Chemical aspects of hydrogen sulfide measurements in physiological samples

• Published in: Biochimica et biophysica acta Vol. 1840; no. 2; pp. 876 - 891
• Main Authors: Nagy, Péter, Pálinkás, Zoltán, Nagy, Attila, Budai, Barna, Tóth, Imre, Vasas, Anita
• Format: Journal Article
• Language: English
• Published: Netherlands Elsevier B.V 01.02.2014
• Subjects: Animals; biophysics; blood; Blood sulfide pool; Cell Physiological Phenomena; Coordination chemistry; Fluorescent Dyes; Humans; hydrogen; Hydrogen sulfide; Hydrogen Sulfide - analysis; membrane proteins; physicochemical properties; Protonation equilibria; reactive oxygen species; Redox chemistry; thermodynamics; Tissue sulfide measurement; toxicity; 3MST; DTT; HSOH; Tissue sulfide measurement; MBB; TRIS; SDB; Hydrogen sulfide; CSE; CBS; MB; Cys; GC; GSH; PBS; DTPA; DTNB; Protonation equilibria; CCO; Coordination chemistry; Blood sulfide pool; RSSH; HEPES; ROS; Redox chemistry; RSOH; cystathionine gamma-lyase; sulfenic acid; glutathione; 4-(2-hydroxyethyl)-1-piperazineethane-sulfonic acid; cytochrome c oxidase; l-cysteine; d,l-dithiotreitol; 3-mercaptopyruvate sulfurtransferase; gas chromatography; persulfide; sulfide dibimane; reactive oxygen species; methylene blue method; cystathionine beta-synthase; diethylenetriamine-pentaacetic-acid; tris(hydroxymethyl)aminomethane; sulfenic acid derivative; monobromobimane method; phosphate buffered saline; 5,5-dithiobis-(2-nitrobenzoic acid)
• ISSN: 0304-4165; 0006-3002; 1872-8006
• DOI: 10.1016/j.bbagen.2013.05.037

Owing to recent discoveries of many hydrogen sulfide-mediated physiological processes, sulfide biology is in the focus of scientific research. However, the promiscuous chemical properties of sulfide pose complications for biological studies, which led to accumulation of controversial observations in the literature. We intend to provide an overview of fundamental thermodynamic and kinetic features of sulfide redox- and coordination-chemical reactions and protonation equilibria in relation to its biological functions. In light of these chemical properties we review the strengths and limitations of the most commonly used sulfide detection methods and recently developed fluorescent probes. We also give a personal perspective on blood and tissue sulfide measurements based on proposed biomolecule–sulfide interactions and point out important chemical aspects of handling sulfide reagent solutions. The diverse chemistries of sulfide detection methods resulted in orders of magnitude differences in measured physiological sulfide levels. Investigations that were aimed to dissect the underlying molecular reasons responsible for these controversies made the important recognition that there are large sulfide reserves in biological systems. These sulfide pools are tightly regulated in a dynamic manner and they are likely to play a major role in regulation of endogenous-sulfide-mediated biological functions and avoiding toxic side effects. Working with sulfide is challenging, because it requires considerable amounts of chemical knowledge to adequately handle reagent sulfide solutions and interpret biological observations. Therefore, we propose that a rigorous chemical approach could aid the reconciliation of the increasing number of controversies in sulfide biology. This article is part of a Special Issue entitled Current methods to study reactive oxygen species - pros and cons and biophysics of membrane proteins. Guest Editor: Christine Winterbourn. •Chemical aspects of biologically relevant sulfide reactions are discussed.•The most frequently used detection methods are reviewed from a chemical perspective.•Advances on fluorescent probe development for sulfide detection are summarized.•A perspective is provided on controversial physiological sulfide measurements.•Practical advice is given to handle sulfide reagent solutions.