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Sulfane sulfur is common inside cells, playing both regulatory and antioxidant roles. However, there are unresolved issues about its chemistry and biochemistry. We report the discovery that reactive sulfane sulfur such as polysulfides and persulfides could be detected by using resonance synchronous spectroscopy (RS). With RS, we showed that inorganic polysulfides at low concentrations were unstable with a half-life about 1 min under physiological conditions due to reacting with glutathione. The protonated form of glutathione persulfide (GSSH) was electrophilic and had RS signal. GSS was nucleophilic, prone to oxidation, but had no RS signal. Using this phenomenon, pK of GSSH was determined as 6.9. GSSH/GSS was 50-fold more reactive than HS/HS towards HO at pH 7.4, supporting reactive sulfane sulfur species like GSSH/GSS may act as antioxidants inside cells. Further, protein persulfides were shown to be in two forms: at pH 7.4 the deprotonated form (R-SS) without RS signal was not reactive toward sulfite, and the protonated form (R-SSH) in the active site of a rhodanese had RS signal and readily reacted with sulfite to produce thiosulfate. These data suggest that RS of sulfane sulfur is likely associated with its electrophilicity. Sulfane sulfur showed species-specific RS spectra and intensities at physiological pH, which may reveal the relative abundance of a reactive sulfane sulfur species inside cells.
This article was published in the following journal.
Name: Redox biology
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Magnetic resonance spectroscopy involving detection of changes in the resonance of carbon-13 nuclei in organic molecules.
A technique applicable to the wide variety of substances which exhibit paramagnetism because of the magnetic moments of unpaired electrons. The spectra are useful for detection and identification, for determination of electron structure, for study of interactions between molecules, and for measurement of nuclear spins and moments. (From McGraw-Hill Encyclopedia of Science and Technology, 7th edition) Electron nuclear double resonance (ENDOR) spectroscopy is a variant of the technique which can give enhanced resolution. Electron spin resonance analysis can now be used in vivo, including imaging applications such as MAGNETIC RESONANCE IMAGING.
Spectroscopy technique which measures changes in organic compounds by tracking the spectral energy of absorption of HYDROGEN atoms.
Spectroscopic method of measuring the magnetic moment of elementary particles such as atomic nuclei, protons or electrons. It is employed in clinical applications such as NMR Tomography (MAGNETIC RESONANCE IMAGING).
NMR spectroscopy on small- to medium-size biological macromolecules. This is often used for structural investigation of proteins and nucleic acids, and often involves more than one isotope.