Interaction Of H2S Research Articles

MoSe2-Layered Nanosheet Decorated SnO2 Hollow Nanofiber-Based Highly Sensitive and Selective Room Temperature H2S Gas Sensor.

In this work, we successfully demonstrated a MoSe2@SnO2 nanocomposite-based room temperature H2S gas sensor. A sensing mechanism was proposed based on experimental results and density functional theory calculations. The FESEM micrographs of the heterostructure formed by hydrothermally grown MoSe2-layered nanosheets and SnO2-hollow nanofiber result in a high surface area for H2S gas adsorption. On exposure to calcination, the electro-spun PVP/SnO2 nanofiber undergoes the Kirkendall phenomenon, resulting in 94.6 nm thick hollow nanofibers. The combination of TMD@SMO shows an abundance of charge transfer, resulting in an excellent response toward H2S gas. The MoSe2@SnO2 detects a low concentration of 500 ppb with a relative response of ∼19.9% at room temperature (RT). The simulation, using density functional theory (DFT), discloses that the adsorption energies ranged from -0.3645 to -0.5193 eV, indicating reduced bond lengths and significant H2S interactions. The sensor proves an excellent sensitivity toward H2S gas, ranging from 100 ppm to 500 ppb, with a LoD of ∼15 ppb at RT. As the sensor worked at RT with accuracy and reliability, consistent performance was observed upon exposure to various humidity levels, making it suitable for exhaled breath gas sensors. The sensor, as developed, also exhibited a good selectivity toward H2S gas in contrast to other gases as well as stability and longevity over time.

Distribution and origin of higher diamondoids in the ultra-deep Paleozoic condensates of the Shunbei oilfield in the Tarim Basin, NW China

Higher diamondoids in the condensates of the Shunbei oilfield were analyzed using GC–MS. The findings indicate that the condensates in the Shunbei oilfield were subjected to a superimposed effect of secondary alterations, including biodegradation, hydrothermal alteration, evaporative fractionation, cracking, and TSR. High local concentrations of thiaadamantanes in oil may result from the interaction of H2S, derived from Cambrian TSR, with Ordovician hydrocarbons, influenced by hydrothermal activities. Comprehensive analysis shows that TSR is local and limited in Ordovician reservoirs in the Shunbei oilfield and has no significant impact on oil chemistry. Comparative studies indicate that the diamondoid concentrations in condensates from the Shunbei oilfield have not been significantly impacted by biodegradation and evaporative fractionation. Parameters related to diamantanes can effectively characterize their geochemical characteristics and secondary alteration. A multi-parameter correlation heat map suggests that higher diamondoids in the condensates of the Shunbei oilfield are not due to high thermal evolution but have been altered by hydrothermal activity. The hydrothermal activity promotes the formation of higher diamondoids in the condensate. The higher diamondoids that are formed by hydrothermal activity offer a new perspective for studying hydrothermal processes. Additionally, this aids in studying the organic-inorganic interactions of ultra-deep organic fluids with their mineralogical and aqueous environments.

Interaction of H2S with perfect and O-covered Pd(100) surface: A first-principles study

Using density functional theory (DFT) calculations, we investigated the dissociative mechanism of H2S adsorption and its dissociation on both clean and oxygen covered Pd (100) surface. For adsorption mechanism, the site preference was considered for H2S and HS monomers on both surfaces. The results suggest that H2S is energetically adsorbed on high symmetry sites, particularly the hollow site, on clean surface and top site on O-covered Pd (100) surface. Chemisorption of HS is stronger than H2S at the favorable hollow site on clean surface and O-covered surface. The energy barriers for S–H bond-breaking during the first H2S dehydrogenation are 0.35, 0.07, 0.32, and 0.16 eV, while for second dehydrogenation are 0.32 and 0.30 eV, respectively. On the oxygen-covered surface, the H2S adsorption site transitions from bridge to the top site and their energy barrier for first-order decomposition is 0.05 eV, significantly lesser than that observed on a clean surface. To examine more, the electronic densities of states as well as d-band center model were used to characterize the interaction of adsorbed H2S with the surfaces. Overall, our findings show that H2S decomposition on these surfaces is exothermic and relatively easy, but the presence of surface oxygen hinders the breaking process of H–S bond due to kinetic and thermodynamic factors.

Signaling Paradigms of H2S-Induced Vasodilation: A Comprehensive Review.

Hydrogen sulfide (H2S), a gas traditionally considered toxic, is now recognized as a vital endogenous signaling molecule with a complex physiology. This comprehensive study encompasses a systematic literature review that explores the intricate mechanisms underlying H2S-induced vasodilation. The vasodilatory effects of H2S are primarily mediated by activating ATP-sensitive potassium (K_ATP) channels, leading to membrane hyperpolarization and subsequent relaxation of vascular smooth muscle cells (VSMCs). Additionally, H2S inhibits L-type calcium channels, reducing calcium influx and diminishing VSMC contraction. Beyond ion channel modulation, H2S profoundly impacts cyclic nucleotide signaling pathways. It stimulates soluble guanylyl cyclase (sGC), increasing the production of cyclic guanosine monophosphate (cGMP). Elevated cGMP levels activate protein kinase G (PKG), which phosphorylates downstream targets like vasodilator-stimulated phosphoprotein (VASP) and promotes smooth muscle relaxation. The synergy between H2S and nitric oxide (NO) signaling further amplifies vasodilation. H2S enhances NO bioavailability by inhibiting its degradation and stimulating endothelial nitric oxide synthase (eNOS) activity, increasing cGMP levels and potent vasodilatory responses. Protein sulfhydration, a post-translational modification, plays a crucial role in cell signaling. H2S S-sulfurates oxidized cysteine residues, while polysulfides (H2Sn) are responsible for S-sulfurating reduced cysteine residues. Sulfhydration of key proteins like K_ATP channels and sGC enhances their activity, contributing to the overall vasodilatory effect. Furthermore, H2S interaction with endothelium-derived hyperpolarizing factor (EDHF) pathways adds another layer to its vasodilatory mechanism. By enhancing EDHF activity, H2S facilitates the hyperpolarization and relaxation of VSMCs through gap junctions between endothelial cells and VSMCs. Recent findings suggest that H2S can also modulate transient receptor potential (TRP) channels, particularly TRPV4 channels, in endothelial cells. Activating these channels by H2S promotes calcium entry, stimulating the production of vasodilatory agents like NO and prostacyclin, thereby regulating vascular tone. The comprehensive understanding of H2S-induced vasodilation mechanisms highlights its therapeutic potential. The multifaceted approach of H2S in modulating vascular tone presents a promising strategy for developing novel treatments for hypertension, ischemic conditions, and other vascular disorders. The interaction of H2S with ion channels, cyclic nucleotide signaling, NO pathways, ROS (Reactive Oxygen Species) scavenging, protein sulfhydration, and EDHF underscores its complexity and therapeutic relevance. In conclusion, the intricate signaling paradigms of H2S-induced vasodilation offer valuable insights into its physiological role and therapeutic potential, promising innovative approaches for managing various vascular diseases through the modulation of vascular tone.

SOS! Hydrogen Sulfide Enhances the Flavonoid Early Warning System in Rice Plants to Cope with Thiocyanate Pollution.

The presence of thiocyanate (SCN-) in irrigation water has adverse effects on both plant growth and crop output. Hydrogen sulfide (H2S) is an important gaseous signaling molecule that can alleviate SCN- stress. Flavonoids are secondary compounds produced by plants and are ubiquitous in the plant kingdom. They play important roles in several physiological and biochemical processes. To investigate the effect of exogenous H2S on the growth of early rice plants under SCN- stress, we carried out a hydroponic experiment focusing on the interaction of exogenous H2S with flavonoids. In this study, a hydroponic experiment was performed to investigate the behavior of SCN- when subjected to varying effective doses (EC20: 24.0 mg/L; EC50: 96.0 mg/L; and EC75: 300.0 mg/L). The findings indicated that the relative growth rate (RGR) of the plants treated with H2S + SCN- was greater than that of the plants treated with SCN- alone. Higher amounts of flavonoids were detected in the shoots than in the roots, with more variability in the shoots. The early warning level results showed that most of the flavonoids were present at levels I and II, while quercetin was present at level IV. Genetic expression variation factor (GEVF) analyses revealed an increase in the quantity of "promoter genes" with increasing SCN- concentration in both rice tissues. Furthermore, administering external H2S while exposing rice tissues to SCN- resulted in a considerable decrease in the levels of reactive oxygen species. This study provides novel insights into the regulation of flavonoid levels in rice plants by exogenous H2S, facilitating enhanced resistance to SCN- stress and promoting sustainable agriculture.

Interaction of melatonin and H2S mitigates NaCl toxicity summer savory (Satureja hortensis L.) through Modulation of biosynthesis of secondary metabolites and physio-biochemical attributes.

As versatile signaling molecules, melatonin (ML) and hydrogen sulfide (H2S) are well-known for their roles in response to abiotic stresses. However, their cross-talk to the regulation of biochemical defence responses and secondary metabolite synthesis during salinity has received less attention. Here, the role of ML-H2S interplay in inducing defensive responses and the biosynthesis of essential oil compounds in summer savoury plants under NaCl treatment was investigated. NaCl treatment, by increasing Na accumulation, disrupting nitrogen metabolism, and inducing oxidative stress, lowered photosynthetic pigments and savoury growth. NaCl treatment also resulted in a decrease in γ-terpinene (10.3%), α-terpinene (21.9%), and p-cymene (15.3%), while an increase in carvacrol (9.1%) was observed over the control. ML and ML + H2S increased the activity of antioxidant enzymes and the level of total phenols and flavonoids, resulting in decreased levels of hydrogen peroxide and superoxide anion and alleviation of oxidative damage under salinity. ML and ML + H2S increased K uptake and restored K/Na homeostasis, thus protecting the photosynthetic apparatus against NaCl-induced toxicity. ML and ML + H2S treatments also improved nitrate/ammonium homeostasis and stimulated nitrogen metabolism, leading to improved summer savoury adaptation to NaCl stress. ML and ML + H2S changed the composition of essential oils, leading to an increase in the monoterpene hydrocarbons and oxygenated monoterpenes in plants stressed with NaCl. However, the addition of an H2S scavenger, hypotaurine, inhibited the protective effects of the ML and ML + H2S treatments under NaCl stress, which could confirm the function of H2S as a signaling molecule in the downstream defence pathway induced by ML.

Metabolic and Functional Interactions of H2S and Sucrose in Maize Thermotolerance through Redox Homeodynamics.

Hydrogen sulfide (H2S) is a novel gasotransmitter. Sucrose (SUC) is a source of cellular energy and a signaling molecule. Maize is the third most common food crop worldwide. However, the interaction of H2S and SUC in maize thermotolerance is not widely known. In this study, using maize seedlings as materials, the metabolic and functional interactions of H2S and SUC in maize thermotolerance were investigated. The data show that under heat stress, the survival rate and tissue viability were increased by exogenous SUC, while the malondialdehyde content and electrolyte leakage were reduced by SUC, indicating SUC could increase maize thermotolerance. Also, SUC-promoted thermotolerance was enhanced by H2S, while separately weakened by an inhibitor (propargylglycine) and a scavenger (hypotaurine) of H2S and a SUC-transport inhibitor (N-ethylmaleimide), suggesting the interaction of H2S and SUC in the development of maize thermotolerance. To establish the underlying mechanism of H2S-SUC interaction-promoted thermotolerance, redox parameters in mesocotyls of maize seedlings were measured before and after heat stress. The data indicate that the activity and gene expression of H2S-metabolizing enzymes were up-regulated by SUC, whereas H2S had no significant effect on the activity and gene expression of SUC-metabolizing enzymes. In addition, the activity and gene expression of catalase, glutathione reductase, ascorbate peroxidase, peroxidase, dehydroascorbate reductase, monodehydroascorbate reductase, and superoxide dismutase were reinforced by H2S, SUC, and their combination under non-heat and heat conditions to varying degrees. Similarly, the content of ascorbic acid, flavone, carotenoid, and polyphenol was increased by H2S, SUC, and their combination, whereas the production of superoxide radicals and the hydrogen peroxide level were impaired by these treatments to different extents. These results imply that the metabolic and functional interactions of H2S and sucrose signaling exist in the formation of maize thermotolerance through redox homeodynamics. This finding lays the theoretical basis for developing climate-resistant maize crops and improving food security.

The sustainable microwave approach to H2S and RSH activation into Di- and Trisulfides in N-Methylpyrrolidone

A reagent- and waste-free method for the transformation of hydrogen sulfide and thiols with С3-С8 hydrocarbons groups into value-added di- and trisulfides is proposed under the microwave irradiation. The hydrogen sulfide solution in N-methylpyrrolidone was used as the reaction medium to occur the interaction with different thiols. The influence of the microwave irradiation power, duration, the temperature and thiol structure on the yield and ratio of target products has been investigated. It is found that the effective microwave power for activation of H2S and RSH should be at least 200 W, while increasing the reaction temperature reduces the contact time. The maximum values for the yield of di- and trisulfides were obtained at 280 W and 100 °C. High selectivity of trisulfide formation was observed in the case of alkanethiols C3-C5, especially for compounds with isomeric hydrocarbons groups. Differences in the mechanisms of H2S interaction with linear and branched thiols based on the formation of alkylhydropolysulfide intermediates have been identified. The proposed scheme of utilization of H2S and low-molecular-weight thiols into organic polysulfides under microwave irradiation was suggested.

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.

The binding energy distribution of H2S: why it is not the major sulphur reservoir of the interstellar ices

Abstract Despite hydrogen sulfide (H2S) has been predicted to be the major reservoir of S-bearing species on the icy mantles of interstellar grains, no solid H2S has been detected so far. A crucial parameter that governs whether or not a species remains frozen onto the grain mantles is its binding energy (BE). We present a new computational study of the H2S BE on a large amorphous water ice surface, constituted by 200 water molecules. The resulting H2S BE distribution ranges from 57 K (0.5 kJ/mol) to 2406 K (20.0 kJ/mol), with the average μ = 984 K (8.2 kJ/mol). We discuss the reasons why the low bound of the newly computed BE distribution, which testifies to the very weak interaction of H2S with the ice surface, has never been found by previous theoretical or experimental works before. In addition, the low H2S BEs may also explain why frozen H2S is not detected in interstellar ices. Following previous molecular dynamics studies that show that the energy of reactions occurring on ice surfaces is quickly absorbed by the water molecules of the ice and conservatively assuming that 10% of the HS + H → H2S formation energy (-369.5 kJ/mol) is left to the newly formed H2S, its energy is more than twice the largest BE and 5 times the average BE and, hence, H2S will most likely leave the water surface.

Hydrogen Sulfide (H2S)/Polysulfides (H2Sn) Signalling and TRPA1 Channels Modification on Sulfur Metabolism.

Hydrogen sulfide (H2S) and polysulfides (H2Sn, n ≥ 2) produced by enzymes play a role as signalling molecules regulating neurotransmission, vascular tone, cytoprotection, inflammation, oxygen sensing, and energy formation. H2Sn, which have additional sulfur atoms to H2S, and other S-sulfurated molecules such as cysteine persulfide and S-sulfurated cysteine residues of proteins, are produced by enzymes including 3-mercaptopyruvate sulfurtransferase (3MST). H2Sn are also generated by the chemical interaction of H2S with NO, or to a lesser extent with H2O2. S-sulfuration (S-sulfhydration) has been proposed as a mode of action of H2S and H2Sn to regulate the activity of target molecules. Recently, we found that H2S/H2S2 regulate the release of neurotransmitters, such as GABA, glutamate, and D-serine, a co-agonist of N-methyl-D-aspartate (NMDA) receptors. H2S facilitates the induction of hippocampal long-term potentiation, a synaptic model of memory formation, by enhancing the activity of NMDA receptors, while H2S2 achieves this by activating transient receptor potential ankyrin 1 (TRPA1) channels in astrocytes, potentially leading to the activation of nearby neurons. The recent findings show the other aspects of TRPA1 channels-that is, the regulation of the levels of sulfur-containing molecules and their metabolizing enzymes. Disturbance of the signalling by H2S/H2Sn has been demonstrated to be involved in various diseases, including cognitive and psychiatric diseases. The physiological and pathophysiological roles of these molecules will be discussed.

Insights into Sulfhemoglobin Detection: UV-Vis and Fluorescence Spectroscopy Correlations

The mechanisms by which drugs and several sulfur chemicals induce sulfhemoglobin formation have not yet been elucidated. However, enzymes producing hydrogen sulfide in mammalian tissues and organs suggest sulfhemoglobin and sulfmyoglobin formation mechanisms are more complex than previously hypothesized. The process involves the interaction of H2S with hemoglobin or myoglobin in the presence of O2 or H2O2 to generate sulfhemoglobin or sulfmyoglobin, respectively. Structurally, the sulfheme product chromophore is a covalent heme modification. This modification involves the incorporation of one sulfur atom within carbon atoms to form a sulfur-carbons ring moiety across the β-β double bond of heme pyrrole B, which shows a characteristic optical band around 623 nm and 618 nm for sulfhemoglobin and sulfmyoglobin, respectively. The results show a linear correlation between the sulfHb electronic charge transfer transition at 623 nm and the emission wavelength of 460 nm upon Soret excitation at 420 nm. The data show no such linear relationship for oxy-Hb or met-aquo Hb. This new approach allows us to measure from 0.02% to 13.5% sulfhemoglobin in mixtures of met-aquo hemoglobin and oxy-hemoglobin. Although additional work is needed, the results suggest that simultaneously monitoring sulfHb electronic transition at 623 nm and emission wavelength at 460 nm upon Soret excitation at 420 nm is a powerful technique to determine the percentage of sulfhemoglobin in blood. The data and techniques presented indicate that fluorescence spectroscopy coupled with UV-vis spectroscopy provides a fast and accurate method for detecting sulfhemoglobin in the blood, facilitating the diagnosis of sulfhemoglobinemia in patients.

Exogenous hydrogen sulphide alleviates senescence of postharvest pakchoi through regulating antioxidant system, endogenous hydrogen sulphide and nitric oxide metabolism

Previous studies showed that hydrogen sulphide (H2S) fumigation retarded the yellowing of detached pakchoi leaves. However, whether H2S regulated specific metabolic pathways and gene expression levels in this process remained unclear. In this study, the effect of H2S, DL-propargylglycine (PAG, H2S synthetic inhibitor) on antioxidant capacity, endogenous H2S synthesis, and endogenous NO synthesis in pakchoi was investigated. After H2S fumigation (40 L L−1, 6 h), the pakchoi stored at 20 °C ± 1 °C with 90–95% relative humidity exhibited the best quality, with the highest chlorophyll content and the lowest respiration rate and malondialdehyde content. Contrarily, PAG accelerated pakchoi senescence. H2S treatment reduced superoxide anion and hydrogen peroxide by increasing the activities of superoxide dismutase, catalase, ascorbate peroxidase, and peroxidase, partially up-regulating the expression of enzyme genes. The increased expression of BcLCD, BcDCD and BcCAS C1 activated L- and D-cysteine desulfhydrase activities so that more endogenous H2S were retained in the pakchoi. Meanwhile, H2S treatment increased cysteine content in pakchoi via up-regulating BcSAT5 expression and enhancing the activities of sulfite reductase and serine acetyltransferase. Moreover, H2S increased endogenous NO primarily by preserving the activities of nitrate reductase and nitrite reductase instead of NO synthase (NOS)-like activity and decreased nitrate and nitrite as well. Overall, exogenous H2S alleviated the senescence of postharvest pakchoi via positively regulating antioxidant system, endogenous H2S and NO metabolism. Moreover, this work described a putative regulatory mechanism and provided some relevant information for future research into the interaction of H2S and NO in this process.

Mechanistic Intimate Insights into the Role of Hydrogen Sulfide in Alzheimer's Disease: A Recent Systematic Review.

In the rapidly evolving field of Alzheimer's Disease (AD) research, the intricate role of Hydrogen Sulfide (H2S) has garnered critical attention for its diverse involvement in both pathological substrates and prospective therapeutic paradigms. While conventional pathophysiological models of AD have primarily emphasized the significance of amyloid-beta (Aβ) deposition and tau protein hyperphosphorylation, this targeted systematic review meticulously aggregates and rigorously appraises seminal contributions from the past year elucidating the complex mechanisms of H2S in AD pathogenesis. Current scholarly literature accentuates H2S's dual role, delineating its regulatory functions in critical cellular processes-such as neurotransmission, inflammation, and oxidative stress homeostasis-while concurrently highlighting its disruptive impact on quintessential AD biomarkers. Moreover, this review illuminates the nuanced mechanistic intimate interactions of H2S in cerebrovascular and cardiovascular pathology associated with AD, thereby exploring avant-garde therapeutic modalities, including sulfurous mineral water inhalations and mud therapy. By emphasizing the potential for therapeutic modulation of H2S via both donors and inhibitors, this review accentuates the imperative for future research endeavors to deepen our understanding, thereby potentially advancing novel diagnostic and therapeutic strategies in AD.

Evaluation of the Reactivity of Methanol and Hydrogen Sulfide Residues with the Ziegler-Natta Catalyst during Polypropylene Synthesis and Its Effects on Polymer Properties.

The study focused on the evaluation of the influence of inhibitory compounds such as hydrogen sulfide (H2S) and methanol (CH3OH) on the catalytic productivity and properties of the polymers in the polymerization process with the Ziegler-Natta catalyst. The investigation involved experimental measurements, computational calculations using DFT, and analysis of various parameters, such as molecular weight, melt flow index, xylene solubility, and reactivity descriptors. The results revealed a clear correlation between the concentration of H2S and methanol and the parameters evaluated. Increasing the H2S concentrations, on average by 0.5 and 1.0 ppm, resulted in a drastic decrease in the polymer's molecular weight. A directly proportional relationship was observed between the flow rate and the H2S concentration. In the case of methanol, the change occurred from 60 ppm, causing a sharp decrease in the molecular weight of the polymer, which translates into an increase in the fluidity index and a decrease in solubility in xylene. The presence of these inhibitors also affected the catalytic activity, causing a reduction in the productivity of the Ziegler-Natta catalyst. Computational calculations provided a deeper understanding of the molecular behavior and reactivity of the studied compounds. The computational calculations yielded significantly lower results compared to other studies, with values of -69.0 and -43.9 kcal/mol for the Ti-CH3OH and H2S interactions, respectively. These results indicate remarkable stability in the studied interactions and suggest that both adsorptions are highly favorable.

Colorimetric and SERS detection of H2S by D (±) galactose functionalized truncated hexagonal bipyramidal silver nanoresonators

We report hereby, a simple and easy to perform experimental protocol for highly selective and real time dual mode (Colorimetric and SERS) detection of hydrogen sulfide (H2S) in aqueous medium through galactose activated silver nanoresonators. The truncated hexagonal bipyramids were clearly seen in TEM images of as prepared silver nanoparticles. The interaction of H2S with these AgNPs induced their etching followed by agglomeration and led optical (greenish yellow to brown) as well as SERS changes. The optical changes were further exploited to determine the H2S from its two spiked samples of human saliva and blood serum each with their percent recovery rates of 91, 82 and 67, 72 respectively. These determinations were totally free from any visual interference from any biothiols like cysteine, homocysteine and glutathione. The optimized silver nanosensor exhibited an excellent linear response in the concentration range of 50–130 nM along with its limit of detection (LOD) as 2.83 nM. Moreover, consecutive additions of different aliquots of H2S to a fixed volume of these silver colloids exhibited stepwise decrease in intensity of their absorption bands in the Raman silent (10–500 cm−1) and Raman finger print regions (500–1800 cm−1) upon their excitation at 532 nm. Our findings are well supported by spectroscopic (FTIR, UV–Vis and Raman) and microscopic (SEM, TEM, DLS and zeta potential).

Gas-Phase Interaction of CO, CO2, H2S, NH3, NO, NO2, and SO2 with Zn12O12 and Zn24 Atomic Clusters.

Atmospheric pollutants pose a high risk to human health, and therefore it is necessary to capture and preferably remove them from ambient air. In this work, we investigate the intermolecular interaction between the pollutants such as CO, CO2, H2S, NH3, NO, NO2, and SO2 gases with the Zn24 and Zn12O12 atomic clusters, using the density functional theory (DFT) at the meta-hybrid functional TPSSh and LANl2Dz basis set. The adsorption energy of these gas molecules on the outer surfaces of both types of clusters has been calculated and found to have a negative value, indicating a strong molecular-cluster interaction. The largest adsorption energy has been observed between SO2 and the Zn24 cluster. In general, the Zn24 cluster appears to be more effective for adsorbing SO2, NO2, and NO than Zn12O12, whereas the latter is preferable for the adsorption of CO, CO2, H2S, and NH3. Frontier molecular orbital (FMO) analysis showed that Zn24 exhibits higher stability upon adsorption of NH3, NO, NO2, and SO2, with the adsorption energy falling within the chemisorption range. The Zn12O12 cluster shows a characteristic decrease in band gap upon adsorption of CO, H2S, NO, and NO2, suggesting an increase in electrical conductivity. Natural bond orbital (NBO) analysis also suggests the presence of strong intermolecular interactions between atomic clusters and the gases. This interaction was recognized to be strong and noncovalent, as determined by noncovalent interaction (NCI) and quantum theory of atoms in molecules (QTAIM) analyses. Overall, our results suggest that both Zn24 and Zn12O12 clusters are good candidate species for promoting adsorption and, thus, can be employed in different materials and/or systems for enhancing interaction with CO, H2S, NO, or NO2.

Fast and slow releasing sulphide donors engender distinct transcriptomic alterations in Atlantic salmon hepatocytes

Hydrogen sulphide (H2S) is a naturally occurring compound generated either endogenously or exogenously and serves both as a gaseous signalling molecule and an environmental toxicant. Though it has been extensively investigated in mammalian systems, the biological function of H2S in teleost fish is poorly identified. Here we demonstrate how exogenous H2S regulates cellular and molecular processes in Atlantic salmon (Salmo salar) using a primary hepatocyte culture as a model. We employed two forms of sulphide donors: the fast-releasing salt form, sodium hydrosulphide (NaHS) and the slow-releasing organic analogue, morpholin-4-ium 4-methoxyphenyl(morpholino) phosphinodithioate (GYY4137). Hepatocytes were exposed to either a low (LD, 20 µg/L) or high (HD, 100 µg/L) dose of the sulphide donors for 24 hrs, and the expression of key sulphide detoxification and antioxidant defence genes were quantified by qPCR. The key sulphide detoxification genes sulfite oxidase 1 (soux) and the sulfide: quinone oxidoreductase 1 and 2 (sqor) paralogs in salmon showed pronounced expression in the liver and likewise responsive to the sulphide donors in the hepatocyte culture. These genes were ubiquitously expressed in different organs of salmon as well. HD-GYY4137 upregulated the expression of antioxidant defence genes, particularly glutathione peroxidase, glutathione reductase and catalase, in the hepatocyte culture. To explore the influence of exposure duration, hepatocytes were exposed to the sulphide donors (i.e., LD versus HD) either transient (1h) or prolonged (24h). Prolonged but not transient exposure significantly reduced hepatocyte viability, and the effects were not dependent on concentration or form. The proliferative potential of the hepatocytes was only affected by prolonged NaHS exposure, and the impact was not concentration dependent. Microarray analysis revealed that GYY4137 caused more substantial transcriptomic changes than NaHS. Moreover, transcriptomic alterations were more marked following prolonged exposure. Genes involved in mitochondrial metabolism were downregulated by the sulphide donors, primarily in NaHS-exposed cells. Both sulphide donors influenced the immune functions of hepatocytes: genes involved in lymphocyte-mediated response were affected by NaHS, whereas inflammatory response was targeted by GYY4137. In summary, the two sulphide donors impacted the cellular and molecular processes of teleost hepatocytes, offering new insights into the mechanisms underlying H2S interactions in fish.

New fluorescent probes based on gallium(III) corrole complexes for the recognition of hydrogen sulfide: A journey from solution to intracellular site

In this work, three fluorescent probes for detection of hydrogen sulfide (H2S) where prepared based on gallium(III) corrole complexes bearing nitro groups at β-pyrrolic positions. Two of the compounds selected, the 3-nitro-5,10,15- tris(pentafluorophenyl)corrolatogallium(III)(pyridine) (CGa-NO2) and the 3,17-dinitro-5,10,15-tris(pentafluorophenyl)corrolatogallium(III)(pyridine) (CGa-2NO2) present one and two nitro groups directly linked to the β-pyrrolic position. The third compound, the (E)-3-(2-nitroprop-1-en-1-yl)-5,10,15-tris(pentafluorophenyl)corrolatogallium(III)(pyridine) (CGa-EtNO2), has a carbon-carbon double bond spacer between the corrole unit and the nitro group. All these derivatives were obtained from 5,10,15-tris(pentafluorophenyl)corrolatogallium(III)(pyridine) (CGa). The precursor CGa and the derivative CGa-EtNO2 behaved as turn-OFF probes, while compound CGa-NO2 responded as a turn-ON probe in the presence of H2S in the pH range of 5–9. Mechanistic studies show that the interaction of H2S with the probes involves its coordination with gallium(III) and in some cases the reduction of the nitro group to a new aminated corrole. While the formation of the coordination complex with H2S is almost immediate, the kinetics of the reduction is slow. Interestingly, for CGa-NO2 the two processes can be explored in a ratiometric sensing of H2S in a non-aqueous solution showing a good linearity over an extended concentration range (5–200 μM). The response of the corroles to H2S in intracellular medium was studied in 2D cultured cells (HeLa).

Effect of Thallium(I) on Growth, Nutrient Absorption, Photosynthetic Pigments, and Antioxidant Response of Dittrichia Plants.

Dittrichia plants were exposed to thallium (Tl) stress (10, 50, and 100 µM) for 7 days. The Tl toxicity altered the absorption and accumulation of other nutrients. In both the roots and the leaves, there was a decline in K, Mg, and Fe content, but an increase in Ca, Mn, and Zn. Chlorophylls decreased, as did the photosynthetic efficiency, while carotenoids increased. Oxidative stress in the roots was reflected in increased lipid peroxidation. There was more production of superoxide (O2.-), hydrogen peroxide (H2O2), and nitric oxide (NO) in the roots than in the leaves, with increases in both organs in response to Tl toxicity, except for O2.- production in the roots, which fluctuated. There was increased hydrogen sulfide (H2S) production, especially in the leaves. Superoxide dismutase (SOD), ascorbate peroxidase (APX), dehydroascorbate reductase (DHAR), monodehydroascorbate reductase (MDHAR), and glutathione reductase (GR) showed increased activities, except for APX and MDHAR in the roots and GR in the leaves. The components of the ascorbate-glutathione cycle were affected. Thus, ascorbate (AsA) increased, while dehydroascorbate (DHA), reduced glutathione (GSH), and oxidized glutathione (GSSG) decreased, except for in the roots at 100 µM Tl, which showed increased GSH. These Tl toxicity-induced alterations modify the AsA/DHA and GSH/GSSG redox status. The NO and H2S interaction may act by activating the antioxidant system. The effects of Tl could be related to its strong affinity for binding with -SH groups, thus altering the functionality of proteins and the cellular redox state.