Quantum Efficiency Of Electron Transport Research Articles

Quantum rate efficiency of the charge transfer mediated by quantum capacitive states

It has been demonstrated that the transfer of electrons between donor and acceptor states is a room-temperature quantum mechanical event wherein quantum capacitive states per se determine the rate of the charge transfer. This analysis establishes quantum capacitance as a key concept governing the rate efficiency with which electrons are transferred between states. This rate efficiency has been particularly demonstrated using redox-active switches assembled over metallic electrodes, where the transfer of charge between the electrode and redox states occurs in a diffusionless regime. This analysis formed the basis for the quantum rate theory of electron transmittance, which predicts (and experimentally confirms) the existence of a limiting value for this charge transfer resistance that complies with the conductance quantum (a conductance constant value of ∼ 77.5 μS or resistance of ∼ 12.9 kΩ). In this study, we evaluated how the quantum rate concept applies to electrochemical reactions in which the transfer of electrons occurs between electrode and redox-free states in solution (electrolyte) mediated by quantum capacitive states within the interface. The quantum capacitive mediation of the electron transfer reaction demonstrates an improvement in electronic communication, with capacitive states effectively acting as a non-adiabatic bridge with a quantum efficiency enabling electrons to hop following a tunnelling mechanism. The quantum efficiency of electron transport surpasses the traditional diffusion-controlled transfer of electrons within a charge transfer resistance limit that complies with ∼ 12.9 kΩ, leading to a maximum electrode-mediated quantum rate efficiency. Applications of the concept allow us to design molecular interfaces with quantum mechanical efficiency for harvesting electrons from the solution phase to solid-state electrodes.

Integrated land-surface hydrological and biogeochemical processes in simulating water, energy and carbon fluxes over two different ecosystems

Understanding the mechanism of the interactions between vegetation dynamics and the water cycle is rather important for determining global and regional water and carbon budgets. In this paper, a physically-based model integrating land-surface hydrological and biogeochemical processes by coupling a hydrological model and a biogeochemical model is developed to simulate the water, energy and carbon fluxes. The model is validated against observed biometric, eddy-covariance flux, soil moisture and temperature data over two different ecosystems. Results show that the model could simulate the vegetation physiological and hydrological processes satisfactorily including net radiation, latent heat, gross primary production (GPP), net ecosystem exchange and soil moisture and temperature. Sensitivity analysis illustrates that evapotranspiration, GPP, net ecosystem production are quite sensitive to plant physiological controls such as the maximum electron transport rate, quantum efficiency of electron transport and runoff parameter. Moreover, results show that a close relationship between photosynthesis and transpiration. Water use efficiency shows a U-bend curve at different time steps and it also indicates a higher value in forest ecosystem than that of grass ecosystem. In the forest ecosystem, evapotranspiration is higher and the surface runoff is lower. Meanwhile it is almost carbon sink during the whole year, while in the grass ecosystem, it shows a carbon source during May to September. This study could provide an effective model for the simulation of water-carbon cycles.

Chilling stress and chilling tolerance of sweet potato as sensed by chlorophyll fluorescence

We studied changes in the chlorophyll (Chl) fluorescence components in chilling-stressed sweet potato (Ipomoea batatas L. Lam) cv. Tainung 57 (TN57, chilling-tolerant) and cv. Tainung 66 (TN66, chilling-susceptible). Plants under 12-h photoperiod and 400 µmol m-2 s-1 irradiance at 24/20 °C (day/night) were treated by a 5-d chilling period at 7/7 °C. Compared to TN66, TN57 exhibited a significantly greater basic Chl fluorescence (F0), maximum fluorescence (Fm), maximum fluorescence yield during actinic irradiation (Fm' ), and the quantum efficiency of electron transport through photosystem 2, PS2 (ΦPS2). Chilling stress resulted in decrease in the potential efficiency of PS2 (Fv/Fm), ΦPS2, non-photochemical fluorescence quenching (NPQ), non-photochemical quenching (qN), and the occurrence of chilling injury in TN66. Chilling increased the likelihood of photoinhibition, characterized by a decline in the Chl fluorescence of both cultivars, and photoinhibition during low temperature stress generally occurred more rapidly in TN66.

Responses of estuarine intertidal microphytobenthic algal assemblages to enhanced ultraviolet B radiation

AbstractAs a result of ozone depletion, ground doses of ultraviolet B (UVB) radiation in the mid latitudes of the Northern Hemisphere have increased since the 1980s, and current predictions indicate no possible alleviation until at least post 2020. Mudflats and sandflats are important coastal‐zone habitats, and support extensive biofilms of benthic microalgae (microphytobenthos). In intertidal situations, these assemblages are exposed to high levels of UVB radiation during periods of tidal exposure. Exposure of intertidal biofilms dominated by epipelic (mud‐inhabiting) diatoms to 0, 0.18 or 0.35 W m−2 UVB radiation for between 4 and 10 days resulted in no significant decreases in the maximum PSII quantum efficiency (Fv/Fm) throughout diel exposure periods. Although the quantum efficiency of electron transport (Fq′/Fm′) showed significant reductions early in some experiments, the major response was an increase in Fq′/Fm′ in UVB exposed biofilms. This increase in Fq′/Fm′ was suggestive of a protective vertical migration down into the sediment. Single‐cell and whole biofilm fluorescence imaging demonstrated, for the first time, that motile diatoms are able to detect UVB radiation independently of UVA or photosynthetically active radiation (PAR) and migrate rapidly down (within 15 min) into the sediments to avoid it. This behavioural acclimation mechanism appears to prevent significant accumulation of UVB induced damage to the algae. UVB exposure had no significant effect of biofilm photosynthesis (measured by 14C carbon fixation), but did alter organic carbon allocation patterns, with significantly less new carbon allocated to intracellular storage (glucan) and extracellular colloidal carbohydrate fractions. Significant reductions in the sediment standing stocks of chlorophyll a (Chl a), colloidal carbohydrates, extracellular polymeric substances (EPS) were seen after 7 days of UVB exposure. This study showed that marine intertidal benthic diatoms use a behavioural strategy to avoid exposure to UVB and that this response is effective as a short‐term protection mechanism against UVB damage. However, altered carbon allocation patterns feed forward over time into changes in biofilm biomass and sediment carbohydrate dynamics. This suggests that continual long‐term exposure to UVB may impact on sediment carbon cycling and trophic interactions and on the stabilization of sediments by microalgal biofilms through their production of extracellular carbohydrates.

Can photosynthesis-related parameters be used to establish the activity of acetolactate synthase–inhibiting herbicides on weeds?

The application of the acetolactate synthase (ALS)–inhibiting herbicide metsulfuron on greenhouse- and field-grown black nightshade and greenhouse-grown ladysthumb resulted in progressive inhibition of the level of carbon dioxide (CO2) fixation, the relative quantum efficiency of electron transport through photosystem I (ΦPSI) and II (ΦPSII), and the leaf chlorophyll content. Photosynthetic-related measurements, measured 2 to 4 d after treatment (DAT) at photon flux densities of 400 to 500 μmol m−2 s−1, provided valuable information before the visual symptoms that first appeared at 7 to 10 DAT with the herbicide. Measurements of the quantum efficiency for electron transport by photosystem II and the loss in leaf chlorophyll content appeared to be two of the most practical parameters to use when designing an early detection method to assess the toxicity of metsulfuron. The use of chlorophyll fluorescence would require a comparison of steady-state ΦPSII measurements for control and treated plants, which could be realized by either measuring in time (before/after application) or space (treated/untreated patch).

Seedling survival in a northern temperate forest understory is increased by elevated atmospheric carbon dioxide and atmospheric nitrogen deposition

AbstractWe tested the main and interactive effects of elevated carbon dioxide concentration ([CO2]), nitrogen (N), and light availability on leaf photosynthesis, and plant growth and survival in understory seedlings grown in an N‐limited northern hardwood forest. For two growing seasons, we exposed six species of tree seedlings (Betula papyrifera, Populus tremuloides, Acer saccharum, Fagus grandifolia, Pinus strobus, and Prunus serotina) to a factorial combination of atmospheric CO2 (ambient, and elevated CO2 at 658 μmol CO2 mol−1) and N deposition (ambient and ambient +30 kg N ha−1 yr−1) in open‐top chambers placed in an understory light gradient. Elevated CO2 exposure significantly increased apparent quantum efficiency of electron transport by 41% (P<0.0001), light‐limited photosynthesis by 47% (P<0.0001), and light‐saturated photosynthesis by 60% (P<0.003) compared with seedlings grown in ambient [CO2]. Experimental N deposition significantly increased light‐limited photosynthesis as light availability increased (P<0.037). Species differed in the magnitude of light‐saturated photosynthetic response to elevated N and light treatments (P<0.016). Elevated CO2 exposure and high N availability did not affect seedling growth; however, growth increased slightly with light availability (R2=0.26, P<0.0001). Experimental N deposition significantly increased average survival of all species by 48% (P<0.012). However, seedling survival was greatest (85%) under conditions of both high [CO2] and N deposition (P<0.009). Path analysis determined that the greatest predictor for seedling survival in the understory was total biomass (R2=0.39, P<0.001), and that carboxylation capacity (Vcmax) was a better predictor for seedling growth and survival than maximum photosynthetic rate (Amax). Our results suggest that increasing [CO2] and N deposition from fossil fuel combustion could alter understory tree species recruitment dynamics through changes in seedling survival, and this has the potential to alter future forest species composition.

The use of multiple-strain algal sensor chips for the detection and identification of volatile organic compounds

Although biosensors detecting a great variety of toxicants have been developed during the last decades, the simultaneous detection and identification of several targets by one biosensor is not possible in the majority of the biosensor systems. In our study we proved the concept of the detection and identification of two different volatile toxic compounds with a non-selective biochip-based algal biosensor. For that purpose we produced array plate biochips to utilise three membrane-immobilised algal strains of genus Klebsormidium and Chlorella in one biosensor system. A novel IMAGING-PAM chlorophyll fluorometer was applied to measure the impact of volatile organic compounds (VOC) on photosynthesis of chip-immobilized algae in terms of quantum efficiency of electron transport (Δ F/ F′ m ). Formaldehyde (FA) vapour was detectable with statistical significance in concentrations relevant to human health from 10 ppb to 10 ppm. The biosensor response recorded within minutes was concentration-dependent and reversible. Moreover, vapours of formaldehyde (0.05–1 ppm) and methanol (MeOH) (200–1000 ppm) were significantly identified by the compound-specific response rate as a quotient of the biosensor responses of the respective algal strains. Using the IMAGING-PAM chlorophyll fluorometer, data sampling proved to be highly efficient. Based on our results we conclude that the principle of the algal sensor chip (ASC) suggests further research on the detection and identification of VOCs and other toxic substances in gaseous environment with that biochip system.

Effects of soil temperature on parameters of a coupled photosynthesis-stomatal conductance model.

To examine the effects of soil temperature on a coupled photosynthesis-stomatal conductance model, seedlings of trembling aspen (Populus tremuloides Michx.), jack pine (Pinus banksiana Lamb.), black spruce (Picea Mariana (Mill.) B.S.P.) and white spruce (Picea glauca (Moench) Voss) were exposed to soil temperatures ranging from 5 to 35 degrees C for 4 months. Light and CO(2) response curves of foliar gas exchange were measured for model parameterization. The effects of soil temperature on four key model parameters, V(cmax) (maximum rate of carboxylation), J(max) (maximum rate of electron transport), alpha (energy conversion efficiency or quantum efficiency of electron transport) and R(d) (daytime dark respiration), were modeled using two third-order polynomial equations and a modified Arrhenius equation. In all species, V(cmax) and J(max) increased with soil temperature up to an optimum, and then decreased with further increases in soil temperature. In the conifers, alpha showed a similar response to soil temperature as V(cmax) and J(max), but soil temperature had no significant effect on alpha in aspen. Soil temperature had no significant effect on R(d) in any species. The three equations described the relationships between soil temperature and the model parameters reasonably well, but performed best for V(cmax) and worst for alpha. No significant relationships were identified between soil temperature and the parameters of the stomatal conductance model.

Photosynthetic responses to phosphorus nutrition in two-year-old maritime pine seedlings.

We analyzed processes limiting photosynthesis in two-year-old, container-grown Pinus pinaster Ait. seedlings subjected to phosphorus (P) deficiency. After withholding P for 3 months, seedlings were supplied P at four relative addition rates (0, 0.005, 0.01 and 0.02 day(-1)) in a nutrient recycling system. At Weeks 12 and 22, responses of photosynthesis to CO(2) and irradiance were measured and the following parameters derived: maximal velocity of carboxylation by Rubisco, V(m); apparent quantum efficiency of electron transport, alpha maximal electron transport rate, J(m); stomatal conductance and relative stomatal limitation of photosynthesis. At Week 22, these measurements were combined with concurrent measurements of chlorophyll fluorescence to determine the quantum yield of PSII, and a theoretical partitioning of total light-driven linear electron flow between fractions used to regenerate carboxylated and oxygenated RuBP. After 12 weeks of treatment, needle P concentrations ranged from 0.04 to 0.15 x 10(-2) g g(DW) (-1), and then remained constant until Week 22. Values of J(m), alpha and V(m) increased with increasing needle P concentration (from 30 to 133 &mgr;mol m(-2) s(-1), 0.02 to 0.25 mol mol(-1) and 13 to 78 &mgr;mol CO(2) m(-2) s(-1) at the lowest and highest needle P concentrations, respectively). Under ambient conditions, net assimilation rates in P-deficient seedlings were limited by V(m) under saturating irradiance, and by J(m) under limiting irradiance, but not by triose-P regeneration. There was no detectable change in the partitioning of total light-driven linear electron flow between the fractions used for carboxylation and oxygenation. Predawn photochemical efficiency of PSII was significantly reduced in seedlings with low P concentrations. Although stomatal conductance tended to decrease with decreasing needle P concentration, relative stomatal limitation was not significantly affected. At Week 22, there was an attenuation of the effects of P nutrition on V(m) and an increase in alpha and J(m) that was probably related to cessation of growth and the seasonal decline in natural irradiance.

Characterization of PSII photochemistry in salt-adapted cells of cyanobacterium Spirulina platensis.

The changes in pigment composition, photosynthesis and PSII photochemistry were investigated in cells of Spirulina platensis adapted to salt stress (<0.75 M NaCl). A decrease in the phycocyanine/chlorophyll and no significant change in the carotenoid/chlorophyll ratio were observed in salt-adapted cells. Salt stress inhibited the apparent quantum efficiency of photosynthesis and PSII activity while stimulating PSI activity and dark respiration significantly. Salt stress also resulted in a decrease in overall activity of the electron transport chain, which could not be restored by diphenylcarbazide, an artificial electron donor to the reaction centres of PSII. Measurements of the polyphasic fluorescence rise in fluorescence transients including phases O, J, I and P showed that salt stress had no effect on the fluorescence yield at phase O but decreased the fluorescence yield at phases J, I and P. Analyses of the JIP test developed from the polyphasic rise of fluorescence transients showed that salt stress led to a decrease in both the maximum quantum efficiency of PSII photochemistry and the maximum quantum efficiency of electron transport beyond the primary quinone electron acceptor. However, salt stress induced no significant changes in the probability of transporting an electron beyond QA , the trapping flux per PSII reaction centre, or the electron transport flux per PSII reaction centre. A theoretical analysis of fluorescence parameters indicated a decrease in the rate constant of excitation energy trapping by PSII reaction centres. In addition, salt stress induced an increase in the complementary area above the fluorescence induction curve in the presence of 3-(3,4-dichlorophenyl)-1,1-dimethylurea, suggesting an increase in the proportion of closed PSII reaction centres in salt-adapted cells. Based on these results, it is suggested that modifications in PSII photochemistry in salt-adapted Spirulina cells maintained a high conversion efficiency of excitation energy, such that no significant change was observed in either the trapping flux or the electron transport flux per PSII reaction centre.

Oxygen-sensitive Differences in the Relationship between Photosynthetic Electron Transport and CO2 Assimilation in C3 and C4 Plants during State Transitions

Wheat (C3) and maize (C4) leaves were exposed to light treatments that were limiting for CO2 assimilation and which excite preferentially photosystem I (PSI) or photosystem II (PSII) and induce State 1 or State 2, respectively. In order to examine the relationships between linear electron transport and CO2 in leaves during State transitions, simultaneous measurements of CO2 assimilation, chlorophyll fluorescence and absorbance at 820 nm were used to estimate the quantum efficiencies of CO2 assimilation and PSII and PSI photochemistry. In wheat leaves with photorespiratory activity, no significant change in quantum efficiency of CO2assimilation was observed during State transitions. This was not the case when photorespiration was inhibited with either 2% O2 or 1000 ppm CO2 and transition from State 2 to State 1 was accompanied by a large decrease (c. 20%) in the quantum efficiency of CO2 assimilation which was not associated with a decrease in the quantum efficiency of electron transport through PSII. Photorespiration appears to buffer the quantum efficiency of CO2 assimilation from changes associated with decreases in the rate of CO2 fixation resulting from imbalances in PPFD absorption by PSI and PSII. When maize leaves were subjected to similar State transitions, no significant change in the quantum efficiency of CO2 assimilation was observed on transition from State 2 to State 1, but on switching back to State 2 a very large decrease (c. 40%) was observed. This decrease could be prevented if leaves were maintained in either 2% O2 or 593 ppm CO2. The possible occurrence of photorespiration in maize leaves on transition from State 1 to State 2, which could result from an inhibition of the CO2 concentrating mechanism, cannot account for the decrease in the quantum efficiency of CO2 assimilation since the relationship between PSII electron transport and CO2 assimilation remained similar throughout the State transitions. Also changes in the phosphorylation status of the light-harvesting chlorophyll a/b protein associated with PSII cannot be implicated in this phenomenon.

Oscillations in photosynthetic carbon assimilation and chlorophyll fluorescence are different in Amaranthus caudatus, a C4 plant, and Spinacia oleracea, a C3 plant

The characteristics of oscillations in photosynthetic carbon fixation and chlorophyll fluorescence in leaves of the C4 plant Amaranthus caudatus L. were compared to those shown by the C3 plant Spinacia oleracea L. As in spinach, oscillations could be observed in Amaranthus when leaves were illuminated after periods of darkening, particularly at temperatures below 20°C, less so or not at all at higher temperatures. However, in contrast to spinach, pronounced oscillations occurred in Amaranthus after a sudden dark/light transition only at low, not at high photon flux densities. Whereas in spinach maxima in carbon uptake were observed slightly after minima in chlorophyll fluorescence had occurred, in Amaranthus maxima in carbon uptake were close to maxima in chlorophyll fluorescence. Since the quantum efficiency of electron transport through photosystem II of the chloroplast electron-transport chain was higher during the minima of chlorophyll fluorescence than during the maxima, the observations suggest that in Amaranthus photosynthetic water oxidation did not occur as synchronously with carbon uptake as in spinach. It is proposed that, in contrast to spinach, photosynthetic oscillations in Amaranthus are related to the diffusional transport of photosynthetic intermediates between mesophyll and bundle-sheath cells.

Control of the Quantum Efficiencies of Photosystems I and II, Electron Flow, and Enzyme Activation following Dark-to-Light Transitions in Pea Leaves

The quantum efficiencies of photosystems I and II (PSI and PSII), [NADP]/[NADPH] ratios, and the activities of chloroplastic fructose-1,6-bisphosphatase and NADP-malate dehydrogenase were measured in intact pea (Pisum sativum L.) leaves in air following the transition from darkness to 750 microeinsteins per square meter per second irradiance. PSII efficiency declined from a low value to a minimum within the first 10 to 15 seconds of irradiance, after which it increased progressively to the steady-state value. The resistance of electron flow between the photosystems was high at this time, but it was not the principal factor limiting electron flow. Oxidation of P700 was restricted by acceptor side processes for approximately the first 60 seconds of illumination. Once the acceptor side limitation was relieved, the oxidation state of P700 was used to estimate the quantum efficiency of electron transport by PSI. This was observed to increase progressively with time. The quantum efficiencies of both photosystems increased in parallel, consistent with a predominant role for noncyclic electron transport. Fructose-1,6-bisphosphatase activity increased in an approximately sigmoidal fashion with time of irradiance, paralleling the changes in the quantum efficiencies of the photosystems. In contrast, the activation of NADP-malate dehydrogenase did not show a lag period but increased with time, reaching a maximum value at about 50 seconds of illumination, after which it declined. The NADP pool was not extensively reduced during the first 10 seconds of illumination, but became so subsequently. It remained in the reduced state until about 60 seconds of illumination and then became relatively oxidized. The empirical relationship between NADP-malate dehydrogenase activity and the reduction state of the NADP pool supports the suggestion that NADP-malate dehydrogenase activity is a useful estimate of the reduction state of the stroma.

Partitioning of Noncyclic Photosynthetic Electron Transport to O2-Dependent Dissipative Processes as Probed by Fluorescence and CO2 Exchange

The partitioning of noncyclic photosynthetic electron transport between net fixation of CO(2) and collective O(2)-dependent, dissipative processes such as photorespiration has been examined in intact leaf tissue from Nicotiana tabacum. The method involves simultaneous application of CO(2) exchange and pulse modulated fluorescence measurements. As either irradiance or CO(2) concentration is varied at 1% O(2) (i.e. absence of significant O(2)-dependent electron flow), the quantum efficiency of PSII electron transport (phi(se)) with CO(2) as the terminal acceptor is a linear function of the ratio of photochemical:nonphotochemical fluorescence quenching coefficients (i.e. q(Q):q(NP)). When the ambient O(2) concentration is raised to 20.5% or 42% the q(Q):q(NP) is assumed to predict the quantum efficiency of total noncyclic electron transport (phi'(se)). A factor which represents the proportion of electron flow diverted to the aforementioned dissipative processes is calculated as (phi'(se) - phi(se))/phi'(se) where phi(se) is now the observed quantum efficiency of electron transport in support of net fixation of CO(2). Examination of changes in electron allocation with CO(2) and O(2) concentration and irradiance at 25 degrees C provides a test of the applicability of the Rubisco model to photosynthesis in vivo.

Photophosphorylation as a function of light intensity

1. If there is a critical light intensity below which photophosphorylation cannot occur, it is much lower than heretofore reported. At exceedingly low light intensities phosphorylation does not increase in a linear manner with increasing light intensity. This non-linearity seems to be a property of the electron transport-dependent phosphorylation reaction and not a property of the electron transport itself. The very slight non-linearity is independent of the H + concentration of the medium between pH 7.0 and 10.0. The quantum efficiency of photophosphorylation is highest at pH 9 although proton accumulation at this pH is extremely inefficient. 2. Photophosphorylation remains an almost linear function of light intensity in the presence of uncouplers such as methylamine, atebrin, Triton X-100 or Ag +. On the other hand uncouplers such as carbonylcyanide 3-chlorophenylhydrazone (CCCP), 2,4-dinitrophenol, gramicidin and valinomycin inhibit phosphorylation much more severely at very low light intensities. The marked decrease in the quantum efficiency of phosphorylation with CCCP and 2,4-dinitrophenol at low light intensities is associated with some decrease in the quantum efficiency of electron transport. Nevertheless a part of the decrease in efficiency is probably attributable to the weakness with which very low rates of electron transport are coupled to phosphorylation.