Total sulfane sulfur bioavailability reflects ethnic and gender disparities in cardiovascular disease

Rajpal, Saurabh; Katikaneni, Pavan; Deshotels, Matthew R.; Pardue, Sibile; Glawe, John; Shen, Xinggui; Akkuş, Nuri İlker; Modi, Kalgi; Bhandari, Ruchi; Dominic, Paari; Reddy, Pratap; Kolluru, Gopi K.; Kevil, Christopher G.

doi:10.1016/j.redox.2018.01.007

Cited by 41 publications

(48 citation statements)

References 36 publications

(65 reference statements)

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“… 110 , 115 Conversely, low levels of hydrogen sulfide are a biomarker of vascular dysfunction in humans. 116 These findings are consistent with the view that increases in cellular resilience are not necessarily mediated by common biological pathways from beginning to end but can be initiated by many distinct pathways that converge upon mitochondria to supply the extra energy for building resilience.…”

Section: Divergence and Convergence Of Biological Mediators Of Stresssupporting

confidence: 89%

Enhancing and Extending Biological Performance and Resilience

et al. 2018

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Human performance, endurance, and resilience have biological limits that are genetically and epigenetically predetermined but perhaps not yet optimized. There are few systematic, rigorous studies on how to raise these limits and reach the true maxima. Achieving this goal might accelerate translation of the theoretical concepts of conditioning, hormesis, and stress adaptation into technological advancements. In 2017, an Air Force-sponsored conference was held at the University of Massachusetts for discipline experts to display data showing that the amplitude and duration of biological performance might be magnified and to discuss whether there might be harmful consequences of exceeding typical maxima. The charge of the workshop was “to examine and discuss and, if possible, recommend approaches to control and exploit endogenous defense mechanisms to enhance the structure and function of biological tissues.” The goal of this white paper is to fulfill and extend this workshop charge. First, a few of the established methods to exploit endogenous defense mechanisms are described, based on workshop presentations. Next, the white paper accomplishes the following goals to provide: (1) synthesis and critical analysis of concepts across some of the published work on endogenous defenses, (2) generation of new ideas on augmenting biological performance and resilience, and (3) specific recommendations for researchers to not only examine a wider range of stimulus doses but to also systematically modify the temporal dimension in stimulus inputs (timing, number, frequency, and duration of exposures) and in measurement outputs (interval until assay end point, and lifespan). Thus, a path forward is proposed for researchers hoping to optimize protocols that support human health and longevity, whether in civilians, soldiers, athletes, or the elderly patients. The long-term goal of these specific recommendations is to accelerate the discovery of practical methods to conquer what were once considered intractable constraints on performance maxima.

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Section: Divergence and Convergence Of Biological Mediators Of Stresssupporting

confidence: 89%

Enhancing and Extending Biological Performance and Resilience

et al. 2018

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“…However, H 2 S levels and metabolism in blood and circulation are currently not well understood 41,63 . Although circulating levels of free or bound H 2 S can be used as cardiovascular risk factors within individual trials 64 , the source for this H 2 S is unclear. Previous studies suggest CBS and CGL are secreted into the bloodstream by the liver and vascular endothelial cells 65 , whereas others propose production in the blood is derived via 3-MST 41 .…”

Section: Discussionmentioning

confidence: 99%

Non-enzymatic hydrogen sulfide production from cysteine in blood is catalyzed by iron and vitamin B6

et al. 2019

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Hydrogen sulfide (H 2 S) plays important roles in metabolism and health. Its enzymatic generation from sulfur-containing amino acids (SAAs) is well characterized. However, the existence of non-enzymatic H 2 S production from SAAs, the chemical mechanism, and its biological implications remain unclear. Here we present non-enzymatic H 2 S production in vitro and in blood via a reaction specific for the SAA cysteine serving as substrate and requires coordinated catalysis by Vitamin B 6 , pyridoxal(phosphate), and iron under physiological conditions. An initial cysteine-aldimine is formed by nucleophilic attack of the cysteine amino group to the pyridoxal(phosphate) aldehyde group. Free or heme-bound iron drives the formation of a cysteine-quinonoid, thiol group elimination, and hydrolysis of the desulfurated aldimine back to pyridoxal(phosphate). The reaction ultimately produces pyruvate, NH 3 , and H 2 S. This work highlights enzymatic production is inducible and robust in select tissues, whereas iron-catalyzed production contributes underappreciated basal H 2 S systemically with pathophysiological implications in hemolytic, iron overload, and hemorrhagic disorders.

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“…Hydrogen sulfide (H 2 S) is a new gasotransmitter that serves many important regulatory roles in biological systems [1]. H 2 S is involved in vascular homeostasis, neurological function, cytoprotection, anti-inflammation, and revascularization [[1], [2], [3]]. However, accumulating evidences imply that H 2 S is converted to reactive sulfane sulfur, which plays the observed roles [[4], [5], [6]].…”

Section: Introductionmentioning

confidence: 99%

Using resonance synchronous spectroscopy to characterize the reactivity and electrophilicity of biologically relevant sulfane sulfur

Liu

Chen

et al. 2019

Redox Biology

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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 2 ). With RS 2 , 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 2 signal. GSS − was nucleophilic, prone to oxidation, but had no RS 2 signal. Using this phenomenon, p K a of GSSH was determined as 6.9. GSSH/GSS − was 50-fold more reactive than H 2 S/HS − towards H 2 O 2 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 2 signal was not reactive toward sulfite, and the protonated form (R-SSH) in the active site of a rhodanese had RS 2 signal and readily reacted with sulfite to produce thiosulfate. These data suggest that RS 2 of sulfane sulfur is likely associated with its electrophilicity. Sulfane sulfur showed species-specific RS 2 spectra and intensities at physiological pH, which may reveal the relative abundance of a reactive sulfane sulfur species inside cells.

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Total sulfane sulfur bioavailability reflects ethnic and gender disparities in cardiovascular disease

Cited by 41 publications

References 36 publications

Enhancing and Extending Biological Performance and Resilience

Enhancing and Extending Biological Performance and Resilience

Non-enzymatic hydrogen sulfide production from cysteine in blood is catalyzed by iron and vitamin B6

Using resonance synchronous spectroscopy to characterize the reactivity and electrophilicity of biologically relevant sulfane sulfur

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