Dissipation Of Excitation Energy Research Articles

A STUDY OF LUMINESCENCE EXCITATION OF POLYMERIC EUROPIUM(III) METHACRYLATE: CASSCF/XMCQDPT2

The lowest singlet and triplet levels of europium(III) methacrylate Eu(Macr)3, including geometry optimization in different excited states, are calculated with the CASSCF/XMCQDPT2 ab initio method. The experimental and calculated data are used to build energy diagrams of Eu(Macr)3 energy levels, describe the luminescence mechanism in the complex, and to reveal the main channels for the dissipation of the electronic excitation energy. Due to the position of its lower triplet levels, europium methacrylate can be used to prepare novel materials with improved optical properties.

Changes in Photo-Protective Energy Dissipation of Photosystem II in Response to Beneficial Bacteria Consortium in Durum Wheat under Drought and Salinity Stresses

The present research aimed at evaluating the harmless dissipation of excess excitation energy by durum wheat (Triticum durum Desf.) leaves in response to the application of a bacterial consortium consisting of four plant growth-promoting bacteria (PGPB). Three pot experiments were carried out under non-stress, drought (at 40% field capacity), and salinity (150 mM NaCl) conditions. The results showed that drought and salinity affected photo-protective energy dissipation of photosystem II (PSII) increasing the rate of non-photochemical chlorophyll fluorescence quenching (NPQ (non-photochemical quenching) and qCN (complete non-photochemical quenching)), as well as decreasing the total quenching of chlorophyll fluorescence (qTQ), total quenching of variable chlorophyll fluorescence (qTV) and the ratio of the quantum yield of actual PSII photochemistry, in light-adapted state to the quantum yield of the constitutive non-regulatory NPQ (PQ rate). Our results also indicated that the PGPB inoculants can mitigate the adverse impacts of stresses on leaves, especially the saline one, in comparison with the non-fertilized (control) treatment, by increasing the fraction of light absorbed by the PSII antenna, PQ ratio, qTQ, and qTV. In the light of findings, our beneficial bacterial strains showed the potential in reducing reliance on traditional chemical fertilizers, in particular in saline soil, by improving the grain yield and regulating the amount of excitation energy.

Dynamical and allosteric regulation of photoprotection in light harvesting complex II.

Major light-harvesting complex of photosystem II (LHCII) plays a dual role in light-harvesting and excited energy dissipation to protect photodamage from excess energy. The regulatory switch is induced by increased acidity, temperature or both. However, the molecular origin of the protein dynamics at the atomic level is still unknown. We carried out temperature-jump time-resolved infrared spectroscopy and molecular dynamics simulations to determine the energy quenching dynamics and conformational changes of LHCII trimers. We found that the spontaneous formation of a pair of local α-helices from the 310-helix E/loop and the C-terminal coil of the neighboring monomer, in response to the increased environmental temperature and/or acidity, induces a scissoring motion of transmembrane helices A and B, shifting the conformational equilibrium to a more open state, with an increased angle between the associated carotenoids. The dynamical allosteric conformation change leads to close contacts between the first excited state of carotenoid lutein 1 and chlorophyll pigments, facilitating the fluorescence quenching. Based on these results, we suggest a unified mechanism by which the LHCII trimer controls the dissipation of excess excited energy in response to increased temperature and acidity, as an intrinsic result of intense sun light in plant photosynthesis.

Strong Anisotropy in Liquid Water upon Librational Excitation Using Terahertz Laser Fields.

Tracking the excitation of water molecules in the homogeneous liquid is challenging due to the ultrafast dissipation of rotational excitation energy through the hydrogen-bonded network. Here we demonstrate strong transient anisotropy of liquid water through librational excitation using single-color pump-probe experiments at 12.3 THz. We deduce a third-order response of χ3 exceeding previously reported values in the optical range by 3 orders of magnitude. Using a theory that replaces the nonlinear response with a material property amenable to molecular dynamics simulation, we show that the rotationally damped motion of water molecules in the librational band is resonantly driven at this frequency, which could explain the enhancement of the anisotropy in the liquid by the external terahertz field. By addition of salt (MgSO4), the hydration water is instead dominated by the local electric field of the ions, resulting in reduction of water molecules that can be dynamically perturbed by THz pulses.

Characterization of fluorescent chlorophyll charge-transfer states as intermediates in the excited state quenching of light-harvesting complex II.

Light-harvesting complex II (LHCII) is the major antenna complex in higher plants and green algae. It has been suggested that a major part of the excited state energy dissipation in the so-called "non-photochemical quenching" (NPQ) is located in this antenna complex. We have performed an ultrafast kinetics study of the low-energy fluorescent states related to quenching in LHCII in both aggregated and the crystalline form. In both sample types the chlorophyll (Chl) excited states of LHCII are strongly quenched in a similar fashion. Quenching is accompanied by the appearance of new far-red (FR) fluorescence bands from energetically low-lying Chl excited states. The kinetics of quenching, its temperature dependence down to 4K, and the properties of the FR-emitting states are very similar both in LHCII aggregates and in the crystal. No such FR-emitting states are found in unquenched trimeric LHCII. We conclude that these states represent weakly emitting Chl-Chl charge-transfer (CT) states, whose formation is part of the quenching process. Quantum chemical calculations of the lowest energy exciton and CT states, explicitly including the coupling to the specific protein environment, provide detailed insight into the chemical nature of the CT states and the mechanism of CT quenching. The experimental data combined with the results of the calculations strongly suggest that the quenching mechanism consists of a sequence of two proton-coupled electron transfer steps involving the three quenching center Chls 610/611/612. The FR-emitting CT states are reaction intermediates in this sequence. The polarity-controlled internal reprotonation of the E175/K179 aa pair is suggested as the switch controlling quenching. A unified model is proposed that is able to explain all known conditions of quenching or non-quenching of LHCII, depending on the environment without invoking any major conformational changes of the protein.

Salicylic Acid Protects Photosystem II by Alleviating Photoinhibition in Arabidopsis thaliana under High Light.

Salicylic acid (SA) is considered to play an important role in plant responses to environmental stresses. However, the detailed protective mechanisms in photosynthesis are still unclear. We therefore explored the protective roles of SA in photosystem II (PSII) in Arabidopsis thaliana under high light. The results demonstrated that 3 h of high light exposure resulted in a decline in photochemical efficiency and the dissipation of excess excitation energy. However, SA application significantly improved the photosynthetic capacity and the dissipation of excitation energy under high light. Western blot analysis revealed that SA application alleviated the decrease in the levels of D1 and D2 protein and increased the amount of Lhcb5 and PsbS protein under high light. Results from photoinhibition highlighted that SA application could accelerate the repair of D1 protein. Furthermore, the phosphorylated levels of D1 and D2 proteins were significantly increased under high light in the presence of SA. In addition, we found that SA application significantly alleviated the disassembly of PSII-LHCII super complexes and LHCII under high light for 3 h. Overall, our findings demonstrated that SA may efficiently alleviate photoinhibition and improve photoprotection by dissipating excess excitation energy, enhancing the phosphorylation of PSII reaction center proteins, and preventing the disassembly of PSII super complexes.

A Flexible LHCII Structure Allows for Fine-Tuning of Excitation Energy Dissipation

The major light-harvesting complex of photosystem II (LHCII) is the main contributor to sunlight energy harvesting in plants. The flexible design of LHCII underlies a photoprotective mechanism whereby this complex switches to a dissipative state in response to high light stress, allowing the rapid dissipation of excess excitation energy (NPQ). In this work, we stabilized the quenched conformation of single LHCII trimers after immobilization of the complexes in polyacrylamide gels to impede protein interactions. A comparison of their pigment excited-state dynamics with quenched LHCII aggregates in buffer revealed the presence of a new spectral band at 515 nm arising after chlorophyll excitation. This is suggested to be the signature of a carotenoid excited state, linked to the quenching of chlorophyll singlet excited states. Our data highlight the marked sensitivity of pigment excited-state dynamics in LHCII to structural changes induced by the environment.

Photosystem II antenna complexes CP26 and CP29 are essential for nonphotochemical quenching in Chlamydomonas reinhardtii.

Photosystems must balance between light harvesting to fuel the photosynthetic process for CO2 fixation and mitigating the risk of photodamage due to absorption of light energy in excess. Eukaryotic photosynthetic organisms evolved an array of pigment‐binding proteins called light harvesting complexes constituting the external antenna system in the photosystems, where both light harvesting and activation of photoprotective mechanisms occur. In this work, the balancing role of CP29 and CP26 photosystem II antenna subunits was investigated in Chlamydomonas reinhardtii using CRISPR‐Cas9 technology to obtain single and double mutants depleted of monomeric antennas. Absence of CP26 and CP29 impaired both photosynthetic efficiency and photoprotection: Excitation energy transfer from external antenna to reaction centre was reduced, and state transitions were completely impaired. Moreover, differently from higher plants, photosystem II monomeric antenna proteins resulted to be essential for photoprotective thermal dissipation of excitation energy by nonphotochemical quenching.

Structural and chemical mechanism underlying formation of Zn2SiO4:Mn crystalline phosphor properties

Zn2SiO4:Mn crystalline phosphor is a substitutional solid solution Zn2-2xMn2xSiO4, with х≤0.13. As the number of activator ions x > 0.13 grows, the mechanism of defect formation changes: some manganese ions change from doubly charged to triply charged, which is accompanied by the emergence of vacancies in the zinc sublattice. It is demonstrated that the coordination number of Mn3+ ions in the structure of willemite is five. The concentration quenching of Zn2SiO4:Mn is associated with the oxidation of a part of activator ions and dissipation of excitation energy on structural defects.

The role of xanthophylls in the supramolecular organization of the photosynthetic complex LHCII in lipid membranes studied by high-resolution imaging and nanospectroscopy

The xanthophyll cycle is a regulatory mechanism operating in the photosynthetic apparatus of plants. It consists of the conversion of the xanthophyll pigment violaxanthin to zeaxanthin, and vice versa, in response to light intensity. According to the current understanding, one of the modes of regulatory activity of the cycle is associated with the influence on a molecular organization of pigment-protein complexes. In the present work, we analyzed the effect of violaxanthin and zeaxanthin on the molecular organization of the LHCII complex, in the environment of membranes formed with chloroplast lipids. Nanoscale imaging based on atomic force microscopy (AFM) showed that the presence of exogenous xanthophylls promotes the formation of the protein supramolecular structures. Nanoscale infrared (IR) absorption analysis based on AFM-IR nanospectroscopy suggests that zeaxanthin promotes the formation of LHCII supramolecular structures by forming inter-molecular β-structures. Meanwhile, the molecules of violaxanthin act as “molecular spacers” preventing self-aggregation of the protein, potentially leading to uncontrolled dissipation of excitation energy in the complex. This latter mechanism was demonstrated with the application of fluorescence lifetime imaging microscopy. The intensity-averaged chlorophyll a fluorescence lifetime determined in the LHCII samples without exogenous xanthophylls at the level of 0.72 ns was longer in the samples containing exogenous violaxanthin (2.14 ns), but shorter under the presence of zeaxanthin (0.49 ns) thus suggesting a role of this xanthophyll in promotion of the formation of structures characterized by effective excitation quenching. This mechanism can be considered as a representation of the overall photoprotective activity of the xanthophyll cycle.

Morphological and Physiological Stress Responses of Lettuce to Different Intensities of Continuous Light.

In this study, specific dynamic changes in growth, oxidative stress, ascorbate metabolism, and chlorophyll fluorescence were monitored during 12 days in lettuce plants exposed to continuous light (CL) of different intensities: low light (LL, 100 μmol·m−2·s−1), medium light (ML, 200 μmol·m−2·s−1), and high light (HL, 300 μmol·m−2·s−1). Lettuce plants grown under CL of higher light intensity gained greater biomass, dry weight ratio, root/shoot ratio, and specific leaf FW, but not leaf area. Both the reactive oxygen species (ROS) production and the lipid peroxidation degree, measured in terms of the malondialdehyde (MDA) levels, were progressively enhanced by increasing the light intensity of CL. Overall, the pool sizes of ascorbate (AsA) and glutathione, as well as the activities of enzymes involved in AsA metabolism, had positive correlations with light intensity under CL. Ascorbate peroxidase and dehydroascorbate reductase presented the maximal and minimal responses to light intensity, respectively, among all the studied enzymes. After 6 days under CL, ML and HL intensity caused reversible photoinhibition, represented by lower values of maximum quantum efficiency (F v /F m), effective quantum yield (ΦPSII), and photochemical quenching (qP) and a higher value of non-photochemical quenching (qN). However, this photoinhibition recovered on day 12 with increasing of F v /F m, ΦPSII, and qP. Taken together, under ML and HL conditions, greater AsA level could help maintain photosynthetic efficiency by elevating excess excitation energy dissipation, though ROS accumulation and lipid peroxidation could not be prevented in the long-term. Likewise, there was no dark period under LL condition, but no photooxidative stress was observed in lettuce. Thus, it is concluded that photooxidative stress induced by CL can be attributed to excessive daily light integral instead of circadian asynchrony.

Effects of UV Radiation on Photosynthesis, Antioxidant Capacity and the Accumulation of Bioactive Compounds in Gracilariopsis longissima, Hydropuntia cornea and Halopithys incurva (Rhodophyta).

The red macroalgae Hydropuntia cornea, Gracilariopsis longissima and Halopithys incurva were cultured for 14d under laboratory conditions, in enriched seawater with a high nutrient content (N-NH4+ and P-PO43- ) and two radiation regimes: PAR (400-700nm) and PAB (280-700nm). The UV radiation effects under high availability of nutrients on growth, photosynthetic pigments (chlorophyll a, carotenoids and phycobiliproteins), photosynthetic activity and biochemical composition were studied. Maximum quantum yield (Fv /Fm ) was not significantly different among the PAR and PAB treatments during the experiment. However, the maximum electronic transport rate (ETRmax ) increased over time, showing the highest values in PAR for H.incurva and H.cornea, whereas for G.longissima it was found in PAB. Photosynthetic efficiency (αETR ) decreased over time in the first two species, but increased in G.longissima. Saturation irradiance (EkETR ) and maximum nonphotochemical quenching (NPQmax ) increased in PAB with time up to 80% and 30%, respectively, indicating a photosynthetic acclimatization like that of sun-type algae. Five MAAs were identified in all species using high performance liquid chromatography (HPLC). The total content of MAAs increased over time, being 30% higher in H.incurva, 40% in G.longissima and 50% in H.cornea in PAB than in the PAR treatment. Finally, the antioxidant activity was also higher in the PAB treatment. All of the species presented an effective mechanism of photoprotection based on the accumulation of photoprotective compounds with antioxidant activity, as well as a high dissipation of excitation energy (high NPQmax ).

Photorespiration is the major alternative electron sink under high light in alpine evergreen sclerophyllous Rhododendron species

Owing to the high leaf mass per area, alpine evergreen sclerophyllous Rhododendron have low values of mesophyll conductance (gm). The resulting low chloroplast CO2 concentration aggravates photorespiration, which requires a higher ATP/NADPH ratio. However, the significance of photorespiration and underlying mechanisms of energy balance in these species are little known. In this study, eight alpine evergreen sclerophyllous Rhododendron species grown in a common garden were tested for their gm, electron flow to photorespiration, and energy balancing. Under saturating light, gm was the most limiting factor for net photosynthesis (AN) in all species, and the species differences in AN were primarily driven by gm rather than stomatal conductance. The total electron flow through photosystem II (ETRII) nearly equaled the electron transport required for Rubisco carboxylation and oxygenation. Furthermore, blocking electron flow to photosystem I with appropriate inhibitors showed that electron flow to plastic terminal oxidase was not observed. As a result, these studied species showed little alternative electron flow mediated by water-water cycle or plastic terminal oxidase. By comparison, the ratio of electron transport consumed by photorespiration to ETRII (JPR/ETRII), ranging from 43%∼55%, was negatively correlated to AN and gm. Furthermore, the increased ATP production required by enhanced photorespiration was regulated by cyclic electron flow around photosystem I. These results indicate that photorespiration is the major electron sink for dissipation of excess excitation energy in the alpine evergreen sclerophyllous Rhododendron species. The coordination of gm, photorespiration and cyclic electron flow is important for sustaining leaf photosynthesis.

Monomeric light harvesting complexes enhance excitation energy transfer from LHCII to PSII and control their lateral spacing in thylakoids

Proper assembly of plant photosystem II, in the appressed region of thylakoids, allows for both efficient light harvesting and the dissipation of excitation energy absorbed in excess. The core moiety of wild type supercomplex is associated with monomeric antennae that, in turn, bind peripheral trimeric LHCII complexes. Acclimation to light environment dynamics involves structural plasticity within PSII-LHCs supercomplexes, including depletion in LHCII and CP24. Here, we report on the acclimation of NoM, an Arabidopsis mutant lacking monomeric LHCs but retaining LHCII trimer. Lack of monomeric LHCs impaired the operation of both photosynthetic electron transport and state transitions, despite the fact that NoM underwent a compensatory over-accumulation of the LHCII complement compared to the wild type. Mutant plants displayed stunted growth compared to the wild type when probed over a range of light conditions. When exposed to short-term excess light, NoM showed higher photosensitivity and enhanced singlet oxygen release than the wild type, whereas long-term acclimation under stress conditions was unaffected. Analysis of pigment-binding supercomplexes showed that the absence of monomeric LHCs did affect the macro-organisation of photosystems: large PSI-LHCII megacomplexes were more abundant in NoM, whereas the assembly of PSII-LHCs supercomplexes was impaired. Observation by electron microscopy (EM) and image analysis of thylakoids highlighted impaired granal stacking and membrane organisation, with a heterogeneous distribution of PSII and LHCII compared to the wild type. It is concluded that monomeric LHCs are critical for the structural and functional optimisation of the photosynthetic apparatus.

Origin of the Concentration Quenching of Luminescence in Zn2SiO4:Mn Phosphors

The analysis of the unified series of single-phase Zn2 – 2xMn2xSiO4 samples (x ≤ 0.2) has provided the possibility to determine the optimal dopant concentration x = 0.13 for the maximum luminescence intensity. It has been established that the dominating mechanism of concentration luminescence quenching and excitation energy dissipation is the oxidation of some Mn2+ activating ions and the growth of defectness in the luminophore due to this process Phosphors.

Integrating temporal and spatial control of electronic transitions for bright multiphoton upconversion

The applications of lanthanide-doped upconversion nanomaterials are limited by unsatisfactory brightness currently. Herein, a general strategy is proposed for boosting the upconversion efficiency in Er3+ ions, based on combined use of a core−shell nanostructured host and an integrated optical waveguide circuit excitation platform. A NaErF4@NaYF4 core−shell nanoparticle is constructed to host the upconversion process for minimizing non-radiative dissipation of excitation energy by surface quenchers. Furthermore, an integrated optical microring resonator is designed to promote absorption of excitation light by the nanoparticles, which alleviates quenching of excited states due to cross-relaxation and phonon-assisted energy transfer. As a result, multiphoton upconversion emission with a large anti-Stokes shift (greater than 1150 nm) and a high energy conversion efficiency (over 5.0%) is achieved under excitation at 1550 nm. These advances in controlling photon upconversion offer exciting opportunities for important photonics applications.

On the Nonmonotonic, Hormetic Photoprotective Response of Plants to Stress.

Accumulated evidence show that reactive species play a dual role in plants as well, with likely biphasic responses. This suggests that photoprotective mechanisms may also show similar patterns because they are highly related to reactive species. The nonphotochemical quenching (NPQ) is an index of heat dissipation of excitation energy in the antenna system. We present here preliminary evidence from some published studies showing significant biphasic response of NPQ to increasing doses of stress, with U-shaped or inverted U-shaped dose–response relationships, typical of hormesis. This evidence provides a remarkable perspective for designing novel studies where the fate of light energy will be seen through the lens of hormesis.

The positive regulation of putrescine on light-harvesting complex II and excitation energy dissipation in salt-stressed cucumber seedlings

Non-photochemical quenching (NPQ) is an important mechanism employed by higher plants to protect themselves against the adverse effects of excess excitation energy. The regulatory mechanism of exogenous putrescine (Put) on the status of light-harvesting complex II (LHCII) and its dissipation of excess excitation energy in cucumber seedlings (Cucumis sativus L.) were investigated under salt stress in this study. Put significantly increased the maximum quantum photochemical efficiency in photosystem II (Fv/Fm), NPQ, and the actual yield of PSII (ΦPSII) under salt stress. Quantum yield of regulated energy dissipation in PSII (ΦNPQ) significantly increased and non-regulated energy dissipation (ΦNO) decreased when was sprayed on stressed plants. Put increased the expression levels of D1, D2, Lhcb4 and PsbS, thereby minimizing degradation to the monomeric and trimeric states of LHCII in the thylakoid membranes of salt-stressed cucumber leaves. In addition, Put up-regulated the activity of transglutaminase (TGase) and significantly increased the levels of total endogenous polyamines in monomeric and trimeric LHCII under salt stress. These results suggest that Put could play a crucial role in dissipating excess excitation energy by regulating endogenously increased polyamines to alter the adaptation of LHCII, which are most probably involved in an improvement of photochemical efficiency in salt stressed-cucumber seedlings.

The PSI-PSII Megacomplex in Green Plants.

Energy dissipation is crucial for land and shallow-water plants exposed to direct sunlight. Almost all green plants dissipate excess excitation energy to protect the photosystem reaction centers, photosystem II (PSII) and photosystem I (PSI), and continue to grow under strong light. In our previous work, we reported that about half of the photosystem reaction centers form a PSI-PSII megacomplex in Arabidopsis thaliana, and that the excess energy was transferred from PSII to PSI fast. However, the physiological function and structure of the megacomplex remained unclear. Here, we suggest that high-light adaptable sun-plants accumulate the PSI-PSII megacomplex more than shade-plants. In addition, PSI of sun-plants has a deep trap to receive excitation energy, which is low-energy chlorophylls showing fluorescence maxima longer than 730 nm. This deep trap may increase the high-light tolerance of PSI by improving excitation energy dissipation. Electron micrographs suggest that one PSII dimer is directly sandwiched between two PSIs with 2-fold rotational symmetry in the basic form of the PSI-PSII megacomplex in green plants. This structure should enable fast energy transfer from PSII to PSI and allow energy in PSII to be dissipated via the deep trap in PSI.

BASF & SINOPEC sign MoU to strengthen chemical production in China

Non-photochemical quenching (NPQ) is an important mechanism employed by higher plants to protect themselves against the adverse effects of excess excitation energy. The regulatory mechanism of exogenous putrescine (Put) on the status of light-harvesting complex II (LHCII) and its dissipation of excess excitation energy in cucumber seedlings (Cucumis sativus L.) were investigated under salt stress in this study. Put significantly increased the maximum quantum photochemical efficiency in photosystem II (Fv/Fm), NPQ, and the actual yield of PSII (ΦPSII) under salt stress. Quantum yield of regulated energy dissipation in PSII (ΦNPQ) significantly increased and non-regulated energy dissipation (ΦNO) decreased when was sprayed on stressed plants. Put increased the expression levels of D1, D2, Lhcb4 and PsbS, thereby minimizing degradation to the monomeric and trimeric states of LHCII in the thylakoid membranes of salt-stressed cucumber leaves. In addition, Put up-regulated the activity of transglutaminase (TGase) and significantly increased the levels of total endogenous polyamines in monomeric and trimeric LHCII under salt stress. These results suggest that Put could play a crucial role in dissipating excess excitation energy by regulating endogenously increased polyamines to alter the adaptation of LHCII, which are most probably involved in an improvement of photochemical efficiency in salt stressed-cucumber seedlings.