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Ring substituted 3-phenyl-1-(2-pyrazinyl)-2-propen-1-ones as potential photosynthesis-inhibiting, antifungal and antimycobacterial agents.

Four series of ring substituted (E)-3-phenyl-1-(2-pyrazinyl)-2-propen-1-ones were prepared by means of modified Claisen-Schmidt condensation of acetylpyrazines with aromatic aldehydes. The structures were confirmed by elemental analysis, IR, 1H NMR and 13C NMR spectra. The compounds were tested for specific biological properties and some derivatives exhibited photosynthesis-inhibiting, antifungal and antimycobacterial properties. The most pronounced effects were observed with compounds substituted with phenolic groups. Ortho-hydroxyl substituted derivatives were more potent than the corresponding para-hydroxyl substituted analogues.

Antifungal Agents↗

A cytochrome b origin of photosynthetic reaction centers: an evolutionary link between respiration and photosynthesis.

The evolutionary origin of photosynthetic reaction centers has long remained elusive. Here, we use sequence and structural analysis to demonstrate an evolutionary link between the cytochrome b subunit of the cytochrome bc(1) complex and the core polypeptides of the photosynthetic bacterial reaction center. In particular, we have identified an area of significant sequence similarity between a three contiguous membrane-spanning domain of cytochrome b, which contains binding sites for two hemes, and a three contiguous membrane-spanning domain in the photosynthetic reaction center core subunits, which contains binding sites for cofactors such as (bacterio)chlorophylls, (bacterio)pheophytin and a non-heme iron. Three of the four heme ligands in cytochrome b are found to be conserved with the cofactor ligands in the reaction center polypeptides. Since cytochrome b and reaction center polypeptides both bind tetrapyrroles and quinones for electron transfer, the observed sequence, functional and structural similarities can best be explained with the assumption of a common evolutionary origin. Statistical analysis further supports a distant but significant homologous relationship. On the basis of previous evolutionary analyses that established a scenario that respiration evolved prior to photosynthesis, we consider it likely that cytochrome b is the evolutionary precursor for type II reaction center apoproteins. With a structural analysis confirming a common evolutionary origin of both type I and type II reaction centers, we further propose a novel "reaction center apoprotein early" hypothesis to account for the development of photosynthetic reaction center holoproteins.

Amino Acid Sequence↗

In situ impact of petrochemicals on the photosynthesis of the seagrass Zostera capricorni.

We used photosynthetic activity (measured as chlorophyll a fluorescence) and photosynthetic pigment concentrations to assess the effect of pulsed exposures of aged crude oil (Champion Crude), dispersant (VDC) and an oil+dispersant mixture on the seagrass Zostera capricorni Aschers in laboratory and field experiments, using custom-made chambers. Samples were exposed for 10 h to 0.25% and 0.1% concentrations of aged crude oil and dispersant as well as mixtures of 0.25% oil+0.05% dispersant and 0.1% oil+0.02% dispersant. During this time and for the subsequent four day recovery period, the maximum and effective quantum yields of photosystem II (Fv/Fm and DeltaF/Fm' respectively) were measured. In the laboratory experiments, both values declined in response to oil exposure and remained low during the recovery period. Dispersant exposure caused a decline in both values during the recovery period, while the mixture of aged crude oil+dispersant had little impact on both quantum yields. In situ samples were less sensitive than laboratory samples, showing no photosynthetic impact due to dispersant and oil+dispersant mixture. Despite an initial decline in DeltaF/Fm', in situ oil-exposed samples recovered by the end of the experiment. Chlorophyll pigment analysis showed only limited ongoing impact in both laboratory and field situations. This study suggests that laboratory experiments may overestimate the ongoing impact of petrochemicals on seagrass whilst the dispersant VDC can reduce the impact of oil on seagrass photosynthesis.

Analysis of Variance↗

Physiological responses to copper in giant clams: a comparison of two methods in revealing effects on photosynthesis in zooxanthellae.

In the present work physiological responses to a short term, sub-lethal exposure to copper (5 microg Cu2 l(-1) were studied on two species of giant clams, Tridacna gigas and Hippopus hippopus. All giant clams (fam. Tridacnidae) maintain a symbiotic relationship with photo-synthesising microalgae (zooxanthellae) and the phytotoxic effects of this copper concentration were approached with two different end points: changes in oxygen production and maximal quantum yield (Fv/Fm). Additionally we measured respiration, whereby Pg:R ratios could be calculated for the system (algae and clam) and used as an indicator of stress. Cu accumulation was only determined for T. gigas and showed significantly higher tissue concentrations in exposed specimens (11.3 microg Cu g(-1) dry wt) compared to the controls (4.2 microg Cu g(-1)). Both species displayed significantly reduced Pg:R ratios due to exposure, mainly explained by lowered gross production. No indication of stress was shown in the fluorescence measurements and possible explanations are discussed in the paper. We propose that inhibitions in the slow kinetics of photosynthesis were not captured by this fluorescence parameter. Accordingly we suggest that measurements of maximum fluorescence yield should be accompanied by complementary parameters when studying pollutants with unclear phytotoxic mechanisms.

Animals↗

Photosynthesis and respiration of a wheat stand at reduced atmospheric pressure and reduced oxygen.

A 34-day functional test was conducted in Johnson Space Center's Variable Pressure Growth Chamber (VPGC) to determine responses of a wheat stand to reduced pressure (70 kPa) and modified partial pressures of carbon dioxide and oxygen. Reduced pressure episodes were generally six to seven hours in duration, were conducted at reduced ppO2 (14.7 kPa), and were interrupted with longer durations of ambient pressure (101 kPa). Daily measurements of stand net photosynthesis (Pn) and dark respiration (DR) were made at both pressures using a ppCO2 of 121 Pa. Corrections derived from leakage tests were applied to reduced pressure measurements. Rates of Pn at reduced pressure averaged over the complete test were 14.6% higher than at ambient pressure, but rates of DR were unaffected. Further reductions in ppO2 were achieved with a molecular sieve and were used to determine if Pn was enhanced by lowered O2 or by lowered pressure. Decreased ppO2 resulted in enhanced rates of Pn, regardless of pressure, but the actual response was dependent on the ratio of ppO2/ppCO2. Over the range of ppO2/ppCO2 of 80 to 200, the rate of Pn declined linearly. Rate of DR was unaffected over the same range and by dissolved O2 levels down to 3.1 ppm, suggesting that normal rhizosphere and canopy respiration occur at atmospheric ppO2 levels as low as 11 kPa. Partial separation of effects attributable to oxygen and those related to reduced pressure (e.g. enhanced diffusion of CO2) was achieved from analysis of a CO2 drawdown experiment. Results will be used for design and implementation of studies involving complete crop growth tests at reduced pressure.

Atmospheric Pressure↗

Redox characteristics of Schiff base manganese and cobalt complexes related to water-oxidizing complex of photosynthesis.

In an effort to obtain synthetic analogues of water-oxidizing complex (WOC) of photosystem II (PS II) of plant photosynthesis, a Schiff base manganese and a cobalt complex, employing Niten, a SALEN type ligand, have been prepared. Cyclic and square wave voltammetric measurements have been performed to assess their redox characteristics. Both complexes undergo several reduction processes in cathodic negative potential region at more or less similar potentials. In view of these reductions being independent of the nature of the metal, they are thought to be ligand-localized. Although similar in negative region, a marked difference in the behavior of the complexes is observed in anodic region. While the cobalt complex is electrochemically inactive in the positive potentials up to +1.0 V vs. Ag/AgCl, the manganese complex displays two oxidation waves at +0.25 and +0.5 V vs. Ag/AgCl. The presence of oxidation wave in manganese complex at +0.5 V vs. Ag/AgCl or +0.7 V vs. NHE suggests that this complex can catalyze the oxidation of water and can, thus, simulate the WOC of PS II.

Cobalt↗

Photosynthesis: new light on biological oxygen production.

In oxygenic photosynthesis, a highly oxidising chlorophyll species strips electrons out of two water molecules, generating molecular oxygen as a waste product. A recent study has provided new insights into the structure of the molecular machinery responsible for biological oxygen production.

Crystallography, X-Ray↗

Photosynthesis: a new twist to biological solar power.

New crystallographic data for the bacterial photoreaction centre have brought an intriguing insight into the structural changes that accompany the primary event in photosynthesis, the conversion of light energy into chemical energy.

Crystallography, X-Ray↗

Biological identity and diversity in photosynthesis and respiration: structure of the lumen-side domain of the chloroplast Rieske protein.

BACKGROUND: The cytochrome b6f complex functions in oxygenic photosynthesis as an integral membrane protein complex that mediates coupled electron transfer and proton translocation. The Rieske [2Fe-2S] protein subunit of the complex functions at the electropositive (p) membrane interface as the electron acceptor for plastoquinol and donor for the cytochrome f subunit, and may have a dynamic role in catalyzing electron and proton transfer at the membrane interface. There are significant structure/function similarities to the cytochrome bc1 complex of the respiratory chain. RESULTS: The 1.83 A crystal structure of a 139-residue C-terminal fragment of the Rieske [2Fe-2S] protein, derived from the cytochrome b6f complex of spinach chloroplasts, has been solved by multiwavelength anomalous diffraction. The structure of the fragment comprises two domains: a small 'cluster-binding' subdomain and a large subdomain. The [2Fe-2S] cluster-binding subdomains of the chloroplast and mitochondrial Rieske proteins are virtually identical, whereas the large subdomains are strikingly different despite a common folding topology. A structure-based sequence alignment of the b6f and bc1 groups of Rieske soluble domains is presented. CONCLUSIONS: The segregation of structural conservation and divergence in the cluster-binding and large subdomains of the Rieske protein correlates with the overall relatedness of the cytochrome b6f and bc1 complexes, in which redox domains in the aqueous p phase are dissimilar and those within the membrane are similar. Distinct sequences and surface charge distributions among Rieske large subdomains may provide a signature for interaction with the p-side oxidant protein and for the pH of the intraorganelle compartment.

Amino Acid Sequence↗

Physiological regulation of carbon fixation in the photosynthesis and calcification of coccolithophorids.

Emiliania huxleyi and Gephyrocapsa oceanica are the predominant coccolithophorid species that produce blooms in the ocean and affect the global environment. These species are capable of carbon fixation by both photosynthesis for organic matter production and by intracellular calcification for coccolith production. Both processes were strongly affected by the nutrient status in a laboratory culture. The coccolith production was stimulated by the addition of a high concentration of sodium bicarbonate and by the depletion of phosphate. Interestingly, when the calcification was stimulated, the increase in cell number during algal growth was greatly suppressed and then the cell volume increased. When the growth rate was increased under nutrient-sufficient conditions, the cells became very small in size and most of them bore few or no coccoliths. The data from laboratory experiments show that the cell growth and calcification proceeded apparently independently at different phases. We, therefore, assume that the coccolithophorid blooms in the ocean might be separated into two phases; firstly, the increase in cell population might be triggered by an adequate supply of nutrients to enhance algal growth and then the calcification might subsequently be stimulated when the nutrients become depleted by substantial algal growth.

Calcification, Physiologic↗

Age-related changes in photosynthesis of woody plants.

Woody peoffnials do not appear to go through a defined senescence phase but do have predictable developmental stages. Reduced photosynthesis and stomatal conductance have been reported at all developmental transitions, although some studies have shown the opposite. What causes these changes and why do results differ among studies? Do these changes result from or cause changes in growth? What are the roles of genetics, size, changing conditions and cumulative environmental stress in aging trees? Definitive answers remain elusive but recent research is helping to clarify some of the processes associated with aging and to point the way for further study.

Photosynthesis↗

Enhancing photosynthesis with sugar signals.

Photosynthesis has long been a target in the quest to maximize crop productivity to feed burgeoning populations. Recent evidence suggests that improved photosynthetic performance can be most easily achieved by modifying sugar-signalling mechanisms that control the expression of genes for whole pathways and processes that determine photosynthetic capacity and source-sink balance, rather than by directly targeting individual 'key' enzymes. Here, we highlight recent progress and support for the hypothesis that genetic modification of trehalose metabolism through its interaction with sugar-signalling pathways can enhance photosynthetic capacity.

Carbohydrate Metabolism↗

The effect of water motion on short-term rates of photosynthesis by marine phytoplankton.

Phytoplankton respond to variations in light intensity as they are mixed through the water column. Changes in pigment content are characteristic of the relatively slow response of 'sun-shade' photoacclimation that occurs on timescales typical of mixing in the open ocean. In estuaries, the variations are much faster and induce correspondingly rapid changes in the activity (rather than abundance) of different components of the photosynthetic apparatus. These components modulate light harvesting and Calvin cycle activity, or protect the pigment bed from excess energy absorption. When the protective capacity is exceeded, photoinhibition occurs. All these mechanisms modulate the rate of photosynthesis in situ.

Light↗

The influence of sugar synthesis and transport rates on bioenergetics and kinetics of higher plant photosynthesis.

We have obtained the theoretical dependences of stromal metabolite steady-state concentrations on external inorganic phosphate (P(i)) concentration. For this purpose, the theoretical model of photosynthesis, earlier described in [Ann. Appl. Biol. 138 (2001) 117], was modified to account for the regulation of starch formation by 3-phosphoglycerate (PGA) to P(i) ratio. When the rate constant of starch synthesis is taken to be independent on PGA/P(i) ratio, the steady-state concentrations of Calvin cycle metabolites and starch were found to change insignificantly as external P(i) concentration increases in wide range. However, as external P(i) range exceeds a critical value, the steady-state concentrations of all metabolites change abruptly. If the rate constant of starch synthesis depends on PGA/P(i) ratio, the steady-state concentrations of stromal metabolites change qualitatively in the same way with the increase of external P(i). However, no abrupt changes of metabolite and starch steady-state levels at high concentration of P(i) are observed. These results testify that the control of starch synthesis by PGA/P(i) ratio makes the photosynthetic system more stable in wide range of external P(i) concentrations.

Biological Transport↗

Electron transfer between membrane complexes and soluble proteins in photosynthesis.

Photosynthesis consists of a series of endergonic redox reactions, with light as the source of energy, chlorophyll as the energy converter, and electrons flowing through membrane and soluble proteins. Here, we give an account of the most recent results on the structure-function relationships of the membrane-embedded complexes cytochrome b(6)-f and photosystem I and of the two soluble proteins (cytochrome c(6) and plastocyanin) that serve as alternative electron carriers between them. Particular attention is paid to the evolutionary aspects of the reaction mechanism and transient protein-protein interactions between the membrane complexes and their partners in cyanobacteria, eukaryotic algae, and plants.

Cytochromes b6↗

Thiol regulation of the thylakoid electron transport chain--a missing link in the regulation of photosynthesis?

Avoidance of over-reduction of the chloroplast ferredoxin pool is of paramount importance for plants in avoiding oxidative stress. The redox state of this pool can be controlled through regulation of the thylakoid electron transport chain. A model is presented for regulation of this chain via a thiol reduction mechanism, possibly involving a thioredoxin. It is shown in isolated thylakoids that electron transport is inhibited by the thiol reducing agent dithiothreitol. The kinetics of this reduction are rapid and readily reversible. The midpoint redox potential is -365 mV at pH 7.7, with a pH dependency of about -90 mV/pH. At physiological pH values, this places the potential of the species titrated between that of ferredoxin and NADPH and thus in the right potential range to be regulating the redox poise of the ferredoxin pool. This is also close to the potential of NADPH-malate dehydrogenase, an enzyme known to be regulated by thioredoxin. Regulation of electron transport by thioredoxin provides a mechanistic link between the regulation of photosynthesis and gene expression by sugars and the redox regulation of gene expression mediated through the plastoquinone pool.

Chlorophyll↗

A look within LHCII: differential analysis of the Lhcb1-3 complexes building the major trimeric antenna complex of higher-plant photosynthesis.

The major antenna complex of higher-plant photosynthesis, LHCII, is composed by the products of three genes, namely, Lhcb1-2-3. In this paper, the biochemical and spectroscopic properties of each of the three gene products were investigated. The three complexes were obtained by overexpression of the apoproteins in bacteria and refolding in vitro with purified pigments, thus allowing detection of differences in the structure/function of the pigment-binding gene products. The analyses showed that Lhcb1 and Lhcb2 complexes have similar pigment binding properties, although not identical, while Lhcb3 is clearly different with respect to both pigment binding and spectral properties and cannot produce homotrimers in vitro. Heterotrimers containing Lhcb3 together with Lhcb1 and/or -2 proteins were obtained upon assembly with Lhcb proteins purified from thylakoids. The major functional characteristics of Lhcb3 with respect to Lhcb1 and -2 consisted in (i) a red-shift of one specific chlorophyll a chromophore, strongly affecting the red-most region of the absorption spectrum and (ii) a different specificity for xanthophylls binding to sites L2 and N1. These properties make Lhcb3 a relative sink for excitation energy in isolated heterotrimers with Lhcb1 + Lhcb2, and potentially, a preferential site of regulation of the antenna function in excess light conditions.

Amino Acid Sequence↗

Photocycle of the flavin-binding photoreceptor AppA, a bacterial transcriptional antirepressor of photosynthesis genes.

The flavoprotein AppA from Rhodobacter sphaeroides contains an N-terminal domain belonging to a new class of photoreceptors designated BLUF domains. AppA was shown to control photosynthesis gene expression in response to blue light and oxygen tension. We have investigated the photocycle of the AppA BLUF domain by ultrafast fluorescence, femtosecond transient absorption, and nanosecond flash-photolysis spectroscopy. Time-resolved fluorescence experiments revealed four components of flavin adenine dinucleotide (FAD) excited-state decay, with lifetimes of 25 ps, 150 ps, 670 ps, and 3.8 ns. Ultrafast transient absorption spectroscopy revealed rapid internal conversion and vibrational cooling processes on excited FAD with time constants of 250 fs and 1.2 ps, and a multiexponential decay with effective time constants of 90 ps, 590 ps, and 2.7 ns. Concomitant with the decay of excited FAD, the rise of a species with a narrow absorption difference band near 495 nm was detected which spectrally resembles the long-living signaling state of AppA. Consistent with these results, the nanosecond flash-photolysis measurements indicated that formation of the signaling state was complete within the time resolution of 10 ns. No further changes were detected up to 15 micros. The quantum yield of the signaling-state formation was determined to be 24%. Thus, the signaling state of the AppA BLUF domain is formed on the ultrafast time scale directly from the FAD singlet excited state, without any apparent intermediate, and remains stable over 12 decades of time. In parallel with the signaling state, the FAD triplet state is formed from the FAD singlet excited state at 9% efficiency as a side reaction of the AppA photocycle.

Bacterial Proteins↗