6-Pyruvoyltetrahydropterin synthase orthologs of either a single or dual domain structure are responsible for tetrahydrobiopterin synthesis in bacteria

6-Pyruvoyltetrahydropterin synthase (PTPS) catalyzes the second step of tetrahydrobiopterin (BH4) synthesis. We previously identified PTPS orthologs (bPTPS-Is) in bacteria which do not produce BH4. In this study we disrupted the gene encoding bPTPS-I in Synechococcus sp. PCC 7942, which produces BH4-glucoside. The mutant was normal in BH4-glucoside production, demonstrating that bPTPS-I does not participate in BH4 synthesis in vivo and bringing us a new PTPS ortholog (bPTPS-II) of a bimodular polypeptide. The recombinant Synechococcus bPTPS-II was assayed in vitro to show PTPS activity higher than human enzyme. Further computational analysis revealed the presence of mono and bimodular bPTPS-II orthologs mostly in green sulfur bacteria and cyanobacteria, respectively, which are well known for BH4-glycoside production. In summary we found new bacterial PTPS orthologs, having either a single or dual domain structure and being responsible for BH4 synthesis in vivo, thereby disclosing all the bacterial PTPS homologs.     

Diagnostic parameters for selecting against novel spruce (Picea abies) decline: IV. Response of photosynthesis and transpiration to SO2+NO2 exposures

The dose- and time-response effects of 3 days of 6 h day-time sequential exposures to NO₂, SO₂ and SO₂+NO₂ of 0.45–1.81 μl l⁻¹ (ppm) SO₂ and 1.50–7.65 μl l⁻¹ NO₂ on photosynthesis, transpiration and dark respiration were examined for nine Carpatho-Ukrainian half-sib families and a population from the GFR ('Westerhof') of Norway spruce [ Piecea abies (L.) Karst.], all in their 5th growing season.
SO₂+NO₂ inhibited photosynthesis and transpiration and stimulated dark respiration more than SO₂ alone. SO₂ and SO₂+NO₂ at the lowest concentrations inhibited night transpiration, but increased it at the highest concentration, the strongest effects being obtained with combined exposures. Photosynthesis of the different half-sib families was affected significantly differently by SO₂+NO₂ exposures. NO₂ alone had no effects.
Sensitivity to transpiration decline correlated negatively with branch density. Height of trees correlated postitively with decline sensitivity in the seed orchard. The distribution of photosynthesis and transpiration sensitivities over all tested half-sib families correlated negatively with the distribution of decline sensitivity of their parents in a rural Danish seed orchard. The relative photosynthesis and transpiration sensitivities may thus serve as diagnostic parameters for selecting against novel spruce decline.     

A Lithium–Sulfur Cell Based on Reversible Lithium Deposition from a Li2S Cathode Host onto a Hostless‐Anode Substrate

The development of lithium–sulfur batteries necessitates a thorough understanding of the lithium‐deposition process. A novel full‐cell configuration comprising an Li₂S cathode and a bare copper foil on the anode side is presented here. The absence of excess lithium allows for the realization of a truly lithium‐limited Li–S battery, which operates by reversible plating and stripping of lithium on the hostless‐anode substrate (copper foil). Its performance is closely tied to the efficiency of lithium deposition, generating valuable insights on the role and dynamic behavior of lithium anode. The Li₂S full cell shows reasonable capacity retention with a Coulombic efficiency of 96% over 100 cycles, which is a tremendous improvement over that of a similar lithium‐plating‐based full cell with LiFePO₄ cathodes. The exceptional robustness of the Li₂S system is attributed to an intrinsic stabilization of the lithium‐deposition process, which is mediated by polysulfide intermediates that form protective Li₂S and Li₂S₂ regions on the deposited lithium. Combined with the large improvements in energy density and safety by the elimination of a metallic lithium anode, the stability and electrochemical performance of the lithium‐plating‐based Li₂S full cell establish it as an important trajectory for Li–S battery research, focusing on practical realization of reversible lithium anodes.     

Decoupling Analysis of Four Selected Countries

We examine decoupling conditions of domestic extraction of materials, energy use, and sulfur dioxide (SO₂) emissions from gross domestic product (GDP) for two BRIC (Brazil, Russia, India and China) countries (i.e., China and Russia) and two Organisation for Economic Co‐operation and Development (OECD) countries (Japan and the United States) during 2000–2007, using a pair of decoupling indicators for resource use (D_r) and waste emissions (D_e) and the decoupling chart, which can distinguish between absolute decoupling, relative decoupling, and non‐decoupling. We find that (1) during 2000–2007, decoupling between environmental indicators and GDP was higher in the two OECD countries as compared with the two BRIC countries. The key reason is that these countries were in different development stages with different economic growth rates. (2) Changes in environmental policies can significantly influence the degree of decoupling in a country. (3) China, Japan, and the United States were more successful in decoupling SO₂ emissions from GDP than in decoupling material and energy use from GDP. The main reason is that, unlike resource use, waste emissions (e.g., SO₂ emissions) can be reduced by effective end‐of‐pipe treatment. (4) The decoupling indicator is different from the changing rate of resource use and waste emissions. If two countries have different GDP growth rates, even though they may have similar values using the decoupling indicator, they may show different rates of change for resource use and waste emissions.     

Toward a Reversible Calcium‐Sulfur Battery with a Lithium‐Ion Mediation Approach

Calcium represents a promising anode for the development of high‐energy‐density, low‐cost batteries. However, a lack of suitable electrolytes has restricted the development of rechargeable batteries with a Ca anode. Furthermore, to achieve a high energy density system, sulfur would be an ideal cathode to couple with the Ca anode. Unfortunately, a reversible calcium‐sulfur (Ca‐S) battery has not yet been reported. Herein, a basic study of a reversible nonaqueous room‐temperature Ca‐S battery is presented. The reversibility of the Ca‐S chemistry and high utilization of the sulfur cathode are enabled by employing a Li⁺‐ion‐mediated calcium‐based electrolyte. Mechanistic insights pursued by spectroscopic, electrochemical, microscopic, and theoretical simulation (density functional theory) investigations imply that the Li⁺‐ions in the Ca‐electrolyte stimulate the reactivation of polysulfide/sulfide species. The coordination of lithium to sulfur reduces the formation of sturdy Ca‐S ionic bonds, thus boosting the reversibility of the Ca‐S chemistry. In addition, the presence of Li⁺‐ions facilitates the ionic charge transfer both in the electrolyte and across the solid electrolyte interphase layer, consequently reducing the interfacial and bulk impedance of Ca‐S batteries. As a result, both the utilization of active sulfur in the cathode and the discharge voltage of Ca‐S batteries are significantly improved.     

Stoichiometric modeling of oxidation of reduced inorganic sulfur compounds (Riscs) in Acidithiobacillus thiooxidans

The prokaryotic oxidation of reduced inorganic sulfur compounds (RISCs) is a topic of utmost importance from a biogeochemical and industrial perspective. Despite sulfur oxidizing bacterial activity is largely known, no quantitative approaches to biological RISCs oxidation have been made, gathering all the complex abiotic and enzymatic stoichiometry involved. Even though in the case of neutrophilic bacteria such as Paracoccus and Beggiatoa species the RISCs oxidation systems are well described, there is a lack of knowledge for acidophilic microorganisms. Here, we present the first experimentally validated stoichiometric model able to assess RISCs oxidation quantitatively in Acidithiobacillus thiooxidans (strain DSM 17318), the archetype of the sulfur oxidizing acidophilic chemolithoautotrophs. This model was built based on literature and genomic analysis, considering a widespread mix of formerly proposed RISCs oxidation models combined and evaluated experimentally. Thiosulfate partial oxidation by the Sox system (SoxABXYZ) was placed as central step of sulfur oxidation model, along with abiotic reactions. This model was coupled with a detailed stoichiometry of biomass production, providing accurate bacterial growth predictions. In silico deletion/inactivation highlights the role of sulfur dioxygenase as the main catalyzer and a moderate function of tetrathionate hydrolase in elemental sulfur catabolism, demonstrating that this model constitutes an advanced instrument for the optimization of At. thiooxidans biomass production with potential use in biohydrometallurgical and environmental applications. Biotechnol. Bioeng. 2013; 110: 2242–2251. © 2013 Wiley Periodicals, Inc.     

A caterpillar (Callopistria floridensis G. (Lepidoptera: Noctuidae)) accumulates arsenic from an arsenic‐hyperaccumulating fern (Pteris vittata L.).

1. The consumption of arsenic is toxic to most biota. However, a noctuid caterpillar was recently reported feeding on a plant known to hyperaccumulate arsenic. 2. The aim of this study was to investigate the effects of arsenic‐rich Pteris vittata L. consumption by Callopistria floridensis G., and measure differences in arsenic concentrations at various stages of development (larval and adult), and associated with exuviae and frass. 3. Callopistria floridensis accumulated extraordinary concentrations of arsenic. The relative accumulation of arsenic was highest in exuviae and larvae. Larvae invariably preferred P. vittata grown on low arsenic soil to P. vittata grown on higher soil arsenic concentrations, and appeared able to selectively forage on lower arsenic concentrations within each treatment. 4. These findings show that C. floridensis is tolerant of arsenic, and successfully develops to adulthood containing elevated concentrations of arsenic. Callopistria floridensis represents the only known terrestrial animal capable of accumulating arsenic, and may have developed novel physiological and behavioural adaptations to regulate the negative effects of arsenic.     

Semi-continuum electrostatic calculations of redox potentials in photosystem I

The midpoint redox potentials (E(m)) of all cofactors in photosystem I from Synechococcus elongatus as well as of the iron-sulfur (Fe(4)S(4)) clusters in two soluble ferredoxins from Azotobacter vinelandii and Clostridium acidiurici were calculated within the framework of a semi-continuum dielectric approach. The widely used treatment of proteins as uniform media with single dielectric permittivity is oversimplified, particularly, because permanent charges are considered both as a source for intraprotein electric field and as a part of dielectric polarizability. Our approach overcomes this inconsistency by using two dielectric constants: optical epsilon(o)=2.5 for permanent charges pre-existing in crystal structure, and static epsilon(s) for newly formed charges. We also take into account a substantial dielectric heterogeneity of photosystem I revealed by photoelectric measurements and a liquid junction potential correction for E(m) values of relevant redox cofactors measured in aprotic solvents. We show that calculations based on a single permittivity have the discrepancy with experimental data larger than 0.7 V, whereas E(m) values calculated within our approach fall in the range of experimental estimates. The electrostatic analysis combined with quantum chemistry calculations shows that (i) the energy decrease upon chlorophyll dimerization is essential for the downhill mode of primary charge separation between the special pair P(700) and the primary acceptor A(0); (ii) the primary donor is apparently P(700) but not a pair of accessory chlorophylls; (iii) the electron transfer from the A branch quinone Q(A) to the iron-sulfur cluster F(X) is most probably downhill, whereas that from the B branch quinone Q(B) to F(X) is essentially downhill.