms of Sb both caused unfavorable effects on A. calamus, but the seedlings did not die and were modestly adaptive and Sb-accumulative. A. calamus, which is easily maintained and cultivated, can serve as a good candidate for phytoremediation of water contaminated with Sb.

Ultrafast Electron Transfer in Organic/Inorganic Hybrid System

In this study, a donor acceptor type molecule based on quinacridone (QA) and diketopyrrolopyrrole (DPP) was synthesized. Through the grafting of DPP-QA molecule on the surface of ZnO nanorod, hybrid nanoconnposite DPP-QA/ZnO was obtained. The fluorescence of DPP-QA was significantly quenched in the hybrid DPP-QA/ZnO nanocomposite. The properties of photoinduced electron transfer in the studied system were investigated by time-resolved fluorescence spectroscopy and femtosecond transient absorption spectroscopy in the visible region. It was found that the electron transfer (ET) time constant in the hybrid system is 1.0 x 109 s(-1) and the quantum yield for ET is 75%. It provides a model system to understand the role of inorganic semicon ductors in the organic/inorganic hybrid photoelectrical and photovoltaic devices.

Effect of naphthalene on photosystem 2 photochemical activity of pea plants.

The effect of a typical polyaromatic hydrocarbon, naphthalene (Naph), on photosystem 2 (PS-2) photochemical activity in thylakoid membrane preparations and 20-day-old pea leaves was studied. Samples were incubated in water in the presence of Naph (0.078, 0.21, and 0.78 mM) for 0.5-24 h under white light illumination (15 μmol photons·m(-2)·s(-1)). The PS-2 activity was determined by studying fast and delayed chlorophyll (Chl) a fluorescence. Incubation of samples in water solutions at Naph concentrations of 0.21 and 0.78 mM led to a decrease in the maximum PS-2 quantum efficiency (Fv/Fm), noticeable changes in the polyphasic induction kinetics of fluorescence (OJIP), and a decrease in the amplitudes of the fast and slow components of delayed fluorescence of Chl a. The rate of release of electrolytes from leaves that were preliminarily incubated with Naph (0.21 mM) was also increased. Significant decrease in the fluorescence parameters in thylakoid membrane preparations was observed at Naph concentration of 0.03 mM and 12-min exposure of the samples. Chlorophyll (a and b) and carotenoid content (mg per gram wet mass) was insignificantly changed. The quantum yields of electron transfer from QA to QB (φET2o) and also to the PS-1 acceptors (φRE1o) were reduced. These results are explained by the increase in the number of QB-non-reducing centers of PS-2, which increased with increasing Naph concentration and exposure time of leaves in Naph solution. The suppression of PS-2 activity was partly abolished in the presence of the electron donor sodium ascorbate. Based on these results, it is suggested that Naph distorts cell membrane intactness and acts mainly on the PS-2 acceptor and to a lesser degree on the PS-2 donor side.

Size-dependent excited state behavior of glutathione-capped gold clusters and their light-harvesting capacity.

Glutathione-protected gold clusters exhibit size-dependent excited state and electron transfer properties. Larger-size clusters (e.g., Au25GSH18) with core-metal atoms display rapid (<1 ps) as well as slower relaxation (~200 ns) while homoleptic clusters (e.g., Au(10-12)GSH(10-12)) exhibit only slower relaxation. These decay components have been identified as metal-metal transition and ligand-to-metal charge transfer, respectively. The short lifetime relaxation component becomes less dominant as the size of the gold cluster decreases. The long-lived excited state and ability to participate in electron transfer are integral for these clusters to serve as light-harvesting antennae. A strong correlation between the ligand-to-metal charge-transfer excited state lifetime and photocatalytic activity was evidenced from the electron transfer to methyl viologen. The photoactivity of these metal clusters shows increasing photocatalytic reduction yield (0.05-0.14) with decreasing cluster size, Au25 < Au18 < Au15 < Au(10-12). Gold clusters, Au18GSH14, were found to have the highest potential as a photosensitizer on the basis of the quantum yield of electron transfer and good visible light absorption properties.

Excited state electron transfer from cobalt coordination compounds anchored to TiO2

There exists an urgent need for stable, earth-abundant inorganic coordination compounds and materials that efficiently harvest sunlight and initiate electron transfer reactions that produce electrical power and/or chemical fuels. It was recently discovered that Co(I) coordination compounds do indeed harvest large fractions of solar photons and efficiently transfer electrons to the acceptor states of TiO2 from metal-to-ligand charge transfer excited states. In some cases the electron transfer quantum yield was ∼46%. Remarkably, and unlike other first row transition metal compounds, the unfilled d-orbitals do not quantitatively quench the excited states and allow for efficient excited state electron transfer. A novel feature of the Co(II/I∗) electron transfer chemistry is a large inner-sphere contribution that results from a change in the coordination number. This short review summarizes the most recent findings that suggest new opportunities for solar energy conversion with first-row transition metal compounds.

Photonic Modulation of Electron Transfer with Switchable Phase Inversion

Photochromes may be reversibly photoisomerized between two metastable states and their properties can influence, and be influenced by, other chromophores in the same molecule through energy or electron transfer. In the photochemically active molecular tetrad described here, a porphyrin has been covalently linked to a fullerene electron acceptor, a quinoline-derived dihydroindolizine photochrome, and a dithienylethene photochrome. The porphyrin first excited singlet state undergoes photoinduced electron transfer to the fullerene to generate a charge-separated state. The quantum yield of charge separation is modulated by the two photochromes: one isomer of each quenches the porphyrin excited state, reducing the quantum yield of electron transfer to near zero. Interestingly, when the molecule is illuminated with white light, the quantum yield decreases as the white light intensity is increased, generating an out-of-phase response of the quantum yield to white light. However, when the same experiment is performed in the presence of additional, steady-state UV illumination, a phase inversion occurs. The quantum yield of electron transfer now increases with increasing white light intensity. Such effects illustrate emergent complexity in a relatively simple system and could find applications in molecular logic, photochemical labeling and drug delivery, and photoprotection for artificial photosynthetic molecules. The photochemistry leading to this behavior is discussed.

Femtosecond Decay and Electron Transfer Dynamics of the Organic Sensitizer D149 and Photovoltaic Performance in Quasi-Solid-State Dye-Sensitized Solar Cells

In this work, the femtosecond upconversion spectroscopy was used for the study of ultrafast decay and electron transfer dynamics of the very promising all-organic sensitizer indoline dye, D149, in inert environments as well as on TiO2 substrates. The inert environments were toluene and acetonitrile solutions as well as poly(methyl methacrylate) (PMMA) films and Al2O3 nanostructured substrates. These were used to investigate relaxation and aggregation induced decays. TiO2 substrates were used to probe interfacial electron transfer dynamics. The excitation was at the S2 band while the dynamics of both S2 and S1 bands were detected. The dynamics of the S2 band in solutions and PMMA film, show a rapid S2–S1 internal conversion, ranging from 0.20 to 0.45 ps depending on the environment. This component becomes <0.10 ps in Al2O3 and in TiO2. The dynamics of the S1 band probe both hot and cold S1 species. In solutions and PMMA, the hot species relax to cold ones within a few tens of picoseconds while the cold ones decay to the ground state within a few hundreds of picoseconds. In Al2O3, the dynamics become much faster because of aggregation induced quenching. In TiO2, the S1 dynamics exhibit three mechanisms of 0.1, 1.3, and 8.6 ps time constants indicating a multiphasic injection mechanism. The electron transfer quantum yield and rate from the S1 band were calculated, using the time-resolved data, and were found to be 0.90 and 3.82 × 1011 s–1, respectively. Finally, quasi-solid-state dye-sensitized solar cells, with D149 as sensitizer, were constructed, and their efficiency was found 5.66%. Similar cells, using the ruthenium complexes N719 and black dye as sensitizers, were also constructed for comparison. It was found that D149 showed higher efficiency than black dye but lower than N719.

Accumulation of chlorophyll catabolites photosensitizes the hypersensitive response elicited by Pseudomonas syringae in Arabidopsis

• The staygreen (SGR) gene encodes a chloroplast-targeted protein which promotes chlorophyll degradation via disruption of light-harvesting complexes (LHCs). • Over-expression of SGR in Arabidopsis (SGR-OX) in a Columbia-0 (Col-0) background caused spontaneous necrotic flecking. To relate this to the hypersensitive response (HR), Col-0, SGR-OX and RNAi SGR (SGRi) lines were challenged with Pseudomonas syringae pv tomato (Pst) encoding the avirulence gene avrRpm1. Increased and decreased SGR expression, respectively, accelerated and suppressed the kinetics of HR-cell death. In Col-0, SGR transcript increased at 6 h after inoculation (hai) when tissue electrolyte leakage indicated the initiation of cell death. • Excitation of the chlorophyll catabolite pheophorbide (Pheide) leads to the formation of toxic singlet oxygen ((1)O(2)). Pheide was first detected at 6 hai with Pst avrRpm1 and was linked to (1)O(2) generation and correlated with reduced Pheide a oxygenase (PaO) protein concentrations. The maximum quantum efficiency of photosystem II (F(v)/F(m)), quantum yield of electron transfer at photosystem II (φPSII), and photochemical quenching (qP) decreased at 6 hai in Col-0 but not in SGRi. Disruption of photosynthetic electron flow will cause light-dependent H(2)O(2) generation at 6 hai. • We conclude that disruption of LHCs, possibly influenced by SGR, and absence of PaO produce phototoxic chlorophyll catabolites and oxidative stress leading to the HR.

Photoinduced Electron Transfer of Oxazine 1/TiO2 Nanoparticles at Single Molecule Level by Using Confocal Fluorescence Microscopy

Kinetics of photoinduced electron transfer (ET) from oxazine 1 dye to TiO(2) nanoparticles (NPs) surface is studied at a single molecule level by using confocal fluorescence microscopy. Upon irradiation with a pulsed laser at 630 nm, the fluorescence lifetimes sampled among 100 different dye molecules are determined to yield an average lifetime of 2.9 +/- 0.3 ns, which is close to the value of 3.0 +/- 0.6 ns measured on the bare coverslip. The lifetime proximity suggests that most interfacial electron transfer (IFET) processes for the current system are inefficient, probably caused by physisorption between dye and the TiO(2) film. However, there might exist some molecules which are quenched before fluorescing and fail to be detected. With the aid of autocorrelation analysis under a three-level energy system, the IFET kinetics of single dye molecules in the conduction band of TiO(2) NPs is evaluated to be (1.0 +/- 0.1) x 10(4) s(-1) averaged over 100 single molecules and the back ET rate constant is 4.7 +/- 0.9 s(-1). When a thicker TiO(2) film is substituted, the resultant kinetic data do not make a significant difference. The trend of IFET efficacy agrees with the method of fluorescence lifetime measurements. The obtained forward ET rate constants are about ten times smaller than the photovoltage response measured in an assembled dye-sensitized solar cell. The discrepancy is discussed. The inhomogeneous and fluctuation characters for the IFET process are attributed to microenvironment variation for each single molecule. The obtained ET rates are much slower than the fluorescence relaxation. Such a small ET quantum yield is yet feasibly detectable at a single molecule level.

Interactive Effects of UV-B Radiation and Chemical Contamination on Physiological Parameters in the Lichen Ramalina lacera

To assess the impact of ultraviolet B (UV-B) radiation under laboratory conditions on lichens from different biomonitoring sites, thalli of the lichen Ramalina lacera were transplanted from a clean air site to nine different polluted sites in Israel. Our objective was to determine the probability of synergistic/antagonistic effects on physiological parameters by considering two stressors: chemical contamination and UV-B. Exposure to both airborne pollutants in the field and subsequent UV-B radiation in the laboratory which led to a severe disintegration of cell membranes, followed by electrolyte leakage, indicate the probability of a synergistic effect. The impairment of the potential quantum yield of electron transfer through photosystem II (PSII) of photosynthesis indicated by a significant decrease of the ratio Fv/Fm, further demonstrated the synergistic effect of both chemical contamination and UV-B radiation. Besides enlarged amounts of stress-ethylene in lichens at contaminated sites, the reduced levels of ethylene production upon UV-B radiation in the present study suggest the likelihood of an antagonistic effect of xenobiotic elements and UV-B radiation as a result of an impaired ethylene-producing system.