Protonation,alkylation, addition and redox reactions of 16, 17 and 18 valence electron [Mo(L)(NO)('S4')] complexes [L = SPh,PMe3, NO; 'S4'2– = 1,2-Bis-(2-mercaptophenylthio)ethane(2-)]

In the quest for complexes modelling functional characteristics of metal sulfur oxidoreductases, a series of molybdenum nitrosyl complexes with sulfur-dominated coordination sphere was synthesized. Treatment of the 16, 17 and 18 valence electron (VE) complexes [Mo(L)(NO)('S₄')] (1–3) [L?=?SPh (1), PMe₃ (2), NO (3), 'S₄'^2–?=?1,2-bis-(2-mercaptophenylthio) ethane(2-)] with the Brönsted acid HBF₄ resulted in formation of different types of products. 1 and 3 were reversibly protonated at one thiolate atom of the 'S₄'^2– ligand;2, however, yielded the phosphonium salt [HPMe₃]BF₄ and the dinuclear [Mo(NO)('S₄')]₂. Alkylation of 1, 2 and 3 by Me₃OBF₄ or Et₃OBF₄ uniformly resulted in high yields of [Mo(L)(NO)(R-'S₄')]BF₄ complexes [L?=?SPh: R?=?Me (5), Et (6); L?=?PMe₃: R?=?Me (7); L?=?NO: R?=?Me (8), Et (9)] in which one thiolate atom of the 'S₄'^2– ligand had become alkylated; the NMR spectra of 5, 6, 8 and 9 indicated that only one out of four theoretically possible diastereoisomers had formed. 5 and 6 were characterized also by single-crystal X-ray structure analyses. A comparison of ν(NO) bands and redox potentials (cyclic voltammetry) of parent complexes and alkylated derivatives showed that alkylation leads to a decrease in electron density at the molybdenum center and to a positive shift in redox potentials. The 16 VE complex 1 could be reduced, also chemically, to give the corresponding 17 VE anion [1]^–, and inserted elemental sulfur into the Mo-SPh bond, forming the 18 VE phenylperthio complex [Mo(η²–SSPh)(NO)('S₄')] (11) which, upon reaction with PPh₃, gave SPPh₃ and regenerated the parent complex 1. These results are discussed with regard to the sequence of proton and electron transfer steps occurring in substrate conversions catalyzed by metal sulfur oxidoreductases.     

Chloroherpeton thalassium gen. nov. et spec. nov., a non-filamentous,flexing and gliding green sulfur bacterium

A flexing and gliding green sulfur bacterium has been isolated from marine sources off the North East coast of the USA. Chloroherpeton thalassium is an obligate phototroph, and requires CO₂ and S^2- for growth; some organic acids can contribute to cell carbon, and N₂ may be fixed. The cells contain typical chlorosomes, and gas vesicles may be present. Bacteriochlorophyll c is the main light harvesting pigment, and a small quantity of bacteriochlorophyll a is also present. Over 80% of the carotenoid is -carotene. DNA base composition of the isolates ranges from 45.0–48.2 mol% G+C.In memory of R. Y. Stanier     

Development of regulation mechanisms for SO42- influx in spring wheat roots

The development of SO₄^2- influx in roots and sulfur transport to shoots was followed in ³⁵S-tracer experiments for sulfur-deficient spring wheat (Triticum aestivum L. cv. Svenno) seedlings pretreated for various time periods (0–24 h) in nutrient solutions with SO₄^2-. Effects of the metabolic inhibitor 2,4-dinitrophenol (DNP) and the protein synthesis inhibitor cycloheximide (CH) on SO₄^2- influx were also evaluated. The SO₄^2- influx appears feedback-regulated by the internal sulfur level of the roots. Regulation may be achieved solely by a rapidly changed SO₄^2- carrier activity through an allosteric effect by the intracellular SO₄^2- concentration of the roots, followed first by induction of carrier synthesis and then by repression of carrier synthesis after transfer of the roots from SO₄^2--deficient nutrient solutions to solutions with SO₄^2-. A Hill plot of the partly sigmoidal relationship between SO₄^2- influx and intracellular sulfur concentration in the roots gave a Hill coefficient of -4.2, indicating negative cooperativity between a minimum number of four interacting allosteric binding sites for sulfur on each carrier entity. DNP-experiments showed that SO₄^2- influx was mainly metabolic, especially after short pretreatment in SO₄^2- at an external SO₄^2- concentration of 0.1 mM. Pretreatment with CH rapidly prevented new SO₄^2- carriers from being formed. Long CH pretreatment (24 h) and different SO₄^2- pretreatments reduced SO₄^2- influx below the non-metabolic level obtained by uptake experiments with DNP, indicating the existence of SO₄^2- carriers mediating passive SO₄^2- transport across the plasmalemma of the root cells. SO₄^2- influx was further decreased for the CH pretreated (24 h) plants by the presence of both CH and DNP in the experimental nutrient solution. This probably indicates the diffusive part of the non-metabolic SO₄^2- influx in the present experiments. Finally, it is suggested that there is a feedback signal between root and shoot, regulating sulfur transport upwards.     

Phloem transport of sulfur in Ricinus

Mature leaves of Ricinus communis fed with ³⁵SO ₄ ^2- in the light export labeled sulfate and reduced sulfur compounds by phloem transport. Only 1–2% of the absorbed radiosulfur is exported to the stem within 2–3 h, roughly 12% of ³⁵S recovered was in reduced form. The composition of phloem translocate moving down the stem toward the root was determined from phloem exudate: 20–40% of the ³⁵S moved in the form of organic sulfur compounds, however, the bulk of sulfur was transported as inorganic sulfate. The most important organic sulfur compound translocated was glutathione, carrying about 70% of the label present in the organic fraction. In addition, methionine and cysteine were involved in phloem sulfur transport and accounted for roughly 10%. Primarily, the reduced forms of both, glutathione and cysteine are prsent in the siever tubes.Abbreviations CySH cysteine - GSH glutathione - GSSG glutathione disulfide - NEM N-ethylmaleimide - CyS-SCy cystine     

Seasonal and spatial patterns of S,Ca, and N dynamics of a Northern Hardwood forest ecosystem

Seasonal dynamics of S, Ca and N were examined at the Huntington Forest, a northern hardwood ecosystem in the central Adirondacks of New York for a period of 34 months (1985–1988). Solute concentrations and fluxes in bulk precipitation, throughfall (TF) and leachates from the forest floor, E horizon and B horizon were quantified. Both above and below-ground elemental fluxes mediated by vegetation (e.g. uptake, litter inputs, and fine roots production) were also determined. The roles of abiotic and biotic processes were ascertained based on both changes in solute concentrations through the strata of the ecosystem as well as differences between dormant and growing seasons. Concentrations of SO₄ ²⁻, NO₃ ⁻, NH₄ ⁺ and Ca²⁺ were greater in TF than precipitation. Forest floor leachates had greater concentrations of SO₄ ²⁻, NO₃ ⁻ + NH₄ ⁺ and Ca²⁺ (9, 6 and 77 μeq L⁻¹, respectively) than TF. There were differences in concentrations of ions in leachates from the forest floor between the dormant and growing seasons presumably due to vegetation uptake and microbial immobilization. Concentrations and fluxes of NO₃ ⁻ and NH; were greatest in early spring followed by a rapid decline which coincided with a demand for N by vegetation in late spring. Vegetation uptake (44.7 kg N ha⁻¹ yr⁻¹ ) could account for the low leaching rates of N0₃ ⁻. Within the mineral soil, changes with soil depth and the absence of seasonal patterns suggest that cation exchange (Ca⁺) or anion sorption (SO₄ ²⁻) are primarily responsible for regulating solute concentrations. The increase in SO₄ ²⁻ concentration after leachates passed through the mineral soil may be attributed to desorption of sulfate that was adsorbed during an earlier period when SO₄ ²⁻ concentrations would have been greater due to elevated S inputs.     

Sulfate reduction and S-oxidation in a moorland pool sediment

In an oligotrophic moorland pool in The Netherlands, S cycling near the sediment/water boundary was investigated by measuring (1) SO₄ ^2– reduction rates in the sediment, (2) depletion of SO₄ ^2– in the overlying water column and (3) release of³⁵S from the sediment into the water column. Two locations differing in sediment type (highly organic and sandy) were compared, with respect to reduction rates and depletion of SO₄ ^2– in the overlying water.Sulfate reduction rates in sediments of an oligotrophic moorland pool were estimated by diagenetic modelling and whole core³⁵SO₄ ^2– injection. Rates of SO₄ ^2– consumption in the overlying water were estimated by changes in SO₄ ^2– concentration over time in in situ enclosures. Reduction rates ranged from 0.27–11.2 mmol m^–2 d^–1. Rates of SO₄ ^2– uptake from the enclosed water column varied from –0.5, –0.3 mmol m^–2 d^–1 (November) to 0.43–1.81 mmol m^–2 d^–1 (July, August and April). Maximum rates of oxidation to SO₄ ^2– in July 1990 estimated by combination of SO₄ ^2– reduction rates and rates of in situ SO₄ ^2– uptake in the enclosed water column were 10.3 and 10.5 mmol m^–2 d^–1 at an organic rich and at a sandy site respectively.Experiments with³⁵S^2– and³⁵SO₄ ^2– tracer suggested (1) a rapid formation of organically bound S from dissimilatory reduced SO₄ ^2– and (2) the presence of mainly non SO₄ ^2–-S derived from reduced S transported from the sediment into the overlying water. A³⁵S^2– tracer experiment showed that about 7% of³⁵S^2– injected at 1 cm depth in a sediment core was recovered in the overlying water column.Sulfate reduction rates in sediments with higher volumetric mass fraction of organic matter did not significantly differ from those in sediments with a lower mass fraction of organic matter.Corresponding author     

Hückel framework study on the superconducting vibronic interaction in (AB) N chains

Superconducting vibronic interaction in the vibronic superconductivity motif has been studied in the Hückel framework for (AB) _N chain systems. Within the on-site and nearest-neighbor approximation a new vibronic constant, /L, has been introduced, of which the importance has been discussed. The effect of the vibronic operator, , has also been studied. It is also concluded that the size-dependence of the superconducting vibronic interaction also exists in the (AB) _N chain systems.On leave from the Changchun Institute of Applied Chemistry, Academia Sinica, Changchun, P. R. China, as an STA fellowship awardee hosted by the Institute of Physical and Chemical Research of Japan.     

Assimilatory sulfur metabolism in Rhodopseudomonas sulfoviridis

Rhodopseudomonas sulfoviridis is unable to grow with sulfate as sole sulfur source. Radioactively labelled sulfate is not incorporated into the cells. Growth only occurs in the presence of reduced sulfur compounds, such as sulfide, thiosulfate, elemental sulfur and cysteine. ATP sulfurylase, adenylylsulfate kinase, O-acetylserine sulfhydrylase and cysteine desulfhydrase are present. Adenylylsulfate sulfotransferase and thiosulfonate reductase are lacking. The enzymes of the sulfate-activating system are not derepressed by O-acetylserine.Non common Abbreviations APS Adenosine 5-phosphosulfate - PAPS 3-phosphoadenosine 5-phosphosulfate     

On the mechanism of photosynthetic electron transfer in Rhodopseudomonas capsulata and Rhodopseudomonas sphaeroides

(1) Current models for the mechanism of cyclic electron transport in Rhodopseudomonas sphaeroides and Rhodopseudomonas capsulata have been investigated by observing the kinetics of electron transport in the presence of inhibitors, or in photosynthetically incompetent mutant strains. (2) In addition to its well-characterized effect on the Rieske-type iron sulfur center, 5-(n-undecyl)-6-hydroxy-4,7-dioxobenzothiazole (UHDBT) inhibits both cytochrome b₅₀ and cytochrome b_?90 reduction induced by flash excitation in Rps. sphaeroides and Rps. capsulata. The concentration dependency of the inhibition in the presence of antimycin (approx. 2.7 mol UHDBT/mol reaction center for 50% inhibition of extent) is very similar to that of its inhibition of the antimycin-insensitive phase of ferricytochrome c re-reduction. UHDBT did not inhibit electron transfer between the reduced primary acceptor ubiquinone (Q^?_I) and the secondary acceptor ubiquinone (Q_II) of the reaction center acceptor complex. A mutant of Rps. capsulata, strain R126, lacked both the UHDBT and antimycin-sensitive phases of cytochrome c re-reduction, and ferricytochrome b₅₀ reduction on flash excitation. (3) In the presence of antimycin, the initial rate of cytochrome b₅₀ reduction increased about 10-fold as the E_h(7.0) was lowered below 180 mV. A plot of the rate at the fastest point in each trace against redox potential resembles the Nernst plot for a two-electron carrier with E_m(7.0) ≈ 125 ± 15 mV. Following flash excitation there was a lag of 100–500 μs before cytochrome b₅₀ reduction began. However, there was a considerably longer lag before significant reduction of cytochrome c by the antimycin-sensitive pathway occurred. (4) The herbicide ametryne inhibited electron transfer between Q^?_I and Q_II. It was an effective inhibitor of cytochrome b₅₀ photoreduction at E_h(7.0) 390 mV, but not at E_h(7.0) 100 mV. At the latter E_h, low concentrations of ametryne inhibited turnover after one flash in only half of the photochemical reaction centers. By analogy with the response to o-phenanthroline, it is suggested that ametryne is ineffective at inhibiting electron transfer from Q^?_I to the secondary acceptor ubiquinone when the latter is reduced to the semiquinone form before excitation. (5) At E_h(7.0) > 200 mV, antimycin had a marked effect on the cytochrome b₅₀ reduction-oxidation kinetics but not on the cytochrome c and reaction center changes or the slow phase III of the electrochromic carotenoid change on a 10-ms time scale. This observation appears to rule out a mechanism in which cytochrome b₅₀ oxidation is obligatorily and kinetically linked to the antimycin-sensitive phase of cytochrome c reduction in a reaction involving transmembrane charge transfer at high E_h values. However, at lower redox potentials, cytochrome b₅₀ oxidation is more rapid, and may be linked to the antimycin-sensitive reduction of cytochrome c. (6) It is concluded that neither a simple linear scheme nor a simple Q-cycle model can account adequately for all the observations. Future models will have to take account of a possible heterogeneity of redox chains resulting from the two-electron gate at the level of the secondary quinone, and of the involvement of cytochrome b_?90 in the rapid reactions of the cyclic electron transfer chain     

Effect of sulphite on adenine nucleotides of the green alga Trebouxia

The amounts of AMP, ADP and ATP were determined after sulfite incubation in photo-organotrophically cultivated cells of the green alga Trebouxia. D