A Possible Evolutionary Origin for the Mn<Subscript>4</Subscript> Cluster in Photosystem II: From Manganese Superoxide Dismutase to Oxygen Evolving Complex

The recently published X-ray absorption fine structure of photosystem II provides a more detailed architecture of the oxygen-evolving complex (OEC) and the surrounding amino acids. In this paper, a comparison between manganese superoxide dismutase, dinuclear manganese catalase enzymes and the oxygen evolving complex in photosystem II is reported. The author suggests that the development of oxygenic photosynthesis occurred in steps, the first of which involved only one manganese ion (Mn(II)) that oxidized two water molecules to hydrogen peroxide and then oxygen.     

Oxidation state changes of the Mn<Subscript>4</Subscript>Ca cluster in Photosystem II

A detailed electronic structure of the Mn₄Ca cluster is required before two key questions for understanding the mechanism of photosynthetic water oxidation can be addressed. They are whether all four oxidizing equivalents necessary to oxidize water to O₂ accumulate on the four Mn ions of the oxygen-evolving complex, or do some ligand-centered oxidations take place before the formation and release of O₂ during the S₃ → [S₄] → S₀ transition, and what are the oxidation state assignments for the Mn during S-state advancement. X-ray absorption and emission spectroscopy of Mn, including the newly introduced resonant inelastic X-ray scattering spectroscopy have been used to address these questions. The present state of understanding of the electronic structure and oxidation state changes of the Mn₄Ca cluster in all the S-states, particularly in the S₂ to S₃ transition, derived from these techniques is described in this review.     

Hollandite as a Functional and Structural Model for the Biological Water Oxidizing Complex: Manganese-Calcium Oxide Minerals as a Possible Evolutionary Origin for the CaMn4 Cluster of the Biological Water Oxidizing Complex

Oxygen evolution was observed upon mixing either hollandite, which has been proposed as a structural model for the biological water oxidizing complex, or hausmannite with an aqueous solution of cerium (IV) ammonium nitrate. Oxygen evolution from water during irradiation with visible light (λ > 400 nm) was also observed upon adding either hollandite or hausmannite to an aqueous solution containing tris (2,2′-bipyridyl)ruthenium(II) chloride and chloro pentaammine cobalt(III) chloride in acetate buffer. These experiments showed that hollandite is a good catalyst for oxygen evolution in presence of cerium (IV) ammonium nitrate or tris (2,2′-bipyridyl)ruthenium (III). Thus, hollandite is not only a structural but also a functional model for the biological water oxidizing complex. Supplemental materials are available for this article. Go to the publisher's online edition of Geomicrobiology Journal to view the free supplemental file.     

Possible Origin of a Minor Virus Specific Protein (A<Subscript>1</Subscript>) in Qβ Particles

RNA phages such as R17, MS2 and f2 (group I of Watanabe¹) consist of a single-stranded RNA, about 180 molecules of coat protein and one of A (or maturation) protein, a component required for the functional integrity of the viral particle, possibly for its adsorption to the host^2–4. The phage genome comprises three cistrons, accounting for the two proteins mentioned above as well as for a component of the viral RNA replicase^5,6.     

Promotion of Energy Transfer and Oxygen Evolution in Spinach Photosystem II by Nano-anatase TiO<Subscript>2</Subscript>

Being a proven photocatalyst, nano-anatase is capable of undergoing electron transfer reactions under light. In previous studies we had proven that nano-anatase improved photosynthesis and greatly promoted spinach growth. The mechanisms by which nano-anatase promotes energy transfer and the conversion efficiency of the process are still not clearly understood. In the present paper, we report the results obtained with the photosystem II (PSII) isolated from spinach and treated by nano-anatase TiO₂ and studied the effect of nano-anatase TiO₂ on energy transfer in PSII by spectroscopy and on oxygen evolution. The results showed that nano-anatase TiO₂ treatment at a suitable concentration could significantly change PSII microenvironment and increase absorbance for visible light, improve energy transfer among amino acids within PSII protein complex, and accelerate energy transport from tyrosine residue to chlorophyll a. The photochemical activity of PSII (fluorescence quantum yield) and its oxygen-evolving rate were enhanced by nano-anatase TiO₂. This is viewed as evidence that nano-anatase TiO₂ can promote energy transfer and oxygen evolution in PSII of spinach.     

Water-splitting manganese complex controls light-induced redox changes of cytochrome <Emphasis Type="Italic">b</Emphasis><Subscript>559</Subscript> in Photosystem II

The effect of water-splitting Mn complex on light-induced redox changes of cytochrome b ₅₅₉ (cyt b ₅₅₉) was studied in spinach photosystem II (PSII) membranes. Photoreduction of the heme iron in the intact PSII membranes was completely suppressed by DCMU, whereas photoreduction and photooxidation of the heme iron in the Mn-depleted PSII membranes were unaffected by DCMU. Interesingly, photoreduction and photooxidation of the heme iron in the Mn-depleted PSII membranes were completely diminished by exogenous superoxide dismutase (SOD), whereas no effect of SOD on photoreduction of the heme iron was observed in the intact PSII membranes. The current work shows that the light-induced redox changes of cyt b ₅₅₉ proceed via a different mechanism in the both types of PSII membranes. In the intact PSII membranes, photoreduction of the heme iron is mediated by plastoquinol. However, in the Mn-depleted PSII membranes, photoreduction and photooxidation of the heme iron are mediated by superoxide anion radical formed in PSII.     

Simulation and optical spectroscopy of a DC discharge in a CH<Subscript>4</Subscript>/H<Subscript>2</Subscript>/N<Subscript>2</Subscript> mixture during deposition of nanostructured carbon films

Two-dimensional numerical simulations of a dc discharge in a CH₄/H₂/N₂ mixture in the regime of deposition of nanostructured carbon films are carried out with account of the cathode electron beam effects. The distributions of the gas temperature and species number densities are calculated, and the main plasmachemical kinetic processes governing the distribution of methyl radicals above the substrate are analyzed. It is shown that the number density of methyl radicals above the substrate is several orders of magnitude higher than the number densities of other hydrocarbon radicals, which indicates that the former play a dominant role in the growth of nanostructured carbon films. The model is verified by comparing the measured optical emission profiles of the H(n ≡ 3), C ₂ ^* , CH*, and CN* species and the calculated number densities of excited species, as well as the measured and calculated values of the discharge voltage and heat fluxes onto the electrodes and reactor walls. The key role of ion–electron recombination and dissociative excitation of H₂, C₂H₂, CH₄, and HCN molecules in the generation of emitting species (first of all, in the cold regions adjacent to the electrodes) is revealed.     

The subcommissural organ expresses D<Subscript>2</Subscript>, D<Subscript>3</Subscript>, D<Subscript>4</Subscript>, and D<Subscript>5</Subscript> dopamine receptors

Dopamine receptors have been found in certain populations of non-neuronal cells in the brain, viz., discrete areas of ciliated ependyma and the ependymal cells of the choroid plexus. We have studied the presence of both tyrosine-hydroxylase-immunoreactive nerve fibers and dopamine receptors in the subcommissural organ (SCO), an ependymal brain gland that is located in the roof of the third ventricle and that secretes, into the cerebrospinal fluid, glycoproteins that aggregate to form Reissners fiber (RF). Antibodies against D₂, D₃, D₄, and D₅ dopamine receptors were used in immunoblots of bovine striatum, fresh SCO, and organ-cultured SCO, and in immunocytochemistry of the bovine, rat, and mouse SCO. Only a few tyrosine-hydroxylase fibers appeared to reach the SCO. However, virtually all the secretory ependymal and hypendymal cells of the SCO immunoreacted with antibodies against D₂, D₄, and D₅ receptors, with the last-mentioned rendering the strongest reaction, especially at the ventricular cell pole of the secretory ependymocytes, suggesting that dopamine might reach the SCO via the cerebrospinal fluid. The antibodies against the four subtypes of receptors revealed corresponding bands in immunoblots of striatum and fresh SCO. Although the cultured SCO displayed dopamine receptors, dopamine had no apparent effect on the expression of the SCO-spondin gene/protein or on the release of RF-glycoproteins (SCO-spondin included) by SCO explants, suggesting that dopamine affects the function(s) of the SCO differently from the secretion of RF-glycoproteins.Financial support was provided by grants PI 030756 and Red CIEN, Instituto de Salud Carlos III, Spain (to J.M.P.F.), and 1030265 from Fondecyt, Chile (to E.M.R.)     

Synthesis of Protein-Inorganic Nanohybrids with Improved Catalytic Properties Using Co<Subscript>3</Subscript>(PO<Subscript>4</Subscript>)<Subscript>2</Subscript>

In the present study, a method for easy and rapid synthesis of lipase nanohybrids was evaluated using cobalt chloride as an encapsulating agent. The synthesized nanohybrids exhibited higher activity (181%) compared to free lipase and improved catalytic properties at higher temperature and in harsh conditions. The nanohybrids retained 84% of their residual activity at 25 °C after 10 days. In addition, these nanohybrids also exhibited high storage stability and reusability. Collectively, the synthesis of carrier-free immobilized biocatalysts was performed rapidly within 24 h at 4 °C. Their high reusability and catalytic activities highlight the broad applicability of this method for catalysis in organic and aqueous media.     

Performance of a generalist grasshopper on a C<Subscript>3</Subscript> and a C<Subscript>4</Subscript> grass: compensation for the effects of elevated CO<Subscript>2</Subscript> on plant nutritional quality

The increasing CO₂ concentration in Earths atmosphere is expected to cause a greater decline in the nutritional quality of C₃ than C₄ plants. As a compensatory response, herbivorous insects may increase their feeding disproportionately on C₃ plants. These hypotheses were tested by growing the grasses Lolium multiflorum C₃) and Bouteloua curtipendula C₄) at ambient (370 ppm) and elevated (740 ppm) CO₂ levels in open top chambers in the field, and comparing the growth and digestive efficiencies of the generalist grasshopper Melanoplus sanguinipes on each of the four plant × CO₂ treatment combinations. As expected, the nutritional quality of the C₃ grass declined to a greater extent than did that of the C₄ grass at elevated CO₂; protein levels declined in the C₃ grass, while levels of carbohydrates (sugar, fructan and starch) increased. However, M. sanguinipes did not significantly increase its consumption rate to compensate for the lower nutritional quality of the C₃ grass grown under elevated CO₂. Instead, these grasshoppers appear to use post-ingestive mechanisms to maintain their growth rates on the C₃ grass under elevated CO₂. Consumption rates of the C₃ and C₄ grasses were also similar, demonstrating a lack of compensatory feeding on the C₄ grass. We also examined the relative efficiencies of nutrient utilization from a C₃ and C₄ grass by M. sanguinipes to test the basis for the C₄ plant avoidance hypothesis. Contrary to this hypothesis, neither protein nor sugar was digested with a lower efficiency from the C₄ grass than from the C₃ grass. A novel finding of this study is that fructan, a potentially large carbohydrate source in C₃ grasses, is utilized by grasshoppers. Based on the higher nutrient levels in the C₃ grass and the better growth performance of M. sanguinipes on this grass at both CO₂ levels, we conclude that C₃ grasses are likely to remain better host plants than C₄ grasses in future CO₂ conditions.     

Photosystem I with benzoquinone analogues incorporated into the A<Subscript>1</Subscript> binding site

Time-resolved FTIR difference spectroscopy has been used to study photosystem I (PSI) particles with three different benzoquinones [plastoquinone-9 (PQ), 2,6-dimethyl-1,4-benzoquinone (DMBQ), 2,3,5,6-tetrachloro-1,4-benzoquinone (Cl₄BQ)] incorporated into the A₁ binding site. If PSI samples are cooled in the dark to 77 K, the incorporated benzoquinones are shown to be functional, allowing the production of time-resolved (P700⁺A₁^??P700A₁) FTIR difference spectra. If samples are subjected to repetitive flash illumination at room temperature prior to cooling, however, the time-resolved FTIR difference spectra at 77 K display contributions typical of the P700 triplet state (³P700), indicating a loss of functionality of the incorporated benzoquinones, that occurs because of double protonation of the incorporated benzoquinones. The benzoquinone protonation mechanism likely involves nearby water molecules but does not involve the terminal iron–sulfur clusters F_A and F_B. These results and conclusions resolve discrepancies between results from previous low-temperature FTIR and EPR studies on similar PSI samples with PQ incorporated.     

Transitional slopes act as hotspots of both soil CO<Subscript>2</Subscript> emission and CH<Subscript>4</Subscript> uptake in a temperate forest landscape

Forest soils are an important component of CO₂ and CH₄ fluxes at the global scale, but the magnitude of these fluxes varies greatly in space and time within a landscape. Understanding the spatial and temporal distributions of these fluxes across complex landscapes remains a major challenge for researchers and land managers alike. We investigated the spatiotemporal variability of soil-atmosphere CO₂ and CH₄ fluxes and the relationships of these fluxes to chemical and physical soil properties distributed across a topographically-heterogeneous landscape. Soil CO₂ and CH₄ fluxes were measured along with soil temperature, moisture, bulk density, texture, carbon, sorption capacity, and dissolved organic matter quality over 2 years along hillslope transects spanning valley bottom, transition zone, and upland landscape positions in a temperate forest watershed. Transition zone soil CO₂ efflux was 54–160% higher than low-lying valley bottoms, and 15–54% higher than uplands. Net seasonal CH₄ uptake was 58–150% higher in transition zone soils than in uplands, while valley bottoms were occasionally large net sources (up to 19 nmol CH₄ m^?2 s^?1). Soil CO₂ efflux and net CH₄ uptake were both positively associated with seasonal temperature, and were highest in soils with relatively high carbon and clay content, and relatively low bulk density, moisture, and sorption capacity. We concluded that: (1) transition zone soils act as landscape hotspots for net CH₄ uptake in addition to CO₂ efflux, and (2) that this spatial distribution is more consistent across seasons for net CH₄ uptake than for CO₂ efflux.     

Activity of C<Subscript>4</Subscript> enzymes in C<Subscript>3</Subscript>-type herbaceous plants

The activity of enzymes characteristic for C₄-type photosynthesis was determined in different organs of two herbaceous plants: Reynoutria japonica Houtt. and Helianthus tuberosus L. The activity of phosphoenolpyruvate carboxylase (PEPC) was usually higher in the roots, some of the stem tissues and petioles in comparison to the leaf blades. The highest activity of malic enzymes (NAD-ME, NADP-ME) and phosphoenolpyruvate carboxykinase (PEPCK) was in the petioles and stem tissues of both plants and the lowest in the leaf blades and the pith of Helianthus tuberosus L.     

Minor Changes in Vegetation and Carbon Gas Balance in a Boreal Mire under a Raised CO<Subscript>2</Subscript> or NH<Subscript>4</Subscript>NO<Subscript>3</Subscript> Supply

Increasing concentrations of carbon dioxide (CO₂) in the atmosphere or continuous nitrogen (N) deposition might alter the carbon (C) cycle in boreal mires and thus have significant impacts on the development of climate change. The atmospheric impact of the C cycle in mires is twofold: C accumulation attenuates and CH₄ release strengthens the natural greenhouse effect. We studied the effects of an increased supply of CO₂ or NH₄NO₃ on the vegetation and annual CO₂ exchange in lawns of a boreal oligotrophic mire in eastern Finland over a 2-year period. Ten study plots were enclosed with mini-FACE (Free Air Carbon Dioxide Enrichment) rings. Five plots were vented with CO₂-enriched air (target 560 ppmv), while their controls were vented with ambient air; five plots were sprayed with NH₄NO₃, corresponding to a cumulative addition of 3 g N m⁻² a⁻¹, while their controls were sprayed with distilled water only. A raised NH₄NO₃ supply seemed to affect the composition of the moss layer. Raised CO₂ did not affect the vegetation, but gross photosynthesis increased significantly. The change in net CO₂ exchange depended on the annual weather conditions. Our results suggest that C accumulation may increase in wet years and compensate for the warming effect caused by the increase in CH₄ release from this mire. In contrast, a relatively dry and warm growing period favors decomposition and can even make the CO₂ balance negative. Along with the increased CH₄ release under raised CO₂, the decreased C accumulation then increases the radiative forcing of boreal mires. Received 22 October 2001; accepted 13 May 2002.     

The polythiophene molecular segment as a sensor model for H<Subscript>2</Subscript>O,HCN, NH<Subscript>3</Subscript>, SO<Subscript>3</Subscript>, and H<Subscript>2</Subscript>S: a density functional theory study

Studying the interaction of some atmospheric gases (H₂O, HCN, NH₃, SO₃ and H₂S) with 3PT oligomers is important in the development of polymeric sensors for gas detection. In the present study, we studied the relaxed geometries, interaction energies, charge analysis, HOMO–LUMO orbital analysis, and UV–vis spectra of all interacted systems using first-principles density functional theory (DFT). All these analyses indicated the potential of polythiophene as an inexpensive polymeric sensor for the analytes mentioned. Interaction energy values of ?19.90, ?19.66, ?14.01, ?8.70, and ?4.76 kJ mol^?1 were achieved for adsorption of SO₃, H₂O, NH₃, HCN, and H₂S on 3PT, respectively. Consequently, clarification of their physical parameters became the major focus of this study.     

Effects of elevated atmospheric CO<Subscript>2</Subscript> on the nutritional ecology of C<Subscript>3</Subscript> and C<Subscript>4</Subscript> grass-feeding caterpillars

It is plausible that the nutritional quality of C₃ plants will decline more under elevated atmospheric CO₂ than will the nutritional quality of C₄ plants, causing herbivorous insects to increase their feeding on C₃ plants relative to C₄ plants. We tested this hypothesis with a C₃ and C₄ grass and two caterpillar species with different diet breadths. Lolium multiflorum (C₃) and Bouteloua curtipendula (C₄) were grown in outdoor open top chambers at ambient (370 ppm) or elevated (740 ppm) CO₂. Bioassays compared the performance and digestive efficiencies of Pseudaletia unipuncta (a grass-specialist noctuid) and Spodoptera frugiperda (a generalist noctuid). As expected, the nutritional quality of L. multiflorum changed to a greater extent than did that of B. curtipendula when grown in elevated CO₂; levels of protein (considered growth limiting) declined in the C₃ grass, while levels of carbohydrates (sugar, starch and fructan) increased. However, neither insect species increased its feeding rate on the C₃ grass to compensate for its lower nutritional quality when grown in an elevated CO₂ atmosphere. Consumption rates of P. unipuncta and S. frugiperda were higher on the C₃ grass than the C₄ grass, the opposite of the result expected for a compensatory response to the lower nutritional quality of the C₄ grass. Although our results do not support the hypothesis that grass-specialist insects compensate for lower nutritional quality by increasing their consumption rates more than do generalist insects, the performance of the specialist was greater than that of the generalist on each grass species and at both CO₂ levels. Mechanisms other than compensatory feeding, such as increased nutrient assimilation efficiency, appear to determine the relative performance of these herbivores. Our results also provide further evidence against the hypothesis that C₄ grasses would be avoided by insect herbivores because a large fraction of their nutrients is unavailable to herbivores. Instead, our results are consistent with the hypothesis that C₄ grasses are poorer host plants primarily because of their lower nutrient levels, higher fiber levels, and greater toughness.     

Synthesis and characterization of core-shell Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>-gold-chitosan nanostructure

Background  

Fe₃O₄-gold-chitosan core-shell nanostructure can be used in biotechnological and biomedical applications such as magnetic bioseparation, water and wastewater treatment, biodetection and bioimaging, drug delivery, and cancer treatment.     

DFT study of isomers of the ruthenium dihydride complex RuH<Subscript>2</Subscript>(CO)<Subscript>2</Subscript>(AsMe<Subscript>2</Subscript>Ph)<Subscript>2</Subscript>

A density functional theory (DFT) study of cct-As, ccc, and cct-CO isomers of the ruthenium dihydride complex RuH₂(CO)₂(AsMe₂Ph)₂ is reported (see Scheme for the labeling isomer 34 structures of RuH₂(CO)₂(AsMe₂Ph)₂). Complex geometries and relative energies of different isomers have been calculated with both B3LYP and M06-2X functionals. The results show that the B3LYP calculated Boltzmann populations of cct-As, ccc, and cct-CO isomers are 65.5, 34.2, and 0.3%, respectively. These are in better agreement with the experimental data than those calculated at the M06-2X level. However, the calculations of ¹H NMR chemical shifts were found to be better described with M06-2X than with B3LYP or with HF level of theories. In addition, a transition state between the two most stable isomers was determined through DFT/(B3LYP or M06-2X) calculations.

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Graphical Abstract Scheme: Labeling structure of RuH₂(CO)₂(AsMe₂Ph)₂