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N2SS2O5 crystallizes in the monoclinic P2_1/c space group. The structure is zero-dimensional and consists of eight ammonia molecules, four hydrogen sulfide molecules, and four sulfino hydrogen sulfite molecules.
Abstract Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4‐vinylpyridine) thin films result in the 3D‐nucleation of clusters consistent with a cubane‐type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few‐atom Cd‐based clusters are consistent with electronic and vibrational spectroscopy and grazing‐incidence total X‐ray scattering measurements of 3D‐cluster‐arrays synthesized at 80 °C. The direct synthesis of few‐atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light‐absorbing materials including solar energy harvesting and conversion applications.
Exposure of soft material templates to alternating volatile chemical precursors can produce inorganic deposition within the permeable template (e.g. a polymer thin film) in a process akin to atomic layer deposition (ALD). While such sequential infiltration synthesis (SIS) processes have now been demonstrated for many metal oxides, we report an SIS process for a transition metal sulfide – CdS. Gas phase dimethyl cadmium and hydrogen sulfide precursors infiltrated into poly(4-vinylpyridine) thin films result in the 3D-nucleation of clusters consistent with a cubane-type Cd 4 S 4 core that are variably terminated with methyl, thiol and hydroxy capping ligands. First principles models and simulation of few-atom Cd-based clusters are consistent with electronic and vibrational spectroscopy and grazing-incidence total X-ray scattering measurements of 3D-cluster-arrays synthesized at 80 °C. The direct synthesis of few-atom transition metal sulfide clusters within polymer thin films will provide a versatile new route to precision architectures for light-absorbing materials including solar energy harvesting and conversion applications.
The gut microbiota–brain axis allows for bidirectional communication between the microbes in our gastrointestinal (GI) tract and the central nervous system. Psychological stress has been known to disrupt the gut microbiome (dysbiosis) leading to anxiety-like behavior. Pathogens administered into the gut have been reported to cause anxiety. Whether commensal bacteria affect the gut–brain axis is not well understood. In this study, we examined the impact of a commensal sulfate-reducing bacteria (SRB) and its metabolite, hydrogen sulfide (H2S), on anxiety-like behavior. We found that mice gavaged with SRB had increased anxiety-like behavior as measured by the open field test. We also tested the effects of magnesium oxide (MgO) on SRB growth both in vitro and in vivo using a water avoidance stress (WAS) model. We found that MgO inhibited SRB growth and H2S production in a dose-dependent fashion. Mice that underwent psychological stress using the WAS model were observed to have an overgrowth (bloom) of SRB (Deferribacterota) and increased anxiety-like behavior. However, WAS-induced overgrowth of SRB and anxiety-like behavioral effects were attenuated in animals fed a MgO-enriched diet. These findings supported a potential MgO-reversible relationship between WAS-induced SRB blooms and anxiety-like behavior.
To develop biological biogas to methanol conversion technology without costly hydrogen sulfide (H 2 S) removal, a high H 2 S tolerant methanotrophic consortium (HTMC), was enriched from an anaerobic digester effluent in presence of 5.64 g/m 3 H 2 S in the gas phase. The HTMC can grow stably and produce methanol under conditions with CH 4 /air mixtures containing 5.64 g/m 3 of H 2 S. There is no significant (p>0.05) difference in cell yield or CH 4 to methanol conversion efficiency between trials with different H 2 S concentrations from 0 g/m 3 to 5.64 g/m 3 . Further, under optimal conditions, a cell yield of 0.333 g cells/g CH 4 , a methanol concentration of 0.28 mg/mL, and a CH 4 to methanol conversion efficiency of 0.22 mol/mol were obtained, respectively. Besides methanotrophs (14.85%) and other bacteria, Cyanobacteria were also identified in the HTMC with a high abundancy (32.16%), which could broaden the application of HTMC for simultaneous utilization of CH 4 and CO 2 from raw biogas.
ABSTRACT The microbiome is an underappreciated contributor to intestinal drug metabolism with broad implications for drug efficacy and toxicity. While considerable progress has been made toward identifying the gut bacterial genes and enzymes involved, the role of environmental factors in shaping their activity remains poorly understood. Here, we focus on the gut bacterial reduction of azo bonds (R-N = N-R’), found in diverse chemicals in both food and drugs. Surprisingly, the canonical azoR gene in Escherichia coli was dispensable for azo bond reduction. Instead, azoreductase activity was controlled by the fumarate and nitrate reduction ( fnr ) regulator, consistent with a requirement for the anoxic conditions found within the gastrointestinal tract. Paired transcriptomic and proteomic analysis of the fnr regulon revealed that in addition to altering the expression of multiple reductases, FNR is necessary for the metabolism of L-Cysteine to hydrogen sulfide, enabling the degradation of azo bonds. Furthermore, we found that FNR indirectly regulates this process through the small noncoding regulatory RNA fnrS . Taken together, these results show how gut bacteria sense and respond to their intestinal environment to enable the metabolism of chemical groups found in both dietary and pharmaceutical compounds. IMPORTANCE This work has broad relevance due to the ubiquity of dyes containing azo bonds in food and drugs. We report that azo dyes can be degraded by human gut bacteria through both enzymatic and nonenzymatic mechanisms, even from a single gut bacterial species. Furthermore, we revealed that environmental factors, oxygen, and L-Cysteine control the ability of E. coli to degrade azo dyes due to their impacts on bacterial transcription and metabolism. These results open up new opportunities to manipulate the azoreductase activity of the gut microbiome through the manipulation of host diet, suggest that azoreductase potential may be altered in patients suffering from gastrointestinal disease, and highlight the importance of studying bacterial enzymes for drug metabolism in their natural cellular and ecological context.
ABSTRACT Hydrogen sulfide is produced during the dissolution of some sulfidic minerals and during the microbial metabolism of reduced sulfur compounds. The sulfide:quinone reductase (SQR) enzyme is able to oxidize H 2 S, and the bioleaching cells Acidithiobacillus ferrooxidans have two SQR genes, only one of which has been characterized. We cloned and overexpressed the two SQR genes in A. ferrooxidans and show that they both have SQR activity. Both AFE_0267 and AFE_1792 are active under anaerobic conditions, but only AFE_1792 is active under aerobic conditions. The effect of the SQR overexpression and the expression of related genes on sulfur metabolism was investigated. The overexpression of SQR improved cell growth and sulfur oxidation, suggesting enhanced SQR activity led to a reduction in H 2 S toxicity as well as providing additional energy through H 2 S oxidation. Additionally, the impact on the oxidation of pyrite and pyrrhotite was investigated. The rate of oxidation of pyrite by the engineered cells was enhanced, and, furthermore, the rate of pyrrhotite oxidation was more than doubled. IMPORTANCE H 2 S is a toxic sulfur intermediate, and the SQR enzyme has evolved to oxidize H 2 S in A. ferrooxidans . In addition to detoxification, H 2 S oxidation provides energy, and overexpression of SQR enhanced aerobic and anaerobic growth on sulfur. The SQR overexpression also enhanced pyrite and pyrrhotite oxidation, which may facilitate the pyrometallurgical processing of a number of critical materials including copper, nickel, and the platinum group metals.
Several hydrogen-rich superconductors have been found to show unprecedentedly high critical temperatures, stimulating investigations into the nature of the superconductivity in these materials. Although their macroscopic superconducting properties are established, microscopic insights into the pairing mechanism remains unclear. Here we characterize the superconducting gap structure in the high-temperature superconductor H 3 S and its deuterium counterpart D 3 S by performing tunnelling spectroscopy measurements. The tunnelling spectra reveal that H 3 S and D 3 S both have a fully gapped structure, which could be well described by a single s-wave Dynes model, with gap values 2Δ of approximately 60 meV and 44 meV, respectively. Furthermore, we observed gap features of another likely H-depleted H x S superconducting phase in a poorly synthesized hydrogen sulfide sample. Our work offers direct experimental evidence for superconductivity in the hydrogen-rich superconductor H 3 S from a microscopic perspective. It validates the phonon-mediated mechanism of superconducting pairing and provides a foundation for further understanding the origins of high-temperature superconductivity in hydrogen-rich compounds.
Underground hydrogen storage (UHS) in geological formations is a key element of the clean energy transition as it enables the decarbonization of the transportation and industrial sectors by decoupling hydrogen production and storage. UHS has many benefits, including low cost, much wider availability, large storage capacity, well-established infrastructure, and increased safety because of geological sealing capabilities. However, the impact of hydrogen (H2) biogeochemical interactions in the presence of subsurface microorganisms is largely neglected from UHS perspectives. These interactions might affect the effectiveness of storage and can even cause H2 to leak into the shallow aquifers. Leakage of H2 into groundwater can change the geochemistry and induce several microbial-driven processes. Microorganisms, such as sulfate-reducers, are naturally abundant in groundwater and consume H2 to produce hydrogen sulfide (H2S), which can contaminate the freshwater drinking groundwater and cause damage to infrastructure. Hydrogen leakage can also trigger microbial reactions responsible for metal mobility, which can impact the water quality. However, the kinetics of these reactions and the temporal impact of hydrogen leakage in groundwater are still unknown. Therefore, a time series hydrogen-groundwater interaction experiment was conducted, and the changes in fluid chemistry and headspace gas composition will be analyzed along with DNA sequencing results to understand the extent and kinetics of biogeochemical reactions that occur if hydrogen leaks into groundwater. In the experiments, Ultra High Purity (UHP) hydrogen gas will be injected into glass vials with groundwater samples, for a designated time period. For each glass-sealed vial, 16S rRNA gene sequencing, IC, ICP-MS, and GC-TCD will be performed. The experiments provide insights into plausible impacts of hydrogen leakage into shallow drinking water aquifers.
One of the long-standing challenges in experimental physics is the observation of room-temperature superconductivity (RTSC). Recently, high temperature conventional superconductivity in hydrogen-rich materials has been reported in several systems under high pressure. The most significant discovery in reaching RTSC is the pressure-driven disproportionation of hydrogen sulfide (H 2 S) to H 3 S with a confirmed Tc of 203 kelvin at 155 gigapascals. As H 2 S readily mixes with hydrogen to form guest-host structures at lower pressures, the comparable size of methane to H 2 S should allow molecular exchange within a large assemblage of van der Waals solids that are (highly) hydrogen-rich with H 2 inclusions that are then the building blocks for novel superconducting compounds at extreme conditions. Here, we report superconductivity in a photochemically transformed carbonaceous sulfur hydride system with a maximum superconducting transition temperature of 287.7 ± 1.2 kelvin (~15° celsius) achieved at 267 ± 10 gigapascals. The superconducting state is observed over a broad pressure range from 140 to 275 gigapascals, with a dramatic upturn in Tc above 220 gigapascals. Superconductivity is established by the observation of zero resistance, magnetic susceptibility up to 190 gigapascals, and reduction of Tc under an external magnetic field up to 9 tesla, with an upper critical magnetic field of ~62 tesla based on Ginzburg–Landau (GL) model at zero temperature. The light, quantum nature of hydrogen limits structural and stoichiometric determination using x-ray scattering techniques. Raman spectroscopy is used to probe the chemical and structural transformations pre-metallization. In conclusion, the introduction of chemical tuning within our reported ternary system could be the path forward to lowering the pressure while preserving the RTSC properties.
Background: Lagoons are common along coastlines worldwide and are important for biogeochemical element cycling, coastal biodiversity, coastal erosion protection and blue carbon sequestration. These ecosystems are frequently disturbed by weather, tides, and human activities. Here, we investigated a shallow lagoon in New England. The brackish ecosystem releases hydrogen sulfide particularly upon physical disturbance, causing blooms of anoxygenic sulfur-oxidizing phototrophs. To study the habitat, microbial community structure, assembly and function we carried out in situ experiments investigating the bloom dynamics over time. Results: Phototrophic microbial mats and permanently or seasonally stratified water columns commonly contain multiple phototrophic lineages that coexist based on their light, oxygen and nutrient preferences. We describe similar coexistence patterns and ecological niches in estuarine planktonic blooms of phototrophs. The water column showed steep gradients of oxygen, pH, sulfate, sulfide, and salinity. The upper part of the bloom was dominated by aerobic phototrophic Cyanobacteria, the middle and lower parts by anoxygenic purple sulfur bacteria (Chromatiales) and green sulfur bacteria (Chlorobiales), respectively. We show stable coexistence of phototrophic lineages from five bacterial phyla and present metagenome-assembled genomes (MAGs) of two uncultured Chlorobaculum and Prosthecochloris species. In addition to genes involved in sulfur oxidation and photopigment biosynthesis the MAGs contained complete operons encoding for terminal oxidases. The metagenomes also contained numerous contigs affiliating with Microviridae viruses, potentially affecting Chlorobi. Our data suggest a short sulfur cycle within the bloom in which elemental sulfur produced by sulfide-oxidizing phototrophs is most likely reduced back to sulfide by Desulfuromonas sp. Conclusions: The release of sulfide creates a habitat selecting for anoxygenic sulfur-oxidizing phototrophs, which in turn create a niche for sulfur reducers. Strong syntrophism between these guilds apparently drives a short sulfur cycle that may explain the rapid development of the bloom. The fast growth and high biomass yield of Chlorobi-affiliated organisms implies that the studied lineages of green sulfur bacteria can thrive in hypoxic habitats. This oxygen tolerance is corroborated by oxidases found in MAGs of uncultured Chlorobi. The findings improve our understanding of the ecology and ecophysiology of anoxygenic phototrophs and their impact on the coupled biogeochemical cycles of sulfur and carbon.
The energetically favorable formation of atomically precise clusters, known as magic size clusters, in the solution phase enables a precision nanoscale synthesis with exquisite uniformity. Here, we report the synthesis of magic size clusters via vapor infiltration of atomic layer deposition precursors directly in a polymer thin film. Sequential infiltration of trimethylindium vapor and hydrogen sulfide gas into poly(methyl methacrylate) leads to the formation of clusters with uniform properties consistent with a magic size cluster-In 6 S 6 (CH 3 ) 6 . While an increase in cluster size might be expected with additional sequential infiltration cycles of the reactive In and S precursors, uniform properties consistent with magic size clusters form in multiple polymers under a range of processing conditions. Ultraviolet-visible absorption spectra of In 6 S 6 (CH 3 ) 6 are largely independent of the number of sequential infiltration cycles and exhibit air stability, both of which are attributed to an energetically favorable synthetic pathway that is evaluated with density functional theory.
Lucina pectinata live in high concentrations of hydrogen sulfide (H 2 S) and contains one hemoglobin, Hemoglobin I (HbI), transporting H 2 S and two hemoglobins, Hemoglobin II (HbII) and Hemoglobin (HbIII), transferring dioxygen to symbionts. HbII and HbIII contain B10 tyrosine (Tyr) and E7 glutamine (Gln) in the heme pocket generating an efficient hydrogen bonding network with the (HbII-HbIII)-O 2 species, leading to very low ligand dissociation rates. The results indicate that the oxy-hemeprotein is susceptible to pH from 4 to 9, at acidic conditions, and as a function of the potassium ferricyanide concentration, 100% of the met-aquo derivative is produced. Without a strong oxidant, pH 5 generates a small concentration of the met-aquo complex. The process is accelerated by the presence of salts, as indicated by the crystallization structures and UV–Vis spectra. The results suggest that acidic pH generates conformational changes associated with B10 and E7 heme pocket amino acids, weakening the (HbII-HbIII)-O 2 hydrogen bond network. The observation is supported by X-ray crystallography, since at pH 4 and 5, the heme-Fe tends to oxidize, while at pH 7, the oxy-heterodimer is present. Additionally, conformational changes are observed at higher pH by the presence of a 605 nm transition associated with the iron heme-Tyr interaction. Therefore, pH is one crucial factor regulating the (HbII-HbIII)-O 2 complex hydrogen-bonding network. Thus, it can be proposed that the hydrogen bonding adjustments between the heme bound O 2 and the Tyr and Gln amino acids contribute to oxygen dissociation from the (HbII-HbIII)-O 2 system.
Superconductivity near room temperature in the sulfur–hydrogen system arises from a sequence of reactions at high pressures, with X-ray diffraction experiments playing a central role in understanding these chemical–structural transformations and the corresponding S:H stoichiometry. Here we document X-ray irradiation acting as both a probe and as a driver of chemical reaction in this dense hydride system. We observe a reaction between molecular hydrogen (H 2 ) and elemental sulfur (S 8 ) under high pressure, induced directly by X-ray illumination, at photon energies of 12 keV using a free electron laser. The rapid synthesis of hydrogen sulfide (H 2 S) at 0.3 GPa was confirmed by optical observations, spectroscopic measurements, and microstructural changes detected by X-ray diffraction. These results document X-ray induced chemical synthesis of superconductor-forming dense hydrides, revealing an alternative production strategy and confirming the disruptive nature of X-ray exposure in studies on high-pressure hydrogen chalcogenides, from water to high-temperature superconductors.
To mitigate climate change and adopt renewable energy, energy storage is crucial and can be done in the form of hydrogen gas (H 2 ). Subsurface geologic reservoirs are positioned to store H 2 on the largest scales for the longest terms of all potential options. However, H 2 injection may boost reactions that consume hydrogen, generate undesired gases, and alter pore structures of geomedia. To explore the extent of H 2 -associated biotic reactions at a near wellbore location, four experiments were conducted under underground storage conditions with wellbore cement cores and, in most instances, shale samples submerged in synthetic formation brine. Post-reaction gas, aqueous, and solid phase samples were analyzed using olfactory screening and, later, gas chromatography (GC-MS), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), and synchrotron micro-scale x-ray fluorescence (μ-XRF). Within a period of 16 weeks, hydrogen sulfide (H 2 S) was generated in systems containing both H 2 and shale. XRF mapping identified a zone enriched in iron(II) and reduced sulfur along the rim of cement cross sections that was largely associated with CO 2 -induced cement carbonation. Shale did not show noticeable alteration, but there is evidence it contributed to the initial inoculation of the system and provided nutrients for microbes via water-rock interactions. Here, this study considers both rock formations and wellbore cement not previously evaluated concurrently. Findings support understanding and modeling of H 2 -associated biogeochemical reactions during underground hydrogen storage.
The binding energy of hydrogen sulfide, ammonia, ethane, ethylene, butadiene, benzene, toluene, pyridine, pyrrole, and thiophene on the basal plane of the semi-conducting 2H-molybdenum sulfide (MoS 2 ) was calculated with the following flavors of Density Functional Theory (DFT): GGA-PW91, PBE-D3, vdW-DF, optPBE, optB86b, optB88, vdW-TS, and BEEF-vdW. The GGA-PW91 binding energies are negligible (<0.07 eV in magnitude) in all cases. The predictions with vdW-DF and PBE-D3 are the closest (error <0.05 eV) to the isosteric heats of adsorption calculated from reported temperature programmed desorption data for thiophene and butadiene. For all dispersion flavors examined here, the magnitude of the dispersion contribution to the binding energy increases linearly with the number of heavy atoms in the adsorbate, with each atom contributing 0.05 eV (BEEF-vdW) – 0.09 eV (optB88-vdW). Further, this implies that the calculated adsorption constants of molecules larger than acridine (i.e., comprising > 14 non-heavy atoms) can vary by more than four orders of magnitude at industrial conditions depending on the chosen method of dispersion correction. Further, dispersion effects fall off rapidly (>0.03 eV/ non-hydrogen atom/Å) as the adsorbate-surface distance increases.
Here, this study investigates the reaction of hydrogen (H 2 ) with pyrite (FeS 2 ), focusing on how temperature and the presence of water influence the reaction pathways and kinetics. Utilizing computational molecular simulations and kinetic analyses, we explore the impact of these factors on the formation of hydrogen sulfide (H 2 S) and related species. First, grand canonical Monte Carlo/molecular dynamics (GCMC/MD) simulations reveal that physical H 2 adsorption occurs in distinct layers on the pyrite surface. In addition, increased temperatures reduce the absolute adsorption capacities. Reactive MD simulations demonstrate that H 2 interacts differently with pyrite under varying conditions. At 298 K, H 2 reacts with pyrite to form HS – , leading to the formation of HS – through covalent bonding with sulfur of pyrite. However, no H 2 S is produced at this temperature, suggesting that a kinetic barrier (i.e., activation energy) may prevent this reaction. At higher temperatures, H 2 S production significantly increases. The presence of water introduces additional complexity to the reaction mechanism. Unlike dry conditions, water enhances H 2 S generation, even at low temperatures. Water also facilitates the formation of additional products, such as SOH, indicating a more intricate chemical environment on the pyrite surface. Our findings identify the association of HS – ions to form H 2 S as the rate-limiting step, with temperature influencing this process. This finding suggests that while the presence of water can create a more dynamic reaction environment, the overall mechanisms leading to H 2 S formation remain consistent. These outcomes suggest the need for developing targeted strategies to manage and control H 2 S emissions within the context of underground hydrogen storage.
Multiplexed gas detection at room temperature is critical for practical applications, such as for tracking the complex chemical environments associated with food decomposition and spoilage. Here, an integrated array of multiple silicon-based, chemical-sensitive field effect transistors (CSFETs) is presented to realize selective, sensitive, and simultaneous measurement of gases typically associated with food spoilage. CSFETs decorated with sensing materials based on ruthenium, silver, and silicon oxide are used to obtain stable room-temperature responses to ammonia (NH 3 ), hydrogen sulfide (H 2 S), and humidity, respectively. For example, one multi-CSFET sensor signal changes from its baseline by 13.34 in response to 1 ppm of NH 3 , 724.45 under 1 ppm H 2 S, and 23.46 under 80% relative humidity, with sensitive detection down to 10 ppb of NH 3 and H 2 S. To demonstrate this sensor for practical applications, the CSFET sensor array is combined with a custom-printed circuit board into a compact, fully integrated, and portable system to conduct real-time monitoring of gases generated by decomposing food. By using existing silicon-based manufacturing methodologies, this room-temperature gas sensing array can be fabricated reproducibly and at low cost, making it an attractive platform for ambient gas measurement needed in food safety applications.