Special Issue "Think Yellow: Reactive Sulfur Species in Redox Biology, Medicine and Agriculture"

A special issue of Antioxidants (ISSN 2076-3921). This special issue belongs to the section "ROS, RNS and RSS".

Deadline for manuscript submissions: closed (30 September 2016).

Special Issue Editors

Dr. Gregory Ian Giles
E-Mail Website
Guest Editor
Department of Pharmacology and Toxicology, University of Otago, P.O. Box 913, Dunedin, New Zealand
Interests: reactive sulfur species; redox drugs; nitric oxide; cancer

Special Issue Information

Dear Colleagues,

Research conducted during the last couple of decades has shown that Reactive Sulfur Species (RSS), i.e., molecules with one or more chemically-reactive sulfur atoms, play a major role in Biology. Such sulfur-containing reactive species embrace a wide range of chemically diverse compounds, each with its own, facet-rich reactivity and biochemical activity. Here, we find rather exotic molecules, such as organic di- and polysulfanes, H2S and inorganic polysulfides, thiosulfinates, thiosulfonates and hypothiocyanous acid, to name just a few. From a chemical perspective, most of these molecules are oxidizing, electrophilic species, often selectively modifying thiol groups in cysteine proteins belonging to the regulatory network shaping the cellular thiolstat; while others, such as H2S, may act as reductants. Indeed, RSS are omnipresent in Biology, and many of them exhibit interesting redox modulating properties which ultimately may be used in the context of chemoprevention, the treatment of certain diseases (e.g., inflammatory and infectious diseases, cancer) and, in the case of plant derived products, as ecologically friendly “green” phytoprotectants in Agriculture.

The concept of RSS was explicitly introduced into the literature in 2001 and, 15 years onwards, RSS are now center stage in many fields of research. Recent developments in RSS research span natural products chemistry and biochemistry, drug development, synthetic sulfur chemistry, nanotechnology and analytics. Many of these discoveries begin to have a significant role in shaping the fields of nutrition, ageing, control of the microbiota, drug and pesticide development, to highlight but a few emerging applications.

This Special Issue, therefore, aims to showcase the diversity and impact of RSS on different aspects of Biology, especially on human and animal health, and to emphasize potential RSS innovations in agriculture. It also strives to explore why those RSS are—often selectively—active, and how they interact with their cellular targets. Eventually, a more contemporary definition of RSS may emerge the in the light of recent developments, which will benchmark those chemically yellow, yet biologically colourful species, for subsequent years to come.

Prof. Claus Jacob
Dr. Gregory Ian Giles
Guest Editors

Manuscript Submission Information

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Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Antioxidants is an international peer-reviewed open access monthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 1200 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Reactive Sulfur Species (RSS)
  • redox active secondary metabolites
  • Cellular Thiolstat
  • redox modulating drugs
  • sulfur biochemistry
  • redox signaling
  • antioxidants
  • sulfide

Published Papers (6 papers)

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Research

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Open AccessArticle
Inorganic Reactive Sulfur-Nitrogen Species: Intricate Release Mechanisms or Cacophony in Yellow, Blue and Red?
Antioxidants 2017, 6(1), 14; https://doi.org/10.3390/antiox6010014 - 15 Feb 2017
Cited by 3
Abstract
Since the heydays of Reactive Sulfur Species (RSS) research during the first decade of the Millennium, numerous sulfur species involved in cellular regulation and signalling have been discovered. Yet despite the general predominance of organic species in organisms, recent years have also seen [...] Read more.
Since the heydays of Reactive Sulfur Species (RSS) research during the first decade of the Millennium, numerous sulfur species involved in cellular regulation and signalling have been discovered. Yet despite the general predominance of organic species in organisms, recent years have also seen the emergence of inorganic reactive sulfur species, ranging from inorganic polysulfides (HSx/Sx2−) to thionitrous acid (HSNO) and nitrosopersulfide (SSNO). These inorganic species engage in a complex interplay of reactions in vitro and possibly also in vivo. Employing a combination of spectrophotometry and sulfide assays, we have investigated the role of polysulfanes from garlic during the release of nitric oxide (NO) from S-nitrosoglutathione (GSNO) in the absence and presence of thiol reducing agents. Our studies reveal a distinct enhancement of GSNO decomposition by compounds such as diallyltrisulfane, which is most pronounced in the presence of cysteine and glutathione and presumably proceeds via the initial release of an inorganic mono- or polysulfides, i.e., hydrogen sulfide (H2S) or HSx, from the organic polysulfane. Albeit being of a preliminary nature, our spectrophotometric data also reveals a complicated underlying mechanism which appears to involve transient species such as SSNO. Eventually, more in depth studies are required to further explore the underlying chemistry and wider biological and nutritional implications of this interplay between edible garlic compounds, reductive activation, inorganic polysulfides and their interplay with NO storage and release. Full article
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Open AccessArticle
The Effects of Allicin, a Reactive Sulfur Species from Garlic, on a Selection of Mammalian Cell Lines
Antioxidants 2017, 6(1), 1; https://doi.org/10.3390/antiox6010001 - 26 Dec 2016
Cited by 13
Abstract
Garlic (Allium sativum L.) has been used as a spice and medicinal plant since ancient times. Garlic produces the thiol-reactive defence substance, allicin, upon wounding. The effects of allicin on human lung epithelium carcinoma (A549), mouse fibroblast (3T3), human umbilical vein endothelial [...] Read more.
Garlic (Allium sativum L.) has been used as a spice and medicinal plant since ancient times. Garlic produces the thiol-reactive defence substance, allicin, upon wounding. The effects of allicin on human lung epithelium carcinoma (A549), mouse fibroblast (3T3), human umbilical vein endothelial cell (HUVEC), human colon carcinoma (HT29) and human breast cancer (MCF7) cell lines were tested. To estimate toxic effects of allicin, we used a standard MTT-test (methylthiazoltetrazolium) for cell viability and 3H-thymidine incorporation for cell proliferation. The glutathione pool was measured using monobromobimane and the formation of reactive species was identified using 2′,7′-dichlorofluoresceine-diacetate. The YO-PRO-1 iodide staining procedure was used to estimate apoptosis. Allicin reduced cell viability and cell proliferation in a concentration dependent manner. In the bimane test, it was observed that cells treated with allicin showed reduced fluorescence, suggesting glutathione oxidation. The cell lines tested differed in sensitivity to allicin in regard to viability, cell proliferation and glutathione oxidation. The 3T3 and MCF-7 cells showed a higher proportion of apoptosis compared to the other cell types. These data show that mammalian cell lines differ in their sensitivity and responses to allicin. Full article
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Open AccessArticle
The Effects of Different Garlic-Derived Allyl Sulfides on Anaerobic Sulfur Metabolism in the Mouse Kidney
Antioxidants 2016, 5(4), 46; https://doi.org/10.3390/antiox5040046 - 05 Dec 2016
Cited by 9
Abstract
Diallyl sulfide (DAS), diallyl disulfide (DADS) and diallyl trisulfide (DATS) are major oil-soluble organosulfur compounds of garlic responsible for most of its pharmacological effects. The present study investigated the influence of repeated intraperitoneally (ip) administration of DAS, DADS and DATS on the total [...] Read more.
Diallyl sulfide (DAS), diallyl disulfide (DADS) and diallyl trisulfide (DATS) are major oil-soluble organosulfur compounds of garlic responsible for most of its pharmacological effects. The present study investigated the influence of repeated intraperitoneally (ip) administration of DAS, DADS and DATS on the total level of sulfane sulfur, bound sulfur (S-sulfhydration) and hydrogen sulfide (H2S) and on the activity of enzymes, which catalyze sulfane sulfur formation and transfer from a donor to an acceptor in the normal mouse kidney, i.e., γ-cystathionase (CSE) and rhodanese (TST). The activity of aldehyde dehydrogenase (ALDH), which is a redox-sensitive protein, containing an –SH group in its catalytic center, was also determined. The obtained results indicated that all tested compounds significantly increased the activity of TST. Moreover, DADS and DATS increased the total sulfane sulfur level and CSE activity in the normal mouse kidney. ALDH activity was inhibited in the kidney after DATS administration. The results indicated also that none of the studied allyl sulfides affected the level of bound sulfur or H2S. Thus, it can be concluded that garlic-derived DADS and DATS can be a source of sulfane sulfur for renal cells but they are not connected with persulfide formation. Full article
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Review

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Open AccessReview
The Reactive Sulfur Species Concept: 15 Years On
Antioxidants 2017, 6(2), 38; https://doi.org/10.3390/antiox6020038 - 23 May 2017
Cited by 17
Abstract
Fifteen years ago, in 2001, the concept of “Reactive Sulfur Species” or RSS was advocated as a working hypothesis. Since then various organic as well as inorganic RSS have attracted considerable interest and stimulated many new and often unexpected avenues in research and [...] Read more.
Fifteen years ago, in 2001, the concept of “Reactive Sulfur Species” or RSS was advocated as a working hypothesis. Since then various organic as well as inorganic RSS have attracted considerable interest and stimulated many new and often unexpected avenues in research and product development. During this time, it has become apparent that molecules with sulfur-containing functional groups are not just the passive “victims” of oxidative stress or simple conveyors of signals in cells, but can also be stressors in their own right, with pivotal roles in cellular function and homeostasis. Many “exotic” sulfur-based compounds, often of natural origin, have entered the fray in the context of nutrition, ageing, chemoprevention and therapy. In parallel, the field of inorganic RSS has come to the forefront of research, with short-lived yet metabolically important intermediates, such as various sulfur-nitrogen species and polysulfides (Sx2−), playing important roles. Between 2003 and 2005 several breath-taking discoveries emerged characterising unusual sulfur redox states in biology, and since then the truly unique role of sulfur-dependent redox systems has become apparent. Following these discoveries, over the last decade a “hunt” and, more recently, mining for such modifications has begun—and still continues—often in conjunction with new, innovative and complex labelling and analytical methods to capture the (entire) sulfur “redoxome”. A key distinction for RSS is that, unlike oxygen or nitrogen, sulfur not only forms a plethora of specific reactive species, but sulfur also targets itself, as sulfur containing molecules, i.e., peptides, proteins and enzymes, preferentially react with RSS. Not surprisingly, today this sulfur-centred redox signalling and control inside the living cell is a burning issue, which has moved on from the predominantly thiol/disulfide biochemistry of the past to a complex labyrinth of interacting signalling and control pathways which involve various sulfur oxidation states, sulfur species and reactions. RSS are omnipresent and, in some instances, are even considered as the true bearers of redox control, perhaps being more important than the Reactive Oxygen Species (ROS) or Reactive Nitrogen Species (RNS) which for decades have dominated the redox field. In other(s) words, in 2017, sulfur redox is “on the rise”, and the idea of RSS resonates throughout the Life Sciences. Still, the RSS story isn’t over yet. Many RSS are at the heart of “mistaken identities” which urgently require clarification and may even provide the foundations for further scientific revolutions in the years to come. In light of these developments, it is therefore the perfect time to revisit the original hypotheses, to select highlights in the field and to question and eventually update our concept of “Reactive Sulfur Species”. Full article
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Open AccessReview
Think Yellow and Keep Green—Role of Sulfanes from Garlic in Agriculture
Antioxidants 2017, 6(1), 3; https://doi.org/10.3390/antiox6010003 - 30 Dec 2016
Cited by 4
Abstract
Reactive sulfur species from garlic have long been renowned for their health benefits and antimicrobial properties. In agriculture the subject matter is now gathering momentum in the search for new bio-pesticides to addressing emerging environmental concerns and tighter restrictions on the use of [...] Read more.
Reactive sulfur species from garlic have long been renowned for their health benefits and antimicrobial properties. In agriculture the subject matter is now gathering momentum in the search for new bio-pesticides to addressing emerging environmental concerns and tighter restrictions on the use of many conventional chemical pesticides. Although the precise modes of action of these garlic-derived bioactives is complex, recent research has provided a number of new insights that deepen our understanding of garlic-derived products, such as garlic extracts and oils. Herein, their activity against various crop-damaging pests is reviewed. In many cases, there seems to be a broad range of activity associated with the sulfur-containing compounds derived from Allium species, which manifests itself in diverse insecticidal, antifungal, and nematicidal activities. These activities open a new understanding to develop this natural chemistry as a “green pesticide”. Full article
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Open AccessReview
Biological Chemistry of Hydrogen Selenide
Antioxidants 2016, 5(4), 42; https://doi.org/10.3390/antiox5040042 - 22 Nov 2016
Cited by 15
Abstract
There are no two main-group elements that exhibit more similar physical and chemical properties than sulfur and selenium. Nonetheless, Nature has deemed both essential for life and has found a way to exploit the subtle unique properties of selenium to include it in [...] Read more.
There are no two main-group elements that exhibit more similar physical and chemical properties than sulfur and selenium. Nonetheless, Nature has deemed both essential for life and has found a way to exploit the subtle unique properties of selenium to include it in biochemistry despite its congener sulfur being 10,000 times more abundant. Selenium is more easily oxidized and it is kinetically more labile, so all selenium compounds could be considered to be “Reactive Selenium Compounds” relative to their sulfur analogues. What is furthermore remarkable is that one of the most reactive forms of selenium, hydrogen selenide (HSe at physiologic pH), is proposed to be the starting point for the biosynthesis of selenium-containing molecules. This review contrasts the chemical properties of sulfur and selenium and critically assesses the role of hydrogen selenide in biological chemistry. Full article
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