Chromatographic Separation of Higher Polythionates S<sub>n</sub>O (n = 3…22) and Their Detection in Cultures of <i>Thiobacillus ferroxidans</i>; Molecular Composition of Bacterial Sulfur Secretions

Steudel, Ralf; Holdt, Gabriele; Göbel, Thomas; Hazeu, W.

doi:10.1002/anie.198701511

Cited by 107 publications

(92 citation statements)

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“…However, the main difference between prokaryotes and eukaryotes is that sulfate reduction operates with bound intermediates in eukaryotes and free intermediates in prokaryotes (1, 23, 24, 26; 1 1 lipids together with the conditions used to obtain mass spectra were responsible for the release of bound elemental sulfur and its conversion into its most stable form (viz. S8), which was detected by mass spectrometry (22,28). Thus, the mass spectra support the conclusion that some atoms of the bound sulfur were indeed at the oxidation level of elemental sulfur, but their precise in vivo structure (Sn) cannot be deduced from our results.…”

Section: Resultssupporting

confidence: 75%

“…The well-known reactivity of sulfur species (27,28) suggests caution in the interpretation of our results; we cannot entirely rule out the possibility that the experimental conditions used for analyses would promote the oxidation of polysulfide, polythionates or HS-to elemental sulfur (27,28 …”

Section: Resultsmentioning

confidence: 97%

“…of elemental sulfur was possible within isolated chloroplasts. DISCUSSION Elemental sulfur formation is a general property of numerous prokaryotes such as photosynthetic and chemoautotrophic sulfur bacteria or cyanobacteria grown on sulfide (6,7,9,18,22,(28)(29)(30); these microorganisms are probably responsible for the accumulation of the large mineral deposits at the earth's surface. During anoxygenic photoassimilation of C02, with Na2S as sole electron donor to PSI (PSII being inhibited by DCMU), several cyanobacteria can accumulate elemental sulfur in the reaction medium in the form of typical refractile granules (6).…”

Section: Resultsmentioning

confidence: 99%

“…During anoxygenic photoassimilation of C02, with Na2S as sole electron donor to PSI (PSII being inhibited by DCMU), several cyanobacteria can accumulate elemental sulfur in the reaction medium in the form of typical refractile granules (6). In chemoautotrophic bacteria, elemental sulfur formation takes place during oxidative processes of H2S and thiosulfate (18,22,28). Elemental sulfur was characterized only in a few eukaryotic cells, such as fungi (21), and there are only three reports on its formation within eukaryotic photosynthetic organisms: two red algae, Erythrophyllum (12) and Ceramium (1 1), and one green alga, Chlorella (16).…”

Section: Resultsmentioning

confidence: 99%

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Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Joyard

Forest²,

Blée³

et al. 1988

Plant Physiol.

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ABSTRACrIncubation of intact spinach (Spinacia oleracea L.) chloroplasts in the presence of 35SO42-resulted in the light-dependent formation of a chloroform-soluble sulfur-containing compound distinct from sulfolipid. We have identified this compound as the most stable form (S%) of elemental sulfur (S°, valence state for S = 0) by mass spectrometry. It is possible that elemental sulfur (S°) was formed by oxidation of bound sulfide, i.e. after the photoreduction of sulfate to sulfide by intact chloroplasts, and released as S% under the experimental conditions used for analysis.Chloroplasts from higher plants have the capacity to reduce sulfate (valence state for S = +6) in a light-dependent process for the formation of sulfolipid (14, 15) (valence state for S = +4) and cysteine (1,23,24,26) (14,15) and was further identified as sulfolipid when its polar head group was analyzed after deacylation (14). In our standard experimental conditions, the major compound (called X, see Ref. 14) represented about 10 to 15% of the newly synthesized chloroformsoluble compounds. Compound X could be either an unknown sulfolipid or a compound formed during the biosynthesis of the various sulfur-containing compounds (such as cysteine) synthesized within the chloroplast, since pathways for sulfolipid and cysteine biosynthesis are tightly related (4,5,10,20). This paper describes the characterization, by using TLC and mass spectrometry, of compound X as elemental sulfur. MATERIALS AND METHODSChloroplast Isolation. Intact and purified chloroplasts were prepared from young spinach (Spinacia oleracea L.) leaves as previously described (13,14).Reaction Mixture. Chloroplasts (120-180 Mg Chl/mL) were incubated in the following mixture: 0.33 M mannitol, 10 mM Tricine-NaOH (pH 7.9), 10 mm NaHCO3, 0.5 mM dithiothreitol, 0.1 mm Na2SO4,0.2 mm Na2HPO4,4 mm ATP, 1 mm sn-glycerol-3-P, 0.2 mM sodium acetate, 0.13 mm Triton X-100 (14). Experiments with radioactive substrate were done in the presence of "SO42 (0.25 MCi/,hmol, New England Nuclear). All solutions were used filtered through sterile 0.22-Mm filters (Millex-GV, Millipore) to prevent contamination by bacteria. Illumination was provided by a 150-W xenon arc lamp (Oriel), giving an irradiance of 1300 W/m2 at the surface of the incubation vessel.Reactions were stopped after 30 min by addition of chloroform/ methanol (1: 1, v/v) and bubbling with argon to prevent oxidation after the incubation (14).Extraction and Chromatography of the Reaction Products. The lipids were extracted under argon according to the method of Hajra (8) and analyzed by mass spectrometry directly after solubilization into carbon disulfide (see below) or after separation (compounds X and X2) by two-dimensional TLC. Compound X was prepared by TLC using precoated silica gel 60 plates (Merck), in the following solvent system (system 1): chloroform/ methanol/water (65:25:4, v/v) in the first dimension and chloroform/acetone/methanol/acetic acid/water (100:40:20:20:10, v/v) in the second one. Compound X2 was prepared after ...

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Section: Resultssupporting

confidence: 75%

Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Joyard

Forest²,

Blée³

et al. 1988

Plant Physiol.

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“…A working hypothesis for the mechanism of sulfur and polythionate production from tetrathionate was developed by Steudel et al (1987). The key reaction in this model is the (enzymic) hydrolysis of tetrathionate to sulfate and sulfane-monosulfonic acid : S,Oi-+ H,O + HS,SO, +HSO, Sulfane-monosulfonic acid is postulated to play an essential role in a chemical process of sulfur chain elongation, ultimately resulting in the production of sulfur as S , and sulfite (Steudel et al, 1987(Steudel et al, ,1988Hazeu et al, 1988;Steudel, 1989 …”

Section: Introductionmentioning

confidence: 99%

Polythionate degradation by tetrathionate hydrolase of Thiobacillus ferrooxidans

et al. 1997

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Cell-free extracts of Thiobacilhs hrrooxidans grown with thiosulfate as energy source and prepared at high ammonium sulfate concentrations and at low pH are capable of polythionate hydrolysis. The enzyme responsible for the hydrolysis of tetrathionate (S,Oi') and pentathionate (5,Oi') was purified to homogeneity. Enzyme activity during the purification procedure was based on a continuous spectrophotometric method that detects soluble intermediates that absorb in the UV region. The end products of hydrolysis of both polythionates by the pure enzyme were thiosulfate, sulfur and sulfate. The purified enzyme has a pH optimum of around 4 and a temperature optimum of 65 OC. The activity is strongly influenced by the presence of sulfate ions. The purified enzyme is a dimer with two identical subunits of molecular mass 52 kDa. During purification of tetrathionate hydrolase, fractions able to hydrolyse trithionate and tetrathionate were separated, indicating that the two substrates are hydrolysed by different enzymes.

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Syntheses of K[Co(tren)(NH3)(SO4)](S4O6)·2(H2O) and of [cis-α-Co(trien)(NH3)Cl](S5O6) – Compounds Produced by Hydrolytic Cleavage of Sulfur–Sulfur Bonds of the Tetrathionate Anion

Chun

Bernal

1999

Eur. J. Inorg. Chem.

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K[Co(tren)(NH3)(SO4)](S4O6)·2(H2O) (1) and [cis‐α‐Co‐(trien)(NH3)Cl](S5O6) (2) have been prepared unexpectedly while attempting to obtain crystals suitable for X‐ray diffraction of [Co(tren)(NH3)Cl](S4O6) (3) and of [cis‐Co(trien)(NH3)Cl](S4O6) (4), respectively. 1 is derived from 3 by hydrolysis of the tetrathionate anion resulting in a sulfato moiety which displaces the chloro ligand from the coordination sphere of the metal center. 2 is derived from 4 by hydrolysis of the tetrathionate anion followed by reformation into pentathionate anion and H2S, as described in previous chromatographic work by Steudel. Compounds 1 and 2 have been characterized by elemental analyses and by single‐crystal X‐ray diffraction studies.

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Chromatographic Separation of Higher Polythionates S_nO (n = 3…22) and Their Detection in Cultures of Thiobacillus ferroxidans; Molecular Composition of Bacterial Sulfur Secretions

Cited by 107 publications

References 19 publications

Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Polythionate degradation by tetrathionate hydrolase of Thiobacillus ferrooxidans

Syntheses of K[Co(tren)(NH3)(SO4)](S4O6)·2(H2O) and of [cis-α-Co(trien)(NH3)Cl](S5O6) – Compounds Produced by Hydrolytic Cleavage of Sulfur–Sulfur Bonds of the Tetrathionate Anion

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Chromatographic Separation of Higher Polythionates SnO (n = 3…22) and Their Detection in Cultures of Thiobacillus ferroxidans; Molecular Composition of Bacterial Sulfur Secretions

Cited by 107 publications

References 19 publications

Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

Polythionate degradation by tetrathionate hydrolase of Thiobacillus ferrooxidans

Syntheses of K[Co(tren)(NH3)(SO4)](S4O6)·2(H2O) and of [cis-α-Co(trien)(NH3)Cl](S5O6) – Compounds Produced by Hydrolytic Cleavage of Sulfur–Sulfur Bonds of the Tetrathionate Anion

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Chromatographic Separation of Higher Polythionates S_nO (n = 3…22) and Their Detection in Cultures of Thiobacillus ferroxidans; Molecular Composition of Bacterial Sulfur Secretions