[TiCp₂S₅] (phase A), [TiCp₂Se₅] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp₂SexS₅-x] (Cp = C₅H₅-) with the initial Se:S ranging from 1:4 to 4:1 (phases B⁻E) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp₂Cl₂]. Their 77Se and 13C NMR spectra were recorded from the CS₂ solution. The definite assignment of the 77Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the 77Se chemical shifts and is supported by 13C NMR spectra of the samples. The following complexes in varying ratios were identified in the CS₂ solutions of the phases B⁻E: [TiCp₂Se₅] (5₁), [TiCp₂Se₄S] (4₁), [TiCp₂Se₃S₂] (3₁), [TiCp₂SSe₃S] (3₆), [TiCp₂SSe₂S₂] (2₅), [TiCp₂SSeS₃] (1₂), and [TiCp₂S₅] (0₁). The disorder scheme in the chalcogen atom positions of the phases B⁻E observed upon crystal structure determinations is consistent with the spectral assignment. The enthalpies of formation calculated for all twenty [TiCp₂SexS5-x] (x = 0⁻5) at DLPNO-CCSD(T)/CBS level including corrections for core-valence correlation and scalar relativistic, as well as spin-orbit coupling contributions indicated that within a given chemical composition, the isomers of most favourable enthalpy of formation were those, which were observed by 77Se and 13C NMR spectroscopy.

The amperometric determination of cysteine, using an electrode based on ternary silver-copper sulfide, is presented. Electrochemical characterizations (using cyclic voltammetry) of three electrode materials revealed that the electrode based on the material that consists of jalpaite (Ag₃CuS₂), doped with a small amount of metallic silver, has the best electrocatalytical performance for cysteine oxidation. For the amperometric determination, 0.142 V at pH 5 and 0.04 V at pH 7 vs. Ag/AgCl, related to the electrocatalytical oxidation of thiol group, were chosen. Electrochemical impedance spectroscopy together with Fourier transform infrared spectroscopy (FTIR) revealed that oxidation takes place on the electrode surface with fouling effect, which does not affect a wide linear working range between 1 μM and 100 μM. Sensitivities, at pH 5 and pH 7, are calculated to be 0.11 μA μM-1 and 0.10 μA μM-1, respectively. The detection limits were determined to be 0.036 μM and 0.024 μM for pH 5 and pH 7, respectively. In the presence of uric acid, folic acid, ascorbic acid, and glucose no interference was noticed. This electrode showed remarkable stability and excellent reproducibility. The electrode was exploited for the determination of cysteine in a dietary supplement with the excellent recoveries.

Bacterial vaginosis (BV) is the most common vaginal infection found in women in the world. Due to increasing drug-resistance of virulent pathogen such as Gardnerella vaginalis (G. vaginalis), more than half of BV patients suffer recurrence after antibotics treatment. Here, metastable iron sulfides (mFeS) act in a Gram-dependent manner to kill bacteria, with the ability to counteract resistant G. vaginalis for BV treatment. With screening of iron sulfide minerals, metastable Fe3 S4 shows suppressive effect on bacterial growth with an order: Gram-variable G. vaginalis >Gram-negative bacteria>> Gram-positive bacteria. Further studies on mechanism of action (MoA) discover that the polysulfide species released from Fe3 S4 selectively permeate bacteria with thin wall and subsequently interrupt energy metabolism by inhibiting glucokinase in glycolysis, and is further synergized by simultaneously released ferrous iron that induces bactericidal damage. Such multiple MoAs enable Fe3 S4 to counteract G. vaginalis strains with metronidazole-resistance and persisters in biofilm or intracellular vacuole, without developing new drug resistance and killing probiotic bacteria. The Fe3 S4 regimens successfully ameliorate BV with resistant G. vaginalis in mouse models and eliminate pathogens from patients suffering BV. Collectively, mFeS represent an antibacterial alternative with distinct MoA able to treat challenged BV and improve women health.

It is highly promising to design and develop efficient and economical electrocatalysts for oxygen evolution reaction (OER) in alkaline solution. In this work, we prepare FeCoNi sulfide composites (including FeS, Co3S4, and Ni3S4) derived from in situ sulfurization of precursor oxides on carbon cloth (CC), which are used to become an OER catalyst. Such catalyst shows excellent OER performance, low overpotential, small Tafel slope, and high electrochemical stability, and it is a promising electrocatalyst for OER in alkaline media.

Polyfluoroaryl sulfide is one of the prevalent motifs ubiquitous in materials and pharmaceutical chemistry. We herein describe a simple yet efficient procedure for their synthesis from readily available thiols and polyfluoroarenes via an SNAr step. We detail specific steps for a gram-scale preparation of 2-((perfluoropyridin-4-yl)thio)benzo[d]thiazole 3 from mercaptobenzothiazole 1 and pentafluoropyridine 2. For complete details on the use and execution of this protocol, please refer to Liao et al. (2022).1.

In this study, a tri-component composite named Zr/SiW12/GO was meticulously prepared through an ultrasonic-assisted method. This composite incorporates zirconium nanoparticles (Lewis acid), a negatively charged Keggin type polyoxometalate, and graphene oxide, and serves as a remarkable heterogeneous catalyst. The Keggin component plays multiple roles as reducing, encapsulating, and bridging agents, resulting in a cooperative effect among the three components that significantly enhances the catalytic activity. The catalytic performance of Zr/SiW12/GO was thoroughly investigated in the oxidation of sulfides to sulfoxides under mild conditions, employing H2O2 as the oxidant. Remarkably, this composite exhibited exceptional stability and could be effortlessly recovered and reused up to four times without any noticeable loss in its catalytic activity.

A mild protocol for the synthesis of diaryl and heteroaryl sulfides is described. In a one-pot procedure, thiols are converted to sulfenyl chlorides and reacted with arylzinc reagents. This method tolerates functional groups including aryl fluorides and chlorides, ketones, as well as N-heterocycles including pyrimidines, imidazoles, tetrazoles, and oxadiazoles. Two compounds synthesized by this method exhibited selective activity against the MCF-7 breast cancer cell line in the micromolar range.

Emerging evidence indicates that vascular stress is an important contributor to the pathophysiology of Alzheimer's disease and related dementias (ADRD). Hydrogen sulfide (H2S) and its metabolites (acid-labile (e.g., iron-sulfur clusters) and bound (e.g., per-, poly-) sulfides) have been shown to modulate both vascular and neuronal homeostasis. We recently reported that elevated plasma sulfides were associated with cognitive dysfunction and measures of microvascular disease in ADRD. Here we extend our previous work to show associations between elevated sulfides and magnetic resonance-based metrics of brain atrophy and white matter integrity. Elevated bound sulfides were associated with decreased grey matter volume, while increased acid labile sulfides were associated with decreased white matter integrity and greater ventricular volume. These findings are consistent with alterations in sulfide metabolism in ADRD which may represent maladaptive responses to oxidative stress.

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.

Palladium-catalyzed oxidative C-H halogenation and acetoxylation reactions of S-unprotected sulfides, selectively directed by pyridinyl groups, allows the formation of C-X bonds (X = I, Br, Cl, OAc) by using simple halosuccinimide or phenyliodine diacetate (PIDA) oxidants. The undesired formation of sulfoxides and/or sulfones, which are usually observed under oxidative conditions, is fully obviated. Under the solvent-dependent conditions that we proposed, sulfide C-H functionalization is achieved in less than 1 h without any direct electrophilic halogenation at the pyridine moiety. N-Directed ortho-C-H activation of aryl also facilitates dibromination reactions which are hardly accessible with sulfone and sulfoxide counterparts because of their higher structural rigidity. This general method gives a straightforward access to polyhalide sulfides, without an organosulfur reduction step or protection-deprotection sequence. Polyhalide sulfides are valuable synthons that give a practical entry to new constrained polyaromatic and biphenyl sulfides, including synthetically challenging unsymmetrical examples.

Fiber shaped supercapacitors are promising candidates for wearable electronics because they are flexible and light-weight. However, a critical challenge of the widespread application of these energy storage devices is their low cell voltages and low energy densities, resulting in limited run-time of the electronics. Here, we demonstrate a 1.5 V high cell voltage and high volumetric energy density asymmetric fiber supercapacitor in aqueous electrolyte. The lightweight (0.24 g cm(-3)), highly conductive (39 S cm(-1)), and mechanically robust (221 MPa) graphene fibers were firstly fabricated and then coated by NiCo2S4 nanoparticles (GF/NiCo2S4) via the solvothermal deposition method. The GF/NiCo2S4 display high volumetric capacitance up to 388 F cm(-3) at 2 mV s(-1) in a three-electrode cell and 300 F cm(-3) at 175.7 mA cm(-3) (568 mF cm(-2) at 0.5 mA cm(-2)) in a two-electrode cell. The electrochemical characterizations show 1000% higher capacitance of the GF/NiCo2S4 as compared to that of neat graphene fibers. The fabricated device achieves high energy density up to 12.3 mWh cm(-3) with a maximum power density of 1600 mW cm(-3), outperforming the thin-film lithium battery. Therefore, these supercapacitors are promising for the next generation flexible and wearable electronic devices.

This paper reports on a novel method to remove Hg0 in the wet scrubbing process using defect-rich colloidal copper sulfides for reducing mercury emissions from non-ferrous smelting flue gas. Unexpectedly, it migrated the negative effect of SO2 on mercury removal performance, while also enhancing Hg0 adsorption. Colloidal copper sulfides demonstrated the superior Hg0 adsorption rate of 306.9 μg·g-1·min-1 under 6% SO2 + 6% O2 atmosphere with a removal efficiency of 99.1%, and the highest-ever Hg0 adsorption capacity of 736.5 mg·g-1, which was 277% higher than all other reported metal sulfides. The Cu and S sites transformation results reveal that SO2 could transform the tri-coordinate S sites into S22- on copper sulfides surfaces, while O2 regenerated Cu2+ via the oxidation of Cu+. The S22- and Cu2+ sites enhanced Hg0 oxidation, and the Hg2+ could strongly bind with tri-coordinate S sites. This study provides an effective strategy to achieve large-capability adsorption of Hg0 from non-ferrous smelting flue gas.

The constant progress in novel nanomaterials synthesis has contributed to the rapid development of nonenzymatic glucose sensors. For working electrodes preparation, drop casting proved to be the most convenient and thus most widely applied method. However, appropriate interpretation of obtained electrochemical signal requires in-depth knowledge of limitations related to this technique. In this study, we prepared solutions based on commonly reported polymers for nanostructures immobilization and investigated their influence on copper sulfides distribution on the electrode. Characterization of suspensions properties and behavior of particles during droplet drying revealed that nonionic polyvinylpyrrolidone (PVP) was favorable for electrodes modification with copper sulfides in comparison with Nafion and chitosan. It ensured homogeneity of the suspension as well as the uniform coverage of the electrode surface with particles, what resulted in increased active surface area and, therefore, higher signal from glucose addition. On the other hand, when cationic chitosan was used as a binder, suspensions were agglomerated and, within dry deposits, a coffee-ring effect was observed. Appropriate adjustment of material and polymer interactions led to enhanced electrode electrochemical performance.

In this paper, we report the synthesis of ZnFe2O4@SiO2@APTES@DHBS-Cu as a novel magnetic nanocatalyst, in a mild and green environment. The structure of the described magnetic compound was characterized by different physicochemical techniques including XRD, EDS, AAS, SEM, FT-IR, X-ray elemental mapping, TGA, and VSM analyses. The prepared magnetic nanoparticles exhibit excellent catalytic activity in synthesizing bis (pyrazolyl)methanes and oxidation of sulfide derivatives under green conditions. The heterogeneous nature of the catalyst was confirmed via the hot filtration experiment. Further, ZnFe2O4@SiO2@APTES@DHBS-Cu showed high efficiency and reusability that could be reused for at least five consecutive runs.

Anaerobic membrane bioreactors reduce the energy cost of wastewater treatment and meet filtration requirements for non-potable reuse. However, sulfides (H2S/HS-) formed during anaerobic treatment exert a high chlorine demand and inhibit UV disinfection by photon shielding at 254 nm. This study evaluated the feasibility of hydrogen peroxide (H2O2) for sulfide oxidation, UV disinfection for inactivation of MS2 bacteriophage, and chlorine to provide a residual for distribution. H2O2 treatment at pH ≥ 8 favored sulfide oxidation to sulfate in 30 min at a 4:1 H2O2:sulfide stoichiometry. Compared to a 6:1 H2O2:sulfide molar ratio, treatment of anaerobic effluent with 0.5 mM sulfides with a 4:1 H2O2:sulfide molar ratio would increase the applied UV fluence needed for 5-log MS2 inactivation from 180 mJ cm-2 to 225 mJ cm-2. However, the lower H2O2 dose reduced the dose of chlorine needed to quench residual H2O2 and provide a residual for distribution. Treatment at the 4:1 H2O2:sulfide molar ratio was favored, because the cost savings in H2O2 and chlorine reagents outweighed the energy savings associated with UV treatment. However, H2O2/UV/chlorine treatment of anaerobic effluent was cost-competitive with conventional treatment of aerobic effluent for non-potable reuse only for < 285 µM sulfides.

The stable isotope ratios of sulfur (δ34S relative to Vienna Cañon Diablo Troilite) in sulfates and sulfides determined by elemental analysis and isotope ratio mass spectrometry (EA/IRMS) have been proven to be a remarkable tool for studies of the (bio)geochemical sulfur cycles in modern and ancient environments. However, the use of EA/IRMS to measure δ34S in arsenides and sulfarsenides may not be straightforward. This difficulty can lead to potential health and environmental hazards in the workplace and analytical problems such as instrument contamination, memory effects, and a non-matrix-matched standardization of δ34S measurements with suitable reference materials. To overcome these practical and analytical challenges, we developed a procedure for sulfur isotope analysis of arsenides, which can also be safely used for EA/IRMS analysis of arsenic sulfides (i.e., realgar, orpiment, arsenopyrite, and arsenian pyrite), and mercury sulfides (cinnabar). The sulfur dioxide produced from off-line EA combustion was trapped in an aqueous barium chloride solution in a leak-free system and precipitated as barium sulfate after quantitative oxidation of hydrogen sulfite by hydrogen peroxide. The derived barium sulfate was analyzed by conventional EA/IRMS, which bracketed the δ34S values of the samples with three international sulfate reference materials. The protocol (BaSO4-EA/IRMS) was validated by analyses of reference materials and laboratory standards of sulfate and sulfides and achieved accuracy and precision comparable with those of direct EA/IRMS. The δ34S values determined by BaSO4-EA/IRMS in sulfides (arsenopyrite, arsenic, and mercury sulfides) samples from different origins were comparable to those obtained by EA/IRMS, and no sulfur isotope fractionations were introduced during sample preparation. We report the first sulfur isotope data of arsenides obtained by BaSO4-EA/IRMS.

Garlic organic sulfides are dietary bioactive components with multiple biofunctions to prevent chronic diseases/inflammation and promote human health. DADS (diallyl disulfide), DATS (diallyl trisulfide), and DTS (diallyl tetrasulfide) are typical organic sulfides with similar structures from garlic. However, the structure-activity relationship of garlic organic sulfides remained unknown. The aim of the present study was to investigate the effect of DADS, DATS, and DTS on the gene expression profiling of human hepatocellular carcinoma cells (HepG2) by application of microarray and specialized analysis software, GO, Bio-Plex-based cytokines assay and IPA and analyze their structure-activity relationship according to antioxidant, anti-inflammatory, and metabolic-related properties. According to the microarray data, with the increase of S atom in garlic organic sulfides, its biological activity was gradually enhanced. In the general catalog of GO, garlic organic sulfides mainly affect biological process, molecular function, and cellular component. RT-qPCR results indicated that the microarray data is trustworthy, and the structure-activity analysis data found that more sulfur atoms have more powerful properties; thus, microarray data of DTS was preceded to the subsequent IPA analysis. The results of IPA analysis showed that the top 5 signaling pathways and molecular functions were disturbed by DTS; the molecular functions with the highest scores affected by DTS are cancer, cell apoptosis, and cell proliferation, which imply that the occurrence or metabolism of these diseases is related to the differential expression of the above-mentioned related genes and the activation of signaling channels, and the core of the most significant molecular network is inflammation. Finally, the results found that the secretions of 6 cytokines in macrophages were significantly inhibited by DTS treatment. This is the first study that analyzed the structure-activity relationship of garlic organic sulfides, which will provide useful genetic information for its multi-biofunction and promote their clinical application in the near future.

Protection against arsenic damage in organisms positioned deep in the tree of life points to early evolutionary sensitization. Here, marine sedimentary records reveal a Proterozoic arsenic concentration patterned to glacial-interglacial ages. The low glacial and high interglacial sedimentary arsenic concentrations, suggest deteriorating habitable marine conditions may have coincided with atmospheric oxygen decline after ~2.1 billion years ago. A similar intensification of near continental margin sedimentary arsenic levels after the Cryogenian glaciations is also associated with amplified continental weathering. However, interpreted atmospheric oxygen increase at this time, suggests that the marine biosphere had widely adapted to the reorganization of global marine elemental cycles by glaciations. Such a glacially induced biogeochemical bridge would have produced physiologically robust communities that enabled increased oxygenation of the ocean-atmosphere system and the radiation of the complex Ediacaran-Cambrian life.

Unsupported Ni-Mo sulfides have been hydrothermally synthesized and purified by HCl leaching to remove Ni sulfides. Unblocking of active sites by leaching significantly increases the catalytic activity for dibenzothiophene hydrodesulfurization. The site-specific rates of both direct (hydrogenolytic) and hydrogenative desulfurization routes on these active sites that consist of coordinatively unsaturated Ni and sulfhydryl groups were identical for all unsupported sulfides. The hydrogenative desulfurization rates were more than an order of magnitude higher on unsupported Ni-Mo sulfides than on Al2O3-supported catalysts, while they were similar for the direct (hydrogenolytic) desulfurization. The higher activity is concluded to be caused by the lower average electronegativity, i.e., higher base strength and polarity, of Ni-Mo sulfides in the absence of the alumina support and the modified adsorption of reactants enabled by multilayer stacking. Beyond the specific catalytic reaction, the synthesis strategy points to promising scalable routes to sulfide materials broadly applied in hydrogenation and hydrotreating.

The use of natural substance to ward off microbial infections has a long history. However, the large-scale production of natural extracts often reduces antibacterial potency, thus limiting practical applications. Here we present a strategy for converting natural organosulfur compounds into nano-iron sulfides that exhibit enhanced antibacterial activity. We show that compared to garlic-derived organosulfur compounds nano-iron sulfides exhibit an over 500-fold increase in antibacterial efficacy to kill several pathogenic and drug-resistant bacteria. Furthermore, our analysis reveals that hydrogen polysulfanes released from nano-iron sulfides possess potent bactericidal activity and the release of polysulfanes can be accelerated by the enzyme-like activity of nano-iron sulfides. Finally, we demonstrate that topical applications of nano-iron sulfides can effectively disrupt pathogenic biofilms on human teeth and accelerate infected-wound healing. Together, our approach to convert organosulfur compounds into inorganic polysulfides potentially provides an antibacterial alternative to combat bacterial infections.