On the Autoxidation of Aqueous Sodium Polysulfide [1]

Steudel, Ralf; Holdt, Gabriele; Nagorka, Regine

doi:10.1515/znb-1986-1208

Cited by 48 publications

(33 citation statements)

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“…Notably, marked accumulation of glutathione occurred in tomato cells carrying resistance genes in response to specific fungal elicitors (May et al, 1996). Localized accumulation of glutathione and subsequent degradation together with chemical oxidative processes (Steudel et al, 1986) could result in the observed depositions. Future work will focus on the identification of Cys degradation pathways, for example the identification of a Cys desulfhydrase (Schmidt, 1987).…”

Section: Discussionmentioning

confidence: 98%

“…The origin of the elemental S production in plants may be from glutathione or Cys degradation, possibly via the action of an, as yet uncharacterized, Cys desulfhydrase (Rennenberg et al, 1987;Schmidt, 1987). It is possible that sulfide is a by-product of the degradation of these thiols and it is this sulfide that is oxidized to form elemental S in a non-enzymic reaction (Steudel et al, 1986).…”

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confidence: 99%

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Elemental Sulfur and Thiol Accumulation in Tomato and Defense against a Fungal Vascular Pathogen

et al. 2002

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The occurrence of fungicidal, elemental S is well documented in certain specialized prokaryotes, but has rarely been detected in eukaryotes. Elemental S was first identified in this laboratory as a novel phytoalexin in the xylem of resistant genotypes of Theobroma cacao, after infection by the vascular, fungal pathogen Verticillium dahliae. In the current work, this phenomenon is demonstrated in a resistant line of tomato, Lycopersicon esculentum, in response to V. dahliae. A novel gas chromatographymass spectroscopy method using isotope dilution analysis with 34 S internal standard was developed to identify unambiguously and quantify 32 S in samples of excised xylem. Accumulation of S in vascular tissue was more rapid and much greater in the disease-resistant than in the disease-susceptible line. Levels of S detected in the resistant variety (approximately 10 g g Ϫ1 fresh weight excised xylem) were fungitoxic to V. dahliae (spore germination was inhibited Ͼ90% at approximately 3 g mL Ϫ1 ). Scanning electron microscopy-energy dispersive x-ray microanalysis confirmed accumulation of S in vascular but not in pith cells and in greater amounts and frequency in the Verticillium spp.-resistant genotype. More intensive localizations of S were occasionally detected in xylem parenchyma cells, vessel walls, vascular gels, and tyloses, structures in potential contact with and linked with defense to V. dahliae. Transient increases in concentrations of sulfate, glutathione, and Cys of vascular tissues from resistant but not susceptible lines after infection may indicate a perturbation of S metabolism induced by elemental S formation; this is discussed in terms of possible S biogenesis.Phytoalexins are defined as low-M r , anti-microbial compounds that are both synthesized by and accumulate in plants after exposure to micro-organisms (Mansfield, 2000). A wide range of organic compounds such as phenolics and terpenoids has been identified as phytoalexins and they are synthesized from remote precursors. Although some phytoalexins are well known for their role in pathogen resistance in plants, the idea that elemental S (S 0 ), which has long been used by man as a protectant fungicide, may similarly function in defense, is relatively new Resende et al., 1996). In the typical, multiple phytoalexin response of resistant cultivars of Theobroma cacao to the vascular pathogen Verticillium dahliae, the most fungitoxic of four phytoalexins was S 0 . It accumulated to fungitoxic levels in xylem and not in other tissues and persisted for Ͼ60 d. This was the first report of S 0 as an induced antimicrobial substance and of any inorganic element (other than structural functions in cell walls of calcium or silicon) contributing directly to active defense . Elemental S formation is a property of many specialized prokaryotes Visser et al., 1997;Reinartz et al., 1998) but until recently had only been described in eukaryotes for a few algae (Ikawa et al., 1973;Izak et al., 1982;Kraus et al., 1984). It appears however, that this phenomenon may be ...

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Section: Discussionmentioning

confidence: 98%

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confidence: 99%

Elemental Sulfur and Thiol Accumulation in Tomato and Defense against a Fungal Vascular Pathogen

et al. 2002

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“…Though the maximum chain length of polysulfides present in yellow to orange solutions is uncertain, most observations suggest coexistence of species with up to six sulfur atoms [11,13]. Consequently, the separation of individual polysulfides is not an easy task.…”

Section: Introductionmentioning

confidence: 99%

Capillary electrophoretic separation of inorganic sulfur–sulfide, polysulfides, and sulfur‐oxygen species

Petre¹,

Larachi²

2006

J of Separation Science

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A CE protocol was developed for the identification and separation of inorganic polysulfides simultaneously with other inorganic sulfur-bearing species coexisting in aqueous hydrosulfide/sulfur solutions. The electrophoretic separation of thiosulfate, sulfate, hydrosulfide, sulfite, tetrathionate, and polysulfides was achieved at pH values between 8.2 and 12.2. The peaks attributed to the polysulfide species were strongly sensitive to pH. CE analysis of hydrosulfide/sulfur solutions at different pH values permitted possible identification of two forms of polysulfides: S4(2-) and S3(2-). Upon exposure to air at ambient temperature, thiosulfate was the main oxidation product of hydrosulfide/sulfur solutions mainly in the first 60 min, when hydrosulfide was rapidly consumed. Analysis of the oxidation reaction products provided retrospectively tentative evidence that the peaks separated and identified as tri- and tetrasulfide may be ascribed to polysulfides.

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“…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: 94%

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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On the Autoxidation of Aqueous Sodium Polysulfide [1]

Cited by 48 publications

References 0 publications

Elemental Sulfur and Thiol Accumulation in Tomato and Defense against a Fungal Vascular Pathogen

Elemental Sulfur and Thiol Accumulation in Tomato and Defense against a Fungal Vascular Pathogen

Capillary electrophoretic separation of inorganic sulfur–sulfide, polysulfides, and sulfur‐oxygen species

Characterization of Elemental Sulfur in Isolated Intact Spinach Chloroplasts

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