Interference of ruthenium red analogues at photosystem II of spinach thylakoids

The effect of ruthenium red analogues on several thylakoid photosynthetic activities has been investigated. RR, RV, RRPh1, RRPh2 and Ph inhibit ATP synthesis and electron flow from water to MV (basal, phosphorylating and uncoupled) as their concentration increases, thus, they act as a Hill reaction inhibitor. They inhibit uncoupled electron transport through PSII from water to DCPIP and partially from DPC to DCPIP. However, these compounds do not affect uncoupled PSI electron transport from DCPIP to MV. Therefore, the target of interaction is at the level of OEC and the span P(680) to Q(A) for RR, RRPh1 and RRPh2. Chlorophyll a fluorescence studies corroborate the already found interference sites and may affect the disconnection between chlorophyll molecules within the LHCII and/or between antennae and RCs, or decreases the exciton to reach the RC and inhibition of PSII occurs. RRPh2 is six times more active than RR. Finally, Ph inhibits electron flow interacting at the level of Q(B).     

Alteration in photosystem II photochemistry of thylakoids isolated from senescing leaves of wheat seedlings

Wheat seedlings, grown for 7 days in the light, were allowed to senesce in the light or dark, and the change in the photosystem II (PS II) photochemistry of chloroplasts isolated from the primary leaves of these seedlings was investigated. The decrease in oxygen evolution and the fast fluorescence results indicated that the impairment of PS II in the leaves of seedlings senescing in the light was different from that in the leaves of seedlings senescing in the dark. Thermoluminescence studies showed a structural modification in the Q_B protein of chloroplasts isolated from leaves senescing in the light and an alteration in the S state transition of chloroplasts isolated from leaves senescing in the dark.     

Protection of photosystem II against UV-A and UV-B radiation in the cyanobacterium Plectonema boryanum: the role of growth temperature and growth irradiance

Plectonema boryanum UTEX 485 cells were grown at 29 degrees C and 150 mumol m-2 s-1 photosynthetically active radiation (PAR) and exposed to PAR combined with ultraviolet-A radiation (UV-A) at 15 degrees C. This induced a time-dependent inhibition of photosystem II (PSII) photochemistry measured as a decrease of the chlorophyll a fluorescence ratio, Fv/Fm, to 50% after 2 h of UV-A treatment compared to nontreated control cells. Exposure of the same cells to PAR combined with UV-A + ultraviolet-B radiation (UV-B) caused only a 30% inhibition of PSII photochemistry relative to nontreated cells. In contrast, UV-A and UV-A + UV-B irradiation of cells cultured at 15 degrees C and 150 mumol m-2 s-1 had minimal effects on the Fv/Fm values. However, cells grown at 15 degrees C and lower PAR irradiance (6 mumol m-2 s-1) exhibited similar inhibition patterns of PSII photochemistry as control cells. The decreased sensitivity of PSII photochemistry of P. boryanum grown at 15 degrees C and 150 mumol m-2 s-1 to subsequent exposure to UV radiation relative to either control cells or cells grown at low temperature but low irradiance was correlated with the following: (1) a reduced efficiency of energy transfer to PSII reaction centers; (2) higher levels of a carotenoid tentatively identified as myxoxanthophyll; (3) the accumulation of scytonemin and mycosporine amino acids; and (4) the accumulation of ATP-dependent caseinolytic proteases. Thus, acclimation of P. boryanum at low temperature and moderate irradiance appears to confer significant resistance to UV-induced photoinhibition of PSII. The role of excitation pressure in the induction of this resistance to UV radiation is discussed.     

Lipids in photosystem II: multifunctional cofactors

To maintain its functionality, photosystem II (PSII) employs several types of auxiliary molecules (cofactors). As shown for PSII from Thermosynechococcus elongatus, lipids previously thought to play mostly the role of a hydrophobic matrix for embedding the membrane proteins, must be considered as a new, multifunctional type of cofactors, playing a vital role in the fine tuning of PSII and in its overall operation. The 2.9 ? resolution crystal structure of cyanobacterial homodimeric PSII showed the position of 25 lipid molecules per monomer, and allowed detailed analysis of individual binding sites as well as functional aspects related to lipids. The positions of the bound lipids suggest that they are essential for the assembly and disassembly of PSII, provide the proper environment for plastoquinone exchange, might tune electron transfer through contacts with chlorophylls and carotenoids, and might serve as an oxygen-outlet system from the lumen.     

Psb30 is a photosystem II reaction center subunit and is required for optimal growth in high light in Chlamydomonas reinhardtii

The psb30 (ycf12) gene is conserved in a wide variety of oxygenic-photosynthetic organisms except angiosperms and some marine cyanobacteria. Psb30 protein is found in cyanobacterial photosystem II (PSII) core complexes and is dispensable for PSII structure and function. The most recent three-dimensional structure of cyanobacterial PSII core complex has revealed that Psb30 is located in proximity of PsbJ, PsbK, and PsbZ. However Psb30 has not yet been detected in PSII complexes from eukaryotic photosynthetic organisms. Here we found the expression of the chloroplast psb30 gene in the green alga Chlamydomonas reinhardtii by immunoblotting and Psb30 is exclusively co-purifies with PSII core complex and is significantly reduced in PSII-deficient mutants. Partial disintegration of PSII core complex and subsequent fractionation of the resulting subcomplexes revealed that Psb30 is exclusively associated with PSII reaction center. We have generated chloroplast transformants in which the psb30 gene is disrupted and the resulting ΔPsb30 cells showed decreased oxygen evolution activity by 15%, grew photosynthetically under moderate light, and displayed increased sensitivity to high light relative to wild type. We conclude that Psb30 is a PSII reaction center subunit and is required for optimal PSII function under high light environments.     

Laser induced photoacoustic spectroscopy in liquid samples: temperature and solvent effects

Summary Laser induced photoacoustic spectroscopy (LIPAS) has been confirmed as an analytical tool, suitable for the determination of inorganic and organic species in aqueous and organic solvents, reaching detection limits two orders of magnitude lower than those obtained with conventional spectrophotometry.A significant influence of the solvent on the enhancement of the magnitude of the LIPAS response waveform of the piezoelectric detector has been found experimentally for inorganic species (neodymium ions) and organic compounds (e.g. -carotene and the cytochrome c), when water was replaced by organic solvents. This is particularly true, when a laser excitation wavelength above 500 nm was used, where the absorption coefficient for H₂O increases drastically.Furthermore, the temperature dependence of the magnitude of the LIPAS signal has been measured, in the range between 20–70°C in samples containing Nd³⁺,-carotene and the macromolecule cytochrome c in various aqueous and organic (polar and non-polar) solvents (H₂O, HClO₄, acetone, ethanol and petrol ether). A very strong enhancement of the LIPAS response was observed with increasing temperature (a factor of two in an interval between 20 and 40°C) for all inorganic and organic substances in aqueous solution. On the other hand, in polar and non-polar organic solvents only a slight decline of the signals of about 20% was found over the same temperature range.     

Kinetic studies of photosystem II in photosynthesis

Abstract— It appears that even if some kinetic aspects of the activation and stimulation phenomena of photosystem II remain not understood. the only interpretation we can propose involves the addition of the effect of two photoreactions on the same photochemical center. The main arguments we developed in favour of this hypothesis are: (1) the formation of one atom of oxygen requires the addition of the effect of two photo-reactions (one photoreaction per electron). (2) after a dark period two quanta must be absorbed by the same photochemical center in order to produce oxygen. (3) the existence of a form of the photochemical substrate in which energy is stored is proved by the fact that. after a preillumination by two flashes, the quantum requirement for the production of one molecule of oxygen can reach a value almost two times lower than the quantum requirement measured in stationary conditions.     

Oxygen evolving complex in photosystem II: better than excellent

The Oxygen Evolving Complex in photosystem II, which is responsible for the oxidation of water to oxygen in plants, algae and cyanobacteria, contains a cluster of one calcium and four manganese atoms. This cluster serves as a model for the splitting of water by energy obtained from sunlight. The recent published data on the mechanism and the structure of photosystem II provide a detailed architecture of the oxygen-evolving complex and the surrounding amino acids. Biomimetically, we expect to learn some strategies from this natural system to synthesize an efficient catalyst for water oxidation, that is necessary for artificial photosynthesis.     

Photophysics of PTCDA and Me-PTCDI thin films: effects of growth temperature

The effect of deposition temperature on the photophysical properties of 3,4,9,10-perylenetetracarboxylic dianhydride (PTCDA) and N,N'-dimethylperylene-3,4,9,10-bis(dicarboximide) (Me-PTCDI) films is investigated with steady-state and time-resolved spectroscopy. Atomic force microscopy (AFM) images of the film surfaces show an increase in the dimensions of crystallites with substrate temperature, culminating in the formation of elongated crystallites on substrates held close to the sublimation temperature. In contrast, despite an improvement in the crystal quality, X-ray diffraction (XRD) studies indicate that the substrate temperature has a negligible effect on the molecular orientation; the PTCDA and Me-PTCDI molecules align parallel and tilted to the substrate surface, respectively. Both materials exhibit characteristic absorption, due to mixing between charge-transfer and Frenkel species, and broad structureless photoluminescence. Growth at elevated temperatures gives rise to increased low-energy absorption, attributed to the formation of charge-transfer species, and enhanced blue-shifted emission, although the effects are less pronounced for Me-PTCDI. Time-correlated single-photon counting data indicate that the enhancement coincides with a lengthening of the fluorescence decays, over the whole emission spectrum.     

Constitution and energetics of photosystem I and photosystem II in the chlorophyll d-dominated cyanobacterium Acaryochloris marina

This mini review presents current topics of discussion about photosystem (PS) I and PS II of photosynthesis in the Acaryochloris marina. A. marina is a photosynthetic cyanobacterium in which chlorophyll (Chl) d is the major antenna pigment (>95%). However, Chl a is always present in a few percent. Chl d absorbs light with a wavelength up to 30 nm red-shifted from Chl a. Therefore, the chlorophyll species of the special pair in PS II has been a matter of debate because if Chl d was the special pair component, the overall energetics must be different in A. marina. The history of this field indicates that a purified sample is necessary for the reliable identification and characterization of the special pair. In view of the spectroscopic data and the redox potential of pheophytin, we discuss the nature of special pair constituents and the localization of the enigmatic Chl a.     

Sr(II)-UPRM-5 titanium silicate framework thermally induced contraction: in situ high temperature XRD and 29Si MAS NMR

The thermally induced contraction process of a titanosilicate prepared with tetraethylammonium hydroxide and ion exchanged with Sr(II) (Sr-UPRM-5) after detemplation has been characterized via in situ high temperature X-ray diffraction (XRD) and (29)Si magic angle spinning nuclear magnetic resonance (MAS NMR). The as-synthesized material was prepared via conventional and microwave-assisted hydrothermal methods, the latter resulting in a reaction time an order of magnitude shorter than the former case. In situ high temperature XRD tests performed on Sr-UPRM-5 indicate that at 120 °C, water coordinated to the structure is released initiating the collapse of the framework. At much higher temperatures, the material eventually becomes an amorphous phase. Indexing of the XRD patterns indicates that lattice constant a was more affected by the heat treatment, probably related to the material's pore system, while the unit cell volume experienced a 44% reduction. (29)Si MAS NMR analyses for as-synthesized UPRM-5 confirmed two different silicon environments: Si(2Si, 2Ti(octa)) and Si(3Si, 1Ti(semi-octa)), which are similar to those exhibited by titanosilicate ETS-4. On the other hand, in situ high temperature (29)Si MAS NMR analyses for Sr-UPRM-5 demonstrated that changes in the silicon environment due to the presence of titanium centers possessing additional multiple coordination states, which arise from elimination of framework coordinated water molecules, are responsible for the structure collapsing. In general, these results underline the importance of avoiding complete removal of tenacious water molecules in order to preserve the Sr-UPRM-5 properties suitable for adsorption and catalysis applications.     

Control of quinone redox potentials in photosystem II: Electron transfer and photoprotection

In O(2)-evolving complex Photosystem II (PSII), an unimpeded transfer of electrons from the primary quinone (Q(A)) to the secondary quinone (Q(B)) is essential for the efficiency of photosynthesis. Recent PSII crystal structures revealed the protein environment of the Q(A/B) binding sites. We calculated the plastoquinone (Q(A/B)) redox potentials (E(m)) for one-electron reduction with a full account of the PSII protein environment. We found two different H-bond patterns involving Q(A) and D2-Thr217, resulting in an upshift of E(m)(Q(A)) by 100 mV if the H bond between Q(A) and Thr is present. The formation of this H bond to Q(A) may be the origin of a photoprotection mechanism, which is under debate. At the Q(B) side, the formation of a H bond between D2-Ser264 and Q(B) depends on the protonation state of D1-His252. Q(B) adopts the high-potential form if the H bond to Ser is present. Conservation of this residue and H-bond pattern for Q(B) sites among bacterial photosynthetic reaction centers (bRC) and PSII strongly indicates their essential requirement for electron transfer function.     

Assembly of the water-oxidizing complex in photosystem II

The efficient incorporation and assembly of calcium, chloride and manganese followed by photoactivation of the water-oxidizing complex (WOC) is a prerequisite for the unique water-splitting activity of photosystem II. This minireview summarizes the recent results on incorporation and storage of the inorganic cofactors, photoactivation of the WOC and assembly of the protein environment at the donor site of PSII in cyanobacteria with a special focus on the role of the Psb27 protein.     

On the dimerization of chlorophyll in photosystem II

In photosystem II, absorbed light energy is transferred to a reaction centre consisting of chlorophyll units. Release of an electron from the reaction centre is the starting point for the charge separation and electron transport chain in PSII. Crystal structures of the reaction centre have identified two chlorophyll monomers forming a dimer with a partial structural overlap, thus being stabilized by van der Waals interactions. However, the magnitude of this interaction is not accurately known. In this work, the structure of the chlorophyll dimer has been optimized for the first time using dispersion-corrected density functional theory (B3LYP-DCP) revealing the magnitude of dimerization to be approximately -17 kcal mol(-1). The dispersion interaction is shown to be of great significance for the chlorophyll dimer stabilization. In addition, the redox potential of the chlorophyll dimer is calculated to be 1283 mV in good agreement with recent experimental data.     

On the effects of high temperature and high pressure on the hydrogen solubility in rhenium

In situ x-ray diffraction experiments on rhenium hydride compressed up to 46 GPa reveal a hydrogen solubility (x) significantly larger than the previously assumed saturation limit of x ~ 0.38(4). In the layered anti-CdI(2)-type structure of rhenium hydride, the hydrogen solubility was found to increase to x ~ 0.5 at 15 GPa over time. When heated to temperatures above 420 K at pressures above 23 GPa, rhenium hydride undergoes an isomorphous phase transition into the NiAs-type structure accompanied by an increase in hydrogen solubility to x ~ 0.85. The formation of fully stoichiometric rhenium hydride is discussed.     

Oxygen evolution loss and structural transitions in photosystem II induced by low intensity UV-B radiation of 280 nm wavelength

UV-B radiation of 280 nm wavelength (UV280) and low intensity (2.0 W/m2) gives rise to an important oxygen evolution (OE) loss in photosystem II (PSII) particles isolated from the thylakoid membrane of plant chloroplasts on the one hand, and to structural changes, or transitions, in the proteins of the PSII complex on the other hand. The latter UV280 effect was studied in this work by Fourier transform infrared (FT-IR) spectroscopy. First, irradiation of the PSII particles with UV280 for about 40 min causes an almost complete loss of OE activity. The remaining OE after 15, 20, 30 and 40 min is respectively 52, 44, 27 and 12% of the OE activity in control PSH particles kept in darkness. Secondly, difference FT-IR spectra of PSII particles irradiated for 30 min, i.e., [PSII irradiated with UV280]-minus-[PSII non-irradiated], show that the UV280 light is at the origin of significant IR absorbance changes in several spectral regions: (i) amide I (1696-1620 cm(-1)) and amide II (1580-1520 cm(-1)), (ii) tyrosine side chain (1620-1580 cm(-1) and 1520-1500 cm(-1), i.e., the v8a, v8b and v19a vibrational modes, respectively), and (iii) chlorophylls (1750-1696 cm(-1)). Thirdly, comparison of the UV-B effect reported here with structural changes induced by heat-stress in PSII proteins [M. Joshi, M. Fragata, Z. Naturforsch. 54c (1999) 35-43] clearly indicates that the stability of the functional centers in the PSII complex is dependent on a dynamic equilibrium between a-helix conformers and extended chain (beta-strand) structures. In this framework, transient 'alpha-helix-to-beta-strand transitions' are susceptible of giving rise in vivo to recurrent changes in the activity of the PSII complex, and as such act as a control mechanism of the photosynthetic function in the thylakoid membrane.     

Overall kinetics of photosystem II: pH Dependence and deuterium isotope effect

The overall kinetics of photosystem II was scanned by means of a double flash technique. Oxygen evolution by pea thylakoids provided with an artificial electron acceptor was measured under a regime of double flashes of variant intervals. The pH optimum in H₂O lies near p¹H 7.2 (p¹H meaning the pH in H₂O), with a first-order rate constant of 800 s⁻¹ at 20°C. In deuterium oxide (D₂O), a plateau of maximum reaction rate was found between p²H 6.6 and 7.8 (p²H meaning the “pH” in D₂O), the highest rate constant being 550 s⁻¹. The apparent kinetic deuterium isotope effect is therefore 1.45. Outside this plateau region, there seems to exist another isotope effect of 1.2 to 1.3. These effects are small but may nevertheless reflect the fact that more than one step of the photosystem II reaction sequence is involved in the splitting of a bond to hydrogen. However, the effects may also be solvent effects or located on the acceptor side of the photosystem.