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Due to their antibacterial activity, sulfur-containing nanomaterials are increasingly being developed into nanodrugs against bacterial infection. Nano iron sulfide (nFeS) is a new nanomaterial that can convert organic sulfur into inorganic sulfur, which has excellent antibacterial activity. However, the inorganic sulfur produced by nFeS can easily change its form or volatilize in aqueous solution, which may affect the efficacy of nFeS. We propose a new strategy to encapsulate nFeS in a hydrogel to preserve inorganic sulfides, and the macroporous structure of the hydrogel can capture bacteria to increase their interaction with nFeS. The in-depth characterization conducted in this study demonstrate that the water swelling characteristics of the lyophilized nFeS-Hydrogel and the ability to effectively maintain the antibacterial active ingredients in nFeS results in more effective killing of harmful bacteria than pure nFeS, while also prolonging the shelf life of antibacterial activity. We discovered that bacteria exhibit a unique mode of cell death when nFeS contained in hydrogels interacts with the cells by producing hydrogen polysulfanes, which increased intracellular ROS levels and reduced GSH levels. Furthermore, the nFeS-Hydrogel was found to reduce inflammation and exhibited excellent biocompatibility. Accordingly, the nFeS-Hydrogel has great application prospects as a fast excipient for clearing infection, reducing inflammation, and accelerating wound healing.

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Specific forms of Cu in wine can influence wine flavour and development. The co-polymer polyvinylimidazole/polyvinylpyrrolidone (PVI/PVP) is known to remove Cu from wine, but its impact on different Cu forms is uncertain. In this study, three Cu fractions in white wine were determined by colorimetry and two Cu fractions in red wine were determined by diatomaceous earth depth filtration and atomic spectroscopy. PVI/PVP, with either silica or chitosan formulations, reduced all three fractions of Cu measured in white wines, and sulfide-bound Cu in red wines. The inefficient removal of organic acid-bound Cu in red wines was linked to the higher pH of red wines. After PVI/PVP treatment, wines showed lower concentrations of hydrogen sulfide, but minimal changes in weaker Cu binding agents. These results demonstrate that PVI/PVP efficiently removes the least desirable form of Cu present in wine, along with its detrimental binding agent (i.e., hydrogen sulfide).

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Glutathione-based products, GSnX, of the reaction of hydrogen sulfide, H2S, S-nitroso glutathione, and GSNO, at varied stoichiometries have been analyzed by liquid chromatography high-resolution mass spectrometry (LC-HRMS) and chemical trapping experiments. A wide variety of glutathione-based species with catenated sulfur chains have been identified including sulfanes (GSSnG), sulfides (GSSnH), and sulfenic acids (GSnOH); sulfinic (GSnO2H) and sulfonic (GSnO3H) acids are also seen in reactions exposed to air. The presence of each species of GSnX within the original reaction mixtures was confirmed using Single Ion Chromatograms (SICs), to demonstrate the separation on the LC column, and given approximate quantification by the peak area of the SIC. Further, confirmation for different GSnX families was obtained by trapping with species-specific reagents. Several unique GSnX families have been characterized, including bridging mixed di- and tetra-valent polysulfanes and internal trithionitrates (GSNHSnH) with polysulfane branches. Competitive trapping experiments suggest that the polysulfane chains are formed via the intermediacy of sulfenic acid species, GSSnOH. In the presence of radical trap vinylcyclopropane (VCP) the relative distributions of polysulfane speciation are relatively unaffected, suggesting that radical coupling is not a dominant pathway. Therefore, we suggest polysulfane catenation occurs via reaction of sulfides with sulfenic acids.

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Sulfur is an essential element in determining the productivity and quality of agricultural products. It is also an element associated with tolerance to biotic and abiotic stress in plants. In agricultural practice, sulfur has broad use in the form of sulfate fertilizers and, to a lesser extent, as sulfite biostimulants. When used in the form of bulk elemental sulfur, or micro- or nano-sulfur, applied both to the soil and to the canopy, the element undergoes a series of changes in its oxidation state, produced by various intermediaries that apparently act as biostimulants and promoters of stress tolerance. The final result is sulfate S+6, which is the source of sulfur that all soil organisms assimilate and that plants absorb by their root cells. The changes in the oxidation states of sulfur S0 to S+6 depend on the action of specific groups of edaphic bacteria. In plant cells, S+6 sulfate is reduced to S-2 and incorporated into biological molecules. S-2 is also absorbed by stomata from H2S, COS, and other atmospheric sources. S-2 is the precursor of inorganic polysulfides, organic polysulfanes, and H2S, the action of which has been described in cell signaling and biostimulation in plants. S-2 is also the basis of essential biological molecules in signaling, metabolism, and stress tolerance, such as reactive sulfur species (RSS), SAM, glutathione, and phytochelatins. The present review describes the dynamics of sulfur in soil and plants, considering elemental sulfur as the starting point, and, as a final point, the sulfur accumulated as S-2 in biological structures. The factors that modify the behavior of the different components of the sulfur cycle in the soil-plant-atmosphere system, and how these influences the productivity, quality, and stress tolerance of crops, are described. The internal and external factors that influence the cellular production of S-2 and polysulfides vs. other S species are also described. The impact of elemental sulfur is compared with that of sulfates, in the context of proper soil management. The conclusion is that the use of elemental sulfur is recommended over that of sulfates, since it is beneficial for the soil microbiome, for productivity and nutritional quality of crops, and also allows the increased tolerance of plants to environmental stresses.

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Cyclic oligochalcogenides (COCs) are emerging as promising systems to penetrate cells. Clearly better than and different to the reported diselenolanes and epidithiodiketopiperazines, we introduce the benzopolysulfanes (BPS), which show efficient delivery, insensitivity to inhibitors of endocytosis, and compatibility with substrates as large as proteins. This high activity coincides with high reactivity, selectively toward thiols, exceeding exchange rates of disulfides under tension. The result is a dynamic-covalent network of extreme sulfur species, including cyclic oligomers, from dimers to heptamers, with up to nineteen sulfurs in the ring. Selection from this unfolding adaptive network then yields the reactivities and selectivities needed to access new uptake pathways. Contrary to other COCs, BPS show high retention on thiol affinity columns. The identification of new modes of cell penetration is important because they promise new solutions to challenges in delivery and beyond.

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Diorganopolysulfanes can be generated when hydrogen sulfide (H2S) and thiols are oxidized in the presence of Cu(II) under conditions usually aimed at removing H2S from wine. This work sought to understand if polysulfanes could act as latent sources of H2S during postbottling storage. The stability of the polysulfanes formed in situ in model wine containing cysteine, H2S, and transition metals was dependent both on the number of sulfur linking atoms (Sn) and on the presence of a reducing agent, such as sulfur dioxide or ascorbic acid. A polysulfane containing three linking sulfur atoms was the most stable, with 84% of the relative initial amount remaining in solution after six months, compared to polysulfanes containing four or more linking sulfur atoms that decomposed rapidly, with 26% remaining after six months. Importantly, sulfur dioxide was associated with the rapid degradation of polysulfanes and subsequent liberation of H2S. Three cysteine- S-sulfonates were also tentatively identified, which gives insight into the possible release mechanisms involved with H2S reappearance.

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PURPOSE OF REVIEW: This article provides a brief overview of natural phytoprotective products of allium with a special focus on the therapeutic potential of diallyl polysulfanes from garlic, their molecular targets and their fate in the living organisms. A comprehensive overview of antimicrobial and anticancer properties of published literature is presented for the reader to understand the effective concentrations of polysulfanes and their sensitivity towards different human pathogenic microbes, fungi, and cancer cell lines. RECENT FINDINGS: The article finds polysulfanes potentials as new generation novel antibiotics and chemo preventive agent. The effective dose rates of polysulfanes for antimicrobial properties are in the range of 0.5-40 mg/L and for anticancer 20-100 µM. The molecular targets for these redox modulators are mainly cellular thiols as well as inhibition and/or activation of certain cellular proteins in cancer cell lines. SUMMARY: Antimicrobial and anticancer activities of polysulfanes published in the literature indicate that with further development, they could be promising candidates for cancer prevention due to their selectivity towards abnormal cells.

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Fermentation-derived volatile sulfur compounds (VSCs) are undesirable in wine and are often remediated in a process known as copper fining. In the present study, the addition of Cu(II) to model and real wine systems containing hydrogen sulfide (H2S) and thiols provided evidence for the generation of disulfides (disulfanes) and organic polysulfanes. Cu(II) fining of a white wine spiked with glutathione, H2S, and methanethiol (MeSH) resulted in the generation of MeSH-glutathione disulfide and trisulfane. In the present study, the mechanisms underlying the interaction of H2S and thiols with Cu(II) is discussed, and a prospective diagnostic test for releasing volatile sulfur compounds from their nonvolatile forms in wine is investigated. This test utilized a combination of reducing agents, metal chelators, and low-oxygen conditions to promote the release of H2S and MeSH, at levels above their reported sensory thresholds, from red and white wines that were otherwise free of sulfidic off-odors at the time of addition.

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A novel approach has been developed for the simultaneous description of reaction kinetics to describe the formation of polysulfide and sulfate anions from the biological oxidation of hydrogen sulfide (H2S) using a quick, sulfide-dependent respiration test. Next to H2S, thiols are commonly present in sour gas streams. We investigated the inhibition mode and the corresponding inhibition constants of six thiols and the corresponding diorgano polysulfanes on the biological oxidation of H2S. A linear relationship was found between the calculated IC50 values and the lipophilicity of the inhibitors. Moreover, a mathematical model was proposed to estimate the biomass activity in the absence and presence of sulfurous inhibitors. The biomass used in the respiration tests originated from a full-scale biodesulfurization reactor. A microbial community analysis of this biomass revealed that two groups of microorganism are abundant, viz. Ectothiorhodospiraceae and Piscirickettsiaceae.

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Natural polysulfanes including diallyltrisulfide (DATS) and diallyltetrasulfide (DATTS) from garlic possess antimicrobial, chemopreventive and anticancer properties. However these compounds exhibit chemical instability and reduced solubility, which prevents their potential clinical applicability. We synthesized six DATS and DATTS derivatives, based on the polysulfane motif, expected to exhibit improved physical and chemical properties and verified their biological activity on human leukemia cells. We identified four novel cytotoxic compounds (IC50 values: compound 1, 24.96±12.37 µM; compound 2, 22.82±4.20 µM; compound 3, 3.86±1.64 µM and compound 5, 40.62±10.07 µM, compared to DATTS: IC50: 9.33±3.86 µM). These polysulfanes possess excellent differential toxicity, as they did not affect proliferating mononuclear blood cells from healthy donors. We further demonstrated ability of active compounds to induce apoptosis in leukemia cells by analysis of nuclear fragmentation and of cleavage of effector and executioner caspases. Apoptosis was preceded by accumulation of cells in G2/M phase with a pro-metaphase-like nuclear pattern as well as microtubular alterations. Prolonged and persistent arrest of cancer cells in early mitosis by the benzyl derivative identifies this compound as the most stable and effective one for further mechanistic and in vivo studies.

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