H2S Generation Research Articles

Effect of H2S and cysteine homeostasis disturbance on ciprofloxacin sensitivity of Escherichia coli in cystine-free and cystine-fed minimal medium.

Endogenous H2S has been proposed to be a universal defense mechanism against different antibiotics. Here, we studied the role of H2S transiently generated during ciprofloxacin (CF) treatment in M9 minimal medium with sulfate or produced by E. coli when fed with cystine. The cysM and mstA mutants did not produce H2S, while gshA generated more H2S in response to ciprofloxacin in cystine-free media. All mutants showed a reduced ability to maintain cysteine homeostasis under these conditions. We found no relationship between H2S generation, cysteine concentration and sensitivity to ciprofloxacin. Excess cysteine, which occurred during E. coli growth in cystine-fed media, triggered continuous H2S production, accelerated glutathione synthesis and cysteine export. This was accompanied by a twofold increase in ciprofloxacin tolerance in all strains except gshA, whose sensitivity increased 5-8-fold at high CF doses, indicating the importance of GSH in restoring the intracellular redox situation during growth in cystine-fed media.

A Spatiotemporally Controlled and Mitochondria-Targeted Prodrug of Hydrogen Sulfide Enables Mild Mitochondrial Uncoupling for the Prevention of Lipid Deposition.

Mild mitochondrial uncoupling offers therapeutic benefits for various diseases like obesity by regulating cellular energy metabolism. However, effective chemical intervention tools for inducing mild mitochondria-targeted uncoupling are limited. Herein, we have developed a mitochondria-targeted H2S prodrug M1 with a unique property of on-demand photoactivated generation of H2S accompanied by self-reporting fluorescence for real-time tracking. Upon photoirradiation, M1 decomposes in mitochondria to generate H2S and a turn-on fluorescent coumarin derivative for the visualization and quantification of H2S. M1 is confirmed to induce reactive oxygen species (ROS)-dependent mild mitochondrial uncoupling, activating mitochondria-associated adenosine monophosphate-activated protein kinase (AMPK) to suppress palmitic acid (PA)-induced lipid deposition in hepatocytes. The uncoupling functions induced by M1 are strictly controlled in mitochondria, representing a fresh strategy to prevent lipid deposition and improve metabolic syndrome by increasing cellular energy expenditure.

Case Study: Understanding H2S Occurrence: Bakken Production Using Sulfur Isotopes

_ Souring—or H2S generation—in the Bakken petroleum system (BPS) production is becoming problematic for oil producers and pipeline operators because of the sporadic occurrence and associated economic and HSE impacts. Paradoxically, crude oil produced from the tight Middle Bakken (MB) and underlying Three Forks (TF) reservoirs of the BPS has historically been light (40 °API to 50 °API) with low sulfur content (<0.2 wt.%), typically exhibiting nonexistent to low (<10 parts per million) H2S concentrations. Additionally, neither the MB nor the TF reservoirs have public records indicating the presence of H2S during drillstem tests (DST). However, based on previous work performed by the University of North Dakota Energy & Environmental Research Center (EERC), the frequency of H2S occurrence in BPS wells has increased from 2010 to 2023. Even though the observed H2S increases correlate with larger, multistage well stimulation and completion practices in the BPS, the unclear geographical and temporal trends make the exact mechanisms responsible for souring an open research question. At least five known mechanisms can potentially lead to H2S occurrence in the oil production stream of BPS wells, including: 1. Thermochemical sulfate reduction (TSR) 2. Bacterial sulfate reduction (BSR) 3. Source rock generation 4. Migration from deeper or shallower H2S reservoirs 5. Geochemical mechanisms related to reservoir stimulation work (Table 1). Understanding the mechanisms of H2S generation might reduce the risk of souring in new wells and enable more effective mitigation and management strategies in the wells already producing H2S. Samples Used in the Study This study is focused on oil and gas operations in the North Dakota portion of the Williston Basin and the H2S occurrences in the BPS, which includes two main oil-producing reservoirs: the MB and the TF. In the simplified stratigraphic sequence, the BPS comprises three distinctive lithofacies. From deepest to shallowest, those lithofacies are the Lower Bakken Shale (LBS), the MB reservoir, and the Upper Bakken Shale (UBS). Underlying the BPS is the TF, the upper part of which is the oil-rich TF reservoir, considered part of the BPS. The UBS and LBS are the source rocks for the oil in MB and TF reservoirs and consist of black, organic-rich, siliciclastic mudstones (i.e., shale). Directly overlying the BPS is the Madison Group, a carbonate-dominated Mississippian section that is subdivided into three formations—the Lodgepole (LP), Mission Canyon (MC), and Charles. The Birdbear Formation lies beneath the TF and on top of the Duperow Formation. Both the Duperow and Birdbear Formations produce oil and are dominated by carbonate deposits of shallow marine limestone and dolostones. A sampling program was developed to investigate areas of the BPS with varying levels of souring in the production stream and multiple organic-rich formations representing potential source rocks, including the UBS, LBS, LP, and MC. The samples were collected from locations and formations with different lithologies and maturity levels. Over 70 sour wells were identified for H2S sampling in western North Dakota.

Protein persulfidation in plants: mechanisms and functions beyond a simple stress response

Abstract Posttranslational modifications (PTMs) can modulate the activity, localization and interactions of proteins and (re)define their biological function. Understanding how changing environments can alter cellular processes thus requires detailed knowledge about the dynamics of PTMs in time and space. A PTM that gained increasing attention in the last decades is protein persulfidation, where a cysteine thiol (-SH) is covalently bound to sulfane sulfur to form a persulfide (-SSH). The precise cellular mechanisms underlying the presumed persulfide signaling in plants are, however, only beginning to emerge. In the mitochondrial matrix, strict regulation of persulfidation and H2S homeostasis is of prime importance for maintaining mitochondrial bioenergetic processes because H2S is a highly potent poison for cytochrome c oxidase. This review summarizes the current knowledge about protein persulfidation and corresponding processes in mitochondria of the model plant Arabidopsis. These processes will be compared to the respective processes in non-plant models to underpin similarities or highlight apparent differences. We provide an overview of mitochondrial pathways that contribute to H2S and protein persulfide generation and mechanisms for H2S fixation and de-persulfidation. Based on current proteomic data, we compile a plant mitochondrial persulfidome and discuss how persulfidation may regulate protein function.

Brass corrosion – dezincification in hydrochloric acid

Abstract Brass is among the utility metals for daily life. We present an easy corrosion experiment for demonstration in high school or first-year undergraduate studies. Almost any kind of brass can be dezincified in 1 m hydrochloric acid. Copper as the noble component remains as salmon pink coating on the workpiece while zinc and lead, the latter being a frequent minor alloying component of brass, are dissolved. Lead can be detected as PbS (in-situ generation of H2S from a splinter of FeS or as PbI2 using KI). Zinc can be analyzed as Rinmann’s green or via a microchemical drop reaction with dithizone.

Predicting thermochemical sulfate reduction reaction process and H2S generation in carbonate reservoirs using comprehensive kinetics modeling

Thermochemical sulfate reduction (TSR) is a critical process controlling hydrogen sulfide (H2S) generation in carbonate reservoirs, posing significant economic and safety challenges for the oil and gas industry. This study develops a comprehensive model that integrates detailed thermal, burial, and hydrocarbon generation histories with key TSR kinetic parameters, such as reaction rate constants and activation energies, to predict TSR evolution and H2S generation accurately. A notable feature of the model is to separate and quantify the contributions of different hydrocarbon species (CH4, C2-5, C6-14, and C15+) to the overall TSR process, using the Arrhenius equation to simulate the temperature-dependent behavior of TSR for each hydrocarbon group. The model also accounts for the in-reservoir thermal cracking of heavier hydrocarbons into light hydrocarbons, ensuring predictions closely align with geological processes. Modeling results show that TSR reactions accelerate the depletion of oil and wet gas components. A large amount of CH4 is generated due to both kerogen thermal cracking and alteration of heavy hydrocarbon. Our modeling also allows for accurate prediction of TSR reactions as well as the timing and extent of H2S and CO2 generation over the history of a reservoir. Applications in the Puguang and Hetianhe gas fields validate the model's broad applicability and reliability, capturing extensive TSR activities and being consistent with the observed data. These results underscore the models' robustness in detailed predictions of TSR dynamics across diverse geological settings and its potential as a valuable tool for managing sour gas production, aiding in risk assessment and resource management.

Concerted Influence of H2O and CO2: Moisture Exposure of Sulfide Solid Electrolyte Li4SnS4.

Although moisture-induced deterioration mechanisms in sulfide solid electrolytes to enhance atmospheric stability have been investigated, the additional impact of CO2 exposure remains unclear. This study investigated the generation of H2S from Li4SnS4 under H2O and CO2 exposure. Li4SnS4 was exposed to Ar gas at a dew point of 0 °C with and without 500 ppm of CO2, and its ion conductive properties were evaluated. Although the lithium-ion conductivity of Li4SnS4 decreased regardless of the presence of CO2, the amount of H2S generated with CO2 was five times higher. To elucidate the underlying mechanism, X-ray diffraction and Raman spectroscopy were used. Without CO2, hydrate Li4SnS4·4H2O formation markedly increased, whereas, with CO2, it increased a little. The difference revealed distinct deterioration mechanisms leading to a decrease in lithium-ion conductivity: without CO2, adsorbed H2O and Li4SnS4·4H2O contributed to the decrease, while with CO2, a weak acid dissociation reaction could reduce the thermodynamic stability of the moisture-exposed Li4SnS4 surface including Li4SnS4·4H2O and adsorbed H2O, promoting H2S release and carbonate formation. This was supported by the recovery of lithium-ion conductivity after vacuum heating. The concerted influence of H2O and CO2 provides valuable insights into the fundamental deterioration mechanisms in sulfide solid electrolytes that could be applied in battery manufacturing processes.

Self-correcting ratiometric fluorescence assay for H2S detection in live cells and releasing agents

Hydrogen sulfide (H2S) is both a biologically significant signaling molecule, and a harmful gas that is generated in the environment; thus, its detection and monitoring are required in range of biological and environmental systems. Most fluorescent probes for H2S detection rely on single-detection fluorescence signals, making them vulnerable to interference from other species in complex microenvironment. In this study, we developed a ratiometric fluorogenic and colorimetric assay for H2S detection, in which pyrene and naphthalimide fluorophores operate together to provide a selective and sensitive detection system. Pyrene maintains fluorescence (always ‘On’), while naphthalimide exhibits an ‘On-Off’ response through thiolysis with H2S. By measuring the ratiometric fluorescence from these moieties, a self-calibrating response can be measured that is resistant to interference from other species in the microenvironments. The probe was used to measure H2S generation from H2S donor substrates and to monitor H2S fluctuations within living cells through selective, ratiometric fluorescence changes and real-time, dual-channel fluorescence imaging.

Microbial assimilatory sulfate reduction-mediated H2S: an overlooked role in Crohn’s disease development

BackgroundH2S imbalances in the intestinal tract trigger Crohn's disease (CD), a chronic inflammatory gastrointestinal disorder characterized by microbiota dysbiosis and barrier dysfunction. However, a comprehensive understanding of H2S generation in the gut, and the contributions of both microbiota and host to systemic H2S levels in CD, remain to be elucidated. This investigation aimed to enhance comprehension regarding the sulfidogenic potential of both the human host and the gut microbiota.ResultsOur analysis of a treatment-naive CD cohorts' fecal metagenomic and biopsy metatranscriptomic data revealed reduced expression of host endogenous H2S generation genes alongside increased abundance of microbial exogenous H2S production genes in correlation with CD. While prior studies focused on microbial H2S production via dissimilatory sulfite reductases, our metagenomic analysis suggests the assimilatory sulfate reduction (ASR) pathway is a more significant contributor in the human gut, given its high prevalence and abundance. Subsequently, we validated our hypothesis experimentally by generating ASR-deficient E. coli mutants ∆cysJ and ∆cysM through the deletion of sulfite reductase and L-cysteine synthase genes. This alteration significantly affected bacterial sulfidogenic capacity, colon epithelial cell viability, and colonic mucin sulfation, ultimately leading to colitis in murine model. Further study revealed that gut microbiota degrade sulfopolysaccharides and assimilate sulfate to produce H2S via the ASR pathway, highlighting the role of sulfopolysaccharides in colitis and cautioning against their use as food additives.ConclusionsOur study significantly advances understanding of microbial sulfur metabolism in the human gut, elucidating the complex interplay between diet, gut microbiota, and host sulfur metabolism. We highlight the microbial ASR pathway as an overlooked endogenous H2S producer and a potential therapeutic target for managing CD.Dka3P5uGJeBhH66pkNJcogVideo

Cystathionine gamma-lyase deficiency exaggerates diethylnitrosamine-induced liver damage in mice

Cystathionine gamma-lyase (CSE) is a key enzyme in reverse transsulfuration pathway and contributes to the majority of H2S generation in liver tissues via cysteine metabolism. Dysfunction of the CSE/H2S system is linked to both chronic and acute liver damage. This study investigated the regulatory role of CSE deficiency on diethylnitrosamine (DEN)-induced liver damage in mice. A single injection of DEN was administered into 4-week-old male CSE knockout (CSE-KO) mice and wild-type (WT) littermates, and the mice were sacrificed at 28 weeks of age. Compared to age-matched WT mice, CSE-KO mice spontaneously developed steatosis with increased oxidative stress and higher expressions of inflammation and fibrosis-related genes at 28-weeks of age. Following DEN injection, CSE-KO mice experienced more severe liver damage in comparison with the WT group as reflected by elevated levels of lipid accumulation, increased activities of alanine aminotransferase and aspartate aminotransferase, higher oxidative stress and fibrosis development, and increased expressions of inflammation and fibrosis-related genes. No visible tumors were observed in both types of mice with DEN treatment. In addition, the expression levels of the three H2S-generating proteins (CSE, cystathionine beta-synthase, and 3-mercaptopyruvate sulfurtransferase) and the H2S production rate in liver tissues were unaffected by DEN. Taken together, our study demonstrates that CSE provides a significant hepatoprotective effect and deficiency of CSE exaggerates DEN-induced liver damage in mice. Based on these findings, it can be suggested that targeting the CSE/H2S signaling pathway could be a potential therapeutic target for the treatment of liver diseases.

Experimental and simulation study on the thermal decomposition of Xishan coal and the pyrolysis of coal with Na2SO4

ABSTRACT Based on the Thermal Decomposition of Xishan coal Experiments and ReaxFF MD Simulations, the study investigated the processes and product changes in the thermal decomposition of coal and the pyrolysis of coal with Na2SO4. The results indicate that the initial temperature of thermal decomposition of Xishan coal is around 300 °C in experiments and approximately 1600 K in molecular simulations. The addition of Na2SO4 advances the initial pyrolysis temperature and promotes the generation of total number and types of products. Xishan coal pyrolysis generates a large number of small molecular gases and free radicals, and the addition of Na2SO4 promotes the generation of CO, CH4, and H2S, as well as the accumulation of a significant number of free radicals. Free Na mainly affects the evolution of N elements, promoting the formation of N into amino groups, and Na easily combines with sulfur-containing intermediates. Through the extraction of sulfur-containing intermediates and the analysis of the influence of free radicals, it was found that S elements Xishan coal ultimately forms H2S. This study microscopically confirms that in the coal with Na2SO4 system, H2S originates from the hybridised sulfur atoms in the carbon chain and free SO 4 2 − .

Design of multifunctional theranostic nanoplatforms with glutathione-triggered H2S generation and H2S-activitated multi-modal therapy

Hydrogen sulfide (H2S) is a specific substance in the tumor microenvironment, and highly expressed H2S can be used to activate some agents for intelligent treatment of tumors. However, not all tumors contain overexpressed hydrogen sulfide. To address this obstacle, we report the design of theranostic nanoplatforms with glutathione-triggered H2S generation and H2S-triggered therapy activation functions, by using hollow mesoporous organosilica nanoparticles (HMON) to load Cu-HMME framework nanodots (CuHF) and garlic extract diallyl trisulfide (DATS). Such CuHF/DATS@HMON with sizes of about 110 nm exhibit obvious quenching fluorescence and is inactive. Importantly, when CuHF/DATS@HMON is mixed with glutathione (GSH) solution, the nucleophilic attack of GSH on trisulfide bonds (−S-S-S-) in DATS generates S-allyl glutathione disulfide (GSSA) and allyl perthiol (ASSH), with the latter releasing H2S upon reduction by GSH, conferring the overexpress of H2S as the first-cascade activation. Furthermore, endogenous H2S can react with CuHF to produce CuS nanoparticles with strong chemodynamic/photothermal effect and to release metal porphyrin ((Cu)HMME) with photodynamic effect, as the second-cascade activation. When CuHF/DATS@HMON is accumulated at the tumor site through EPR effect, DATS in the CuHF/DATS@HMON can react with endogenous glutathione (GSH) in cancer cells to in situ generate H2S, and then H2S can vulcanize CuHF to generate CuS nanoparticles and (Cu)HMME complexes, thus realizing chemokinetic, photodynamic and photothermal multi-mode therapy to inhibit tumor growth. At the same time, the tetrasulfide bonds (−S-S-S-S-) in HMON allow the material to be slowly broken down and metabolized. Therefore, this study not only provides a general design for constructing tumor-microenvironment-responsive agents, but also provides some insights for multi-modal therapy of cancers.

The interplay of hydrogen sulfide and microRNAs in cardiovascular diseases: insights and future perspectives.

Hydrogen sulfide (H2S) is recognized as the third gasotransmitter, after nitric oxide (NO) and carbon monoxide (CO). It is known for its cardioprotective properties, including the relaxation of blood vessels, promotion of angiogenesis, regulation of myocardial cell apoptosis, inhibition of vascular smooth muscle cell proliferation, and reduction of inflammation. Additionally, abnormal H2S generation has been linked to the development of cardiovascular diseases (CVD), such as pulmonary hypertension, hypertension, atherosclerosis, vascular calcification, and myocardial injury. MicroRNAs (miRNAs) are non-coding, conserved, and versatile molecules that primarily influence gene expression by repressing translation and have emerged as biomarkers for CVD diagnosis. Studies have demonstrated that H2S can ameliorate cardiac dysfunction by regulating specific miRNAs, and certain miRNAs can also regulate H2S synthesis. The crosstalk between miRNAs and H2S offers a novel perspective for investigating the pathophysiology, prevention, and treatment of CVD. The present analysis outlines the interactions between H2S and miRNAs and their influence on CVD, providing insights into their future potential and advancement.

Dynamic changes of endogenous H2S generation during responding to developmental and environmental signals in Solanum lycopersicum L.

Increasing studies have confirmed the functions of hydrogen sulfide (H2S) as a gas signal molecule (gasotransmitter) in a variety of physiological activities in plants. However, the dynamic changes of endogenous H2S generation, especially the response speed and degree of H2S-generation-associated members, to both developmental and environmental cues in Solanum lycopersicum L. are still poorly understood. Here, we identified and charactered the H2S-generation-associated enzymes in tomato, including O-acetylserine (mercaptan) lyases (OAS-TL), L/D-Cysteine desulfhydrases (L/D-CDes) and nitrogen fixation S (NIFS)-like enzymes, possessing LCD-like activity. Analysis of cis-regulatory elements (CREs) showed that the promoter regions of these H2S-generation-associated genes contained lots of light-, hormone- and stresses-responsive CREs, and transcriptional factors (TFs) binding sites, suggesting that the regulatory mechanism of endogenous H2S generation might involve TFs mediated transcriptional regulation or/and interacting with phytohormones signals. Levels of endogenous H2S exhibited diversity in different organs and developmental stages in tomato, and the top and second highest level of H2S in flowers and ripened fruits hinted the significance of H2S signal in tomato reproduction and fruit development. Furthermore, the expression of SlOAS4, SlLCD, SlDCD2, SlNFS1, and SlNFS2 enhanced continuously during fruit ripening, and the SlOAS4 expression exhibited the most significant up-regulation. The SlDCD enzymatic activity responded more quickly to fruit development cues, while the SlLCD remained at a higher level almost throughout the whole fruit ripening. During environmental stimulus, it was found that the transcriptions of SlDCD2 and SlOAS2 responded faster and stronger to heat stress, while SlOAS4 and SlLCD were activated more quickly and significantly by drought stress. Both SlLCD and SlDCD enzymatic activities could be enhanced by drought and heat stress to varying degrees, and it seemed that the SlLCD was activated to a greater extent and remained at the higher activity for a longer period. With the extension of exogenous phytohormones (ABA, SA, GA, JA, ACC, NAA) treatment, the SlLCD activity and the endogenous H2S content increased in a specific time-dependent manner, and ABA, SA and NAA had more rapid effects on SlLCD activity. By widely explored the dynamic responses of endogenous H2S generation, our study would provide some references for understanding the regulatory mechanism upstream of H2S signaling in tomato growth developments and environmental adaptations.

Targeting glioma stem cells with thyroid hormone suppression: Phase 1/2 trial of methimazole in patients with progressive grade 4 gliomas.

2044 Background: Gaseous hydrogen sulfide (H2S), a by-product of cysteine metabolism, inhibits the growth of glioblastoma (GBM) cells and impairs GBM progression in mice. Likewise, H2S generation and sulfhydration are decreased in human GBM specimens as compared to non-tumor controls. Thus, boosting H2S production is a novel strategy for GBM treatment. Suppression of thyroid hormone (TH) signaling increases endogenous production of H2S. We hypothesize that methimazole-induced hypothyroidism will enhance the efficacy of chemotherapy in WHO grade 4 gliomas by boosting H2S production capacity (HPC) within the tumor. The goal of this trial is to provide proof of concept that suppression of TH signaling, via methimazole and subsequent augmentation of H2S synthesis and signaling, is feasible in patients with WHO grade 4 gliomas (G4G). Methods: This modified phase 1/2 study evaluates the safety and efficacy of methimazole + chemotherapy with pharmacodynamic correlates in patients with progressive G4G. The main objective is a 10% increase in HPC and a 1.5-fold increase in peripheral blood sulfhydration signaling (SS). Patients who are planned for a clinically-indicated resection receive pre-op (5-7 days) and post-op methimazole with the addition of investigator’s choice of chemotherapy 1 month after starting post op methimazole. Patients receive methimazole + chemotherapy until progression. Resected tumor will be assayed for HPC and for proteins relevant to H2S production. Peripheral blood lead-acetate assays for HPC and SS are obtained at baseline, pre-op, intra-op, post-op, before the addition of chemotherapy, and before each cycle of methimazole + chemo. Key eligibility criteria: progressive G4G for whom a clinically-indicated resection is planned, and normal thyroid function with no history of thyroid disease. Patients may have had unlimited prior regimens including bevacizumab. Results: To date six patients (4 male) ages 49-59 years have enrolled. At all time points tested post-methimazole treatment relative to baseline age/sex matched no-methimazole control patients, there were significant increases in plasma H2S production capacity (table). Conclusions: In this early cohort, it appears methimazole treatment in recurrent GBM patients enhances HPC on a systemic level. Next steps will be to measure sulfide signaling and sulfhydration alterations in patient tumor samples. The protocol is being modified to allow earlier addition (2 weeks) of post-op chemotherapy. Clinical trial information: NCT05607407 . [Table: see text]

Sodium nitroprusside modulates oxidative and nitrosative processes in Lycopersicum esculentum L. under drought stress

Key messageSodium nitroprusside mediates drought stress responses in tomatoes by modulating nitrosative and oxidative pathways, highlighting the interplay between nitric oxide, hydrogen sulfide, and antioxidant systems for enhanced drought tolerance.While nitric oxide (NO), a signalling molecule, enhances plant tolerance to abiotic stresses, its precise contribution to improving tomato tolerance to drought stress (DS) through modulating oxide-nitrosative processes is not yet fully understood. We aimed to examine the interaction of NO and nitrosative signaling, revealing how sodium nitroprusside (SNP) could mitigate the effects of DS on tomatoes. DS-seedlings endured 12% polyethylene glycol (PEG) in a 10% nutrient solution (NS) for 2 days, then transitioned to half-strength NS for 10 days alongside control plants. DS reduced total plant dry weight, chlorophyll a and b, Fv/Fm, leaf water potential (ΨI), and relative water content, but improved hydrogen peroxide (H2O2), proline, and NO content. The SNP reduced the DS-induced H2O2 generation by reducing thiol (–SH) and the carbonyl (–CO) groups. SNP increased not only NO but also the activity of l-cysteine desulfhydrase (L-DES), leading to the generation of H2S. Decreases in S-nitrosoglutathione reductase (GSNOR) and NADPH oxidase (NOX) suggest a potential regulatory mechanism in which S-nitrosylation [formation of S-nitrosothiol (SNO)] may influence protein function and signaling pathways during DS. Moreover, SNP improved ascorbate (AsA) and glutathione (GSH) and reduced oxidized glutathione (GSSG) levels in tomato plants under drought. Furthermore, the interaction of NO and H2S, mediated by L-DES activity, may serve as a vital cross-talk mechanism impacting plant responses to DS. Understanding these signaling interactions is crucial for developing innovative drought-tolerance strategies in crops.

A multifunctional protein-based hydrogel with Au nanozyme-mediated self generation of H2S for diabetic wound healing

Diabetics usually suffer from chronic impaired wound healing due to facile infection, excessive inflammation, diabetic neuropathy, and peripheral vascular disease. Hence, the development of effective diabetic wound therapy remains a critical clinical challenge. Hydrogen sulfide (H2S) regulates inflammation, oxidative stress, and angiogenesis, suggesting a potential role in promoting diabetic wound healing. Herein, we propose a first example of fabricating an antibiotic-free antibacterial protein hydrogel with self-generation of H2S gas (H2S-Hydrogel) for diabetic wound healing by simply mixing bovine serum albumin‑gold nanoclusters (BSA-AuNCs) with Bis[tetrakis(hydroxymethyl)phosphonium] sulfate (THPS) at room temperature within a few minutes. In this process, the amino group in BAS and the aldehyde group in THPS are crossed together by Mannich reaction. At the same time, tris(hydroxymethyl) phosphorus (trivalent phosphorus) from THPS hydrolysis could reduce disulfide bonds in BSA to sulfhydryl groups, and then the sulfhydryl group generates H2S gas under the catalysis of BSA-AuNCs. THPS in H2S-Hydrogel can destroy bacterial biofilms, while H2S can inhibit oxidative stress, promote proliferation and migration of epidermal/endothelial cells, increase angiogenesis, and thus significantly increase wound closure. It would open a new perspective on the development of effective diabetic wound dressing.

A one-dimensional diffusive transport model to evaluate H2S generation in salt caverns hydrogen storage sites

Salt caverns are considered a potential hydrogen storage site given the ductility, tightness, and chemical inertness of halite. In addition, unlike porous media, salt caverns require less cushion gas and allow more cycles of injection and production within a year. However, hydrogen is an electron donor for many hydrogenotrophic microorganisms including halophilic sulfate-reducing microbes (SRM) and hydrogen sulfide (H2S) can be generated in a cavern once sulfate and hydrogen become available in the aqueous phase. As salt deposits are often associated with large amounts of impurities such as anhydrite and gypsum, their dissolution during the leaching phase can release the required sulfate ions for SRMs to produce H2S once hydrogen diffuses and dissolves in the brine at the bottom of the cavern. In this study, a one-dimensional diffusive transport model was developed using PHREEQC to simulate sulfate reduction and H2S generation in a cavern at the gas-brine interface. The solution of Fick's diffusion equation was used to calculate the hydrogen concentration at each level of the 1D model while the kinetic rates of reactions were derived from reported experimental and field site observations of brine samples taken from salt caverns. The results obtained indicated that hydrogen consumption at the gas-brine interface can trigger H2S and methane formations. This is followed by a reduction in sulfate and carbonate concentration and a slight increase in pH due to the reduction of protons in the solution. It was also observed that the presence of Fe2+ ions can reduce the amount of the hydrogen sulfide production while Ca2+ ions slightly favour sulfate reduction due to the production of methane. Although the kinetic reaction rate of the reactions in the model is subject to a certain degree of uncertainty, the workflow and results this study can serve as a guide for the future storage of hydrogen in salt caverns.

Integrating machine learning algorithm with sewer process model to realize swift prediction and real-time control of H2S pollution in sewer systems

The frequent occurrence of safety incidents in sewer systems due to the emergency toxicity of hydrogen sulfide (H2S) necessitate timely and efficient prediction, early warning and real-time control. However, various factors influencing H2S generation and emission leads to a substantial computational burden for the existing dynamic sewer process models and fails to timely control the H2S exposure risk. The present study proposed a swift prediction model (SPM) that combined the validated dynamic sewer process model (the biofilm-initiated sewer process model, BISM) with a high-speed machine learning algorithm (MLA), achieving accurately and swiftly predict the dissolved sulfide (DS) concentration and H2S concentration in a specific sewer network. Based on Gradient Boosting Decision Tree-based SPM, the simulated concentrations of DS and H2S are 1.95 mg S/L and 214 ppm, respectively, which are closely to the field-measured values of 1.82 mg S/L and 219 ppm. Notably, SPM achieved a computation time of less than 0.3 s, and a significant improvement over BISM (> 5000 s) for the same task. Moreover, the real-time and dynamic dosing scheme facilitated by SPM outperformed the conventional constant dosing scheme provided by dynamic sewer process model, which significantly improved the H2S control completion rate from 69 % to 100 %, and achieved a significant reduction in chemical dosage. In conclusion, the integration of dynamic sewer process models with MLA addresses the inadequacy of monitoring data for MLA training, and thus pursues swift prediction of H2S generation and emission, and achieving real-time, effective, and economic control of H2S in complex sewer networks.

Pan-inhibition of the three H2S synthesizing enzymes restrains tumor progression and immunosuppression in breast cancer

BackgroundHydrogen sulfide (H2S) is a significant endogenous mediator that has been implicated in the progression of various forms of cancer including breast cancer (BC). Cystathionine-β-synthase (CBS), cystathionine-γ-lyase (CSE), and 3-mercaptopyruvate sulfurtransferase (3MST) are the three principal mammalian enzymes responsible for H2S production. Overexpression of CBS, CSE and 3MST was found to be associated with poor prognosis of BC patients. Moreover, H2S was linked to an immune-suppressive tumor microenvironment in BC. Recently it was observed that BC cells, in response to single or dual inhibition of H2S synthesizing enzymes, develop an escape mechanism by overexpressing alternative sources of H2S generation. Thus, the aim of this work is to escape the H2S compensatory mechanism by pan repressing the three enzymes using microRNAs (miRNAs) and to investigate their impact on the oncogenic and immunogenic profile of BC cells.MethodsBC female patients (n = 25) were recruited. In-silico analysis was used to identify miRNAs targeting CBS, CSE, and 3MST. MDA-MB-231 cells were cultured and transfected using oligonucleotides. Total RNA was extracted using Biazol, reverse transcribed and quantified using qRT-PCR. H2S levels were measured using AzMc assay. BC hallmarks were assessed using trans-well migration, wound healing, MTT, and colony forming assays.ResultsmiR-193a and miR-548c were validated by eight different bioinformatics software to simultaneously target CBS, CSE and 3MST. MiR-193a and miR-548c were significantly downregulated in BC tissues compared to their non-cancerous counterparts. Ectopic expression of miR-193a and miR-548c in MDA-MB-231 TNBC cells resulted in a marked repression of CBS, CSE, and 3MST transcript and protein levels, a significant decrease in H2S levels, reduction in cellular viability, inhibition of migration and colony forming ability, repression of immune-suppressor proteins GAL3 GAL9, and CD155 and upregulation of the immunostimulatory MICA and MICB proteins.ConclusionThis study sheds the light onto miR-193a and miR-548c as potential pan-repressors of the H2S synthesizing enzymes. and identifies them as novel tumor suppressor and immunomodulatory miRNAs in TNBC.