Organosulfur Research Articles

Palladium-anchored calix[4]arene-derived porous organic polymer towards efficient hydrolytic cleavage of carbon disulfide

The release of carbon disulfide can have adverse effects on our environment and human health. The stability of carbon disulfide and the slow kinetics of hydrolysis can make it challenging to achieve efficient and practical cleavage of the CS bonds. Herein, a calix[4]arene-based porous organic polymer (CPOP-1) is innovatively synthesized through an optimized polycondensation reaction using C-Methylcalix[4]resorcinarene and hexafluoro-hexaazatriphenylene as monomers. Subsequently, palladium-induced calix[4]arene-based porous organic polymer was also synthesized via strong Pd−N coordination bonds to construct the metal-induced porous catalyst (CPOP-2). The polymeric catalyst active center [Pd2+(N^N)(NO3-)2] demonstrated outstanding catalytic hydrolysis performance (11.14 μmol g-1 h-1) in 10.5 h which is significantly enhanced by ca.13.2 times as compared to reported mononuclear Bpy-Pd(NO3)2, and 7.07 times than model trinuclear complex catalyst HATN-Pd-1, respectively. The control experiments revealed that POP catalysts showcased robust stability, prolonged effectiveness, and feasible recyclability during the hydrolytic cleavage of carbon disulfide at room temperature in aqueous solutions. Furthermore, the coordination environment of [Pd2+(N^N)] was validated through XPS, EXAFS, and isotope labeling measurements, and the hydrolysis cleavage products were confirmed e. g. CO2, sulfide, and protons. More importantly, a reaction mechanism was formulated coupled with theoretical calculations, and simulations. The proposed mechanism involves sequential OH- nucleophilic attacks on the carbon atoms of insert-coordinated CS2 and COS, leading to the cleavage of double CS bonds and the formation of CO bonds. The concurrent dissociation of the C−S bond and liberation of CO2 result in an intermediate structure characterized by [(N^N)Pd2+](SH-)2. This intermediate motif serves as the source of the thermodynamic driving force for the reaction.

Metal-Ligand Cooperation with Thiols as Transient Cooperative Ligands: Acceleration and Inhibition Effects in (De)Hydrogenation Reactions.

ConspectusOver the past two decades, we have developed a series of pincer-type transition metal complexes capable of activating strong covalent bonds through a mode of reactivity known as metal-ligand cooperation (MLC). In such systems, an incoming substrate molecule simultaneously interacts with both the metal center and ligand backbone, with one part of the molecule reacting at the metal center and another part at the ligand. The majority of these complexes feature pincer ligands with a pyridine core, and undergo MLC through reversible dearomatization/aromatization of this pyridine moiety. This MLC platform has enabled us to perform a variety of catalytic dehydrogenation, hydrogenation, and related reactions, with high efficiency and selectivity under relatively mild conditions.In a typical catalytic complex that operates through MLC, the cooperative ligand remains coordinated to the metal center throughout the entire catalytic process, and this complex is the only catalytic species involved in the reaction. As part of our ongoing efforts to develop new catalytic systems featuring MLC, we have recently introduced the concept of transient cooperative ligand (TCL), i.e., a ligand that is capable of MLC when coordinated to a metal center, but the coordination of which is reversible rather than permanent. We have thus far employed thiol(ate)s as TCLs, in conjunction with an acridanide-based ruthenium(II)-pincer catalyst, and this has resulted in remarkable acceleration and inhibition effects in various hydrogenation and dehydrogenation reactions. A cooperative thiol(ate) ligand can be installed in situ by the simple addition of an appropriate thiol in an amount equivalent to the catalyst, and this has been repeatedly shown to enable efficient bond activation by MLC without the need for other additives, such as base. The use of an ancillary thiol ligand that is not fixed to the pincer backbone allows the catalytic system to benefit from a high degree of tunability, easily implemented by varying the added thiol. Importantly, thiols are coordinatively labile enough under typical catalytic conditions to leave a meaningful portion of the catalyst in its original unsaturated form, thereby allowing it to carry out its own characteristic catalytic activity. This generates two coexisting catalyst populations─one that contains a thiol(ate) ligand and another that does not─and this may lead to different catalytic outcomes, namely, enhancement of the original catalytic activity, inhibition of this activity, or the occurrence of diverging reactivities within the same catalytic reaction mixture. These thiol effects have enabled us to achieve a series of unique transformations, such as thiol-accelerated base-free aqueous methanol reforming, controlled stereodivergent semihydrogenation of alkynes using thiol as a reversible catalyst inhibitor, and hydrogenative perdeuteration of C═C bonds without using D2, enabled by a combination of thiol-induced acceleration and inhibition. We have also successfully realized the unprecedented formation of thioesters through dehydrogenative coupling of alcohols and thiols, as well as the hydrogenation of organosulfur compounds, wherein the cooperative thiol serves as a reactant or product. In this Account, we present an overview of the TCL concept and its various applications using thiols.

Anti-adipogenesis and anti-obesity potential of alliin mediated by modulating glycolipid metabolism via activating PPARγ signaling.

Garlic exhibits hypolipidemic, hypoglycemic, and cardiovascular benefits. The inconsistent results of garlic preparations on adipogenesis have caused more confusion in the public and academia. The compounds responsible for the anti-adipogenesis effect of garlic remain unknown. The present study aimed to verify the real anti-adipogenesis and anti-obesity component in garlic and explored its possible effects in metabolic syndrome. We verified the real anti-adipogenesis and anti-obesity components of garlic in 3T3-L1 preadipocytes and a 10-week-high fat diet (HFD)-induced obese mice. In vitro, two water-soluble and four typical lipid-soluble compounds of garlic were tested for their anti-adipogenesis. Then, the water-soluble compound, alliin, and two processing methods produced garlic oils, were evaluated in vivo study. Mice received oral administration of alliin (25mg/kg) and garlic oils (15mg/kg) daily for 8weeks. Serum lipids, parameters of obesity, and indicators involved in regulating glycolipid metabolism were examined. Our findings confirmed that both water-soluble and lipid-soluble organosulfur compounds of garlic contributed to garlic's anti-adipogenesis effect, in which water-soluble sulfides, especially alliin, exhibited greater potency. Alliin possessed potent effects of anti-obesity and improvement in glucose and lipid metabolism in HFD-induced obese mice. Alliin mediated these effects partly attributed to its modulation of enzymatic activities within glycolipid metabolism and activating PPARγ signaling pathway. In contrast to odorous lipid-soluble sulfides, alliin is odorless, stable, and safe, and is an ideal nutraceutical or even medicinal candidates for the treatment of metabolic diseases. Alliin could be used to standardize the quality of garlic products.

The stable sulfur isotope and abundance fluxes of reduced inorganic sulfur and organic sulfur phases recorded in the Permian-Triassic transition of the Meishan type section

Sulfur cycle fluxes implicated in the Permian-Triassic mass extinction have traditionally been studied by the sulfur phase abundances in sedimentary rocks and the stable sulfur isotopic value (δ34S) of seawater sulfate inferred from mineral sulfate analyses. This information might be complemented by studies of the reduced inorganic sulfur and organic sulfur produced following bacterial sulfate reduction. To explore this potential the δ34S and concentration analyses of total reduced inorganic sulfur (TRIS) and organic sulfur – separately in the forms of kerogen (Ker) and individual organosulfur compounds, specifically dibenzothiophenes (DBTs) – has been conducted on sediments across the Late Permian to Early Triassic marine type section of Meishan-1 (South China). The relatively steady δ34S profiles (e.g., < 5 ‰ variation) of all sulfur phases measured through much of the late Permian were indicative of a primary seawater sulfate control, but other biogeochemical modulators caused prominent δ34S fluctuations of TRIS and DBT adjacent to the extinction event. The late Triassic δ34STRIS profile of Meishan-1 displayed a notable 34S enrichment (+15 ‰ increase) in bed 22–24 sediments concomitant with lower δ34SDBT values (−7 ‰ decrease), whereas co-eval δ34SKerS values remained relatively constant. The contrasting δ34SDBT and δ34SKerS data suggests the dynamic behavior of specific diagenetic sulfurisation processes may be resolved by the δ34S of discrete organic sulfur compounds (i.e., dibenzothiophenes, DBTs), but dissipated by the sulfurisation collective represented by the bulk kerogen fraction. The inverse isotopic trend observed between DBT and TRIS resulted in negative Δδ34SDBT-TRIS values identifying an organic sulfurisation pathway(s) with an unusual preference over pyrite (FeS2) for the lighter stable sulfur isotope. A redox control of the δ34SDBTs and δ34STRIS deviations in the bed 22–24 extinction interval was confirmed by coincident variation in TRIS/(TRIS + KerS) and pyrite (Py) and highly reactive (HR) iron ratios (FePy/FeHR). The iron (Fe) speciation data indicated a transition to ferruginous conditions, ruling out Fe2+ limitation as a factor in the bias against 34S evident in DBT formation. The 34S depletion of the DBTs promoted by the ferruginous setting may arise from the rapid and irreversible reaction of organic substrates with labile sulfur anions (e.g. HS-) or be supported by an especially localised sediment–water depositional microenvironment. Our study highlights the potential of incorporating stable sulfur isotope analytics of reduced and organic sulfur phases, particularly of specific organic compounds, into a holistic assessment of the dynamic sulfur biochemical periods of Earth’s past.

Modeling the Effect of Sulfur Composition in Dispersed Systems Involving Organosulfur Compounds

Background:: Organosulfur compounds within petroleum have far-reaching consequences for the refining industry, combustion of petroleum products, and environmental quality. They induce corrosion in refining equipment, hamper the efficient burning of petroleum products, and contribute to environmental degradation. In high-density asphalt crudes, these compounds are predominantly concentrated within asphaltenes. However, crude oils with extremely high sulfur content, may be distributed across the four constituent families defined by the SARA analysis of crude oil composition. These compounds, characterized by differing polarities, can trigger the formation of a dispersed phase, whose destabilization results in tube clogging issues. Methods:: The research problem focuses on understanding how sulfur composition affects the formation of a dispersed phase in low-polarity organic dispersion media for sulfur-containing hydrocarbons. It is investigated because the presence of sulfur in crude oil significantly affects the behavior of dispersed phases, which can result in operational and environmental quality issues to comprehensively assess the impact of sulfur composition on the dynamics and stability of this dispersed phase, we introduce a mesoscopic model based on the master equation. This model considers the molecular structure of system components and their molecular properties, established through computational quantum chemistry and statistical thermodynamics tools Results:: While our research focuses on a two-phase system, our theoretical insights suggest that increased sulfur content escalates the likelihood of destabilizing the dispersed phase. This adverse effect can be mitigated by incorporating additives capable of reducing the polarizability of the dispersion medium. The novelty lies in the development of a stochastic model to predict the dynamics of dispersed phase formation in sulfur-containing hydrocarbons. This model considers molecular interactions and stochastic processes, offering insights into the influence of sulfur composition on phase behavior. Conclusion:: A stochastic model, based on molecular structure, predicts accelerated formation with increased sulfur concentration, reaching non-equilibrium steady states. Limitations include ad hoc transition probabilities and the exclusion of factors like density and viscosity. Real crudes, with complex compositions, may exhibit different behavior. The presence of sulfur in the dispersion medium enhances the stability of the dispersed system. Our work sheds light on the intricate interplay between sulfur content and the performance of petroleum systems, offering potential solutions to mitigate these issues. Quantitative results include accelerated dispersed phase formation with increased sulfur concentration. Qualitatively, molecular interactions and stochastic processes were explored, highlighting sulfur's impact on phase dynamics.

Antibacterial Activity of the Allium sativum Crude Extract against Methicillin-resistant Staphylococcus aureus

Garlic contains various components, such as allicin, ajoenes, and allyl sulfides, which are organosulfur compounds. It exhibits antimicrobial activities in all forms, including garlic powder, garlic extract, and garlic oil. Additionally, it exerts anti-inflammatory, antibacterial, antibiofilm, and antifungal effects. The drastic increase in drug-resistant organisms worldwide, especially methicillin-resistant Staphylococcus aureus (MRSA) strains, has led to treatment failure in various infectious diseases. To overcome this issue, we aimed to assess the antibacterial activity of garlic extract against MRSA and explore its action mechanism against penicillin-binding proteins (PBPs) in this study. Mueller–Hinton agar was used for the agar well diffusion test. Moreover, bactericidal activity was determined using the Mueller–Hinton agar and spot tests. Molecular docking was performed using AUTODOCK to evaluate the PBP-binding ability of allicin. A wide zone of inhibition was observed for MRSA, and molecular docking revealed a strong interaction between PBP3 of S. aureus and allicin. Overall, our findings revealed the antibacterial activity of garlic extract against MRSA, a prevalent gram-positive coccus causing healthcare-associated infections. In addition to its affordability, the beneficial effects of garlic suggest its therapeutic potential for MRSA treatment in combination with cefoxitin.

Mechanism of antibacterial activity of diallyl sulfide against Bacillus cereus

World health organization (WHO) recognizes antimicrobial resistance as a silent pandemic. It is estimated that 10 million deaths will occur annually due to antimicrobial resistant infections by 2050. Phytochemicals exhibit activity against drug resistant bacteria, offering potential for developing novel antibacterial agents. Garlic organosulphur compounds exhibit potent activity against a variety of drug-resistant bacteria. Identifying their mechanism of action is critical to assess their potential to be developed as novel antibacterial agents. Diallyl sulfide (DAS) is a component of garlic essential oil with antibacterial activity. In this study antibacterial activity of DAS was investigated against Bacillus cereus, a common foodborne pathogen. DAS exhibited activity against B. cereus with a minimum inhibitory concentration (MIC) of 54.75 mM. The presence of DAS significantly reduced the growth of B. cereus. The study also investigated the mechanism of antibacterial activity of DAS against B. cereus. Treating B. cereus with sub-MIC and MIC concentration of DAS resulted in a dose and time-dependent leakage of intracellular proteins. The protein leakage was enhanced at acidic pH. Scanning electron microscopy (SEM) of B. cereus treated with DAS showed deformation in the cell membrane. Thus, the data indicate that DAS exerts its antibacterial activity by compromising the membrane integrity of B. cereus. The study demonstrates DAS could be used to control B. cereus infections. The findings indicate that DAS has a membrane altering activity, suggesting that development of resistance to this mechanism is less likely and the compound could be novel antibacterial or a good adjuvant for antibiotics.

Detection and quantification of organosulfur species in the Tagish Lake Meteorite by highly sensitive LC‐MS

AbstractWe analyzed the methanol extracts of six pristine specimens of the Tagish Lake meteorite (TL1, TL4, TL5A, TL6, TL7, and TL10a) and heated and unheated samples of Allende using high‐performance liquid chromatography coupled with high‐resolution, accurate mass–mass spectrometry (HPLC‐HRAM‐MS). All samples contained ppm levels of sulfate and methyl sulfate. The most abundant organosulfur compound in the methanol extracts of the Tagish Lake and Allende samples was methyl sulfate, which was likely formed primarily via an esterification reaction between intrinsic sources of methanol and sulfate. A homologous series of polythionic acids was also observed in the extracts of the Tagish Lake specimens and Allende. The polythionic acids were the most abundant soluble inorganic sulfur species found in the meteorites. Our results were confirmed using retention time, accurate mass, isotope matching, and tandem mass spectrometry (MS/MS). Hydroxymethanesulfonic acid, previously reported in Tagish Lake, was found only in an unheated Allende sample and in low abundance. Here, we propose possible sulfate formation pathways that begin with interstellar dimethyl sulfide, dimethyl disulfide, methyl sulfide, or methanethiol via cold, nebular processes within the interstellar medium and continue via MSA as an intermediary compound ending within planetary bodies with sulfate and methyl sulfate as the final products.

Lignocellulosic waste biosorbents infused with deep eutectic solvents for biogas desulfurization

This paper introduces an innovative method for treating biogas streams, employing lignocellulosic biosorbents infused with environmentally friendly solvents known as deep eutectic solvents (DES). The primary focus of this study was the elimination of volatile organosulfur compounds (VSCs) from model biogas. Biosorbents, including energetic poplar wood, antipka tree, corncobs, and beech wood, were used, each with varying levels of lignin and hemicellulose content. The selection of the DES with the greatest potential for VSC removal was carried out using COnductor-like Screening MOdel for Realistic Solvents (COSMO-RS) modeling. The chosen DES consisted of quaternary ammonium salts and glycols, specifically, tetrapropylammonium bromide and 1,2-hexanediol (1:3). The physicochemical properties of the new DES, such as the viscosity, density, and melting point, were evaluated. The biosorbents were treated with the selected DES after shredding, purifying, and sieving. Comprehensive analysis techniques, including thermogravimetric analysis, scanning electron microscopy, and X-ray diffraction, were employed on the modified biosorbents both before and after modification. The subsequent step involved the adsorption of VSCs from biogas. The results of this study demonstrated the superior performance of a novel sorbent based on corn cob modified by DES compared to commercially available alternatives. The sorption capacity ranged from 103.8 to 112.1 mg/g for various VSCs. The adsorption process using the new biosorbent can be described by the pseudo second order kinetic model, as well as the Yoon-Nelson and Adams-Bohart models. The high efficacy of the VSCs removal was attributed to the concurrent operation of the absorption and adsorption processes. The resulting sorbent was also characterized by its ability to regenerate repeatedly without significant loss of sorption capacity of the new sorbents.

Sulforaphane and ophthalmic diseases.

Sulforaphane (SFN) is an organosulfur compound categorized as an isothiocyanate (ITC), primarily extracted from cruciferous vegetables like broccoli and cabbage. The molecular formula of sulforaphane (SFN) is C6H11NOS2. SFN is generated by the hydrolysis of glucoraphanin (GRP) through the enzyme myrosinase, showing notable properties including anti-diabetic, anti-inflammatory, antimicrobial, anti-angiogenic, and anticancer attributes. Ongoing clinical trials are investigating its potential in diseases such as cancer, neurodegenerative diseases, diabetes-related complications, chronic kidney disease, cardiovascular disease, and liver diseases. Several animal carcinogenesis models and cell culture models have shown it to be a very effective chemopreventive agent, and the protective effects of SFN in ophthalmic diseases have been linked to multiple mechanisms. In murine models of diabetic retinopathy and age-related macular degeneration, SFN delays retinal photoreceptor cell degeneration through the Nrf2 antioxidative pathway, NF-κB pathway, AMPK pathway, and Txnip/mTOR pathway. In rabbit models of keratoconus and cataract, SFN has been shown to protect corneal and lens epithelial cells from oxidative stress injury by activating the Keap1-Nrf2-ARE pathway and the Nrf-2/HO-1 antioxidant pathway. Oral delivery or intraperitoneal injection at varying concentrations are the primary strategies for SFN intake in current preclinical studies. Challenges remain in the application of SFN in eye disorders due to its weak solubility in water and limited bioavailability because of the presence of blood-ocular barrier systems. This review comprehensively outlines recent research on SFN, elucidates its mechanisms of action, and discusses potential therapeutic benefits for eye disorders such as age-related macular degeneration (AMD), diabetic retinopathy (DR), cataracts, and other ophthalmic diseases, while also indicating directions for future clinical research to achieve efficient SFN treatment for ophthalmic diseases.

Greening up the fight against emerging contaminants: algae-based nanoparticles for water remediation

AbstractNanoparticles are commonly used for different purposes, including as photocatalysts, biosensors, antibacterial, antifungal, and anticancer agents. Recently, the synthesis of nanoparticles via biological techniques has become popular due to cost efficiency, sustainability, and the least secondary pollutants generation. Plants, algae, and microorganisms are primarily used to synthesize bio-nanoparticles. Algae-based nanoparticles have gained more attention due to their catalytic activity against emerging organic contaminants such as dyes, phenols, and organosulfur compounds. Nevertheless, a systemic evaluation of the potential of algae-based nanoparticles in environmental remediation is yet to be conducted. This paper reviews recent progress in the biosynthesis of algae-based nanoparticles and the potential use of algae-based nanoparticles in environmental remediation. Furthermore, the review examines the factors that affect the properties and behaviors of algae-based nanoparticles. Additionally, the review briefly discusses other medical and industrial applications as well as advantages over physically and chemically synthesized nanoparticles. Challenges associated with the production process and usage of algae-based nanoparticles are also discussed, including the difficulty of predicting the properties of nanoparticles and adapting to large-scale processes. Overall, algae-based nanoparticles have several advantages, including their high stability and surface activity due to the presence of surface functional groups from algae species used for the synthesis of algae-based nanoparticles. However, further research is required to address the knowledge gaps and potential key research areas. Graphical Abstract

Activity of propyl-propane-thiosulfinate and propyl-propane-thiosulfonate against carbapenem-resistant Gram-negative bacteria.

Organosulfur compounds derived from plants of the Allium genus, such as propyl-propane-thiosulfinate (PTS) and propyl-propane-thiosulfonate (PTSO), have been proposed as an alternative in antibiotic resistance. The aim of this study was to compare the activity of these substances with other antibiotics against clinical isolates of carbapenem-resistant (CAR-R) and carbapenem-susceptible (CAR-S) Gram-negative bacteria. A total of 126 clinical isolates of CAR-R and 155 CAR-S bacteria were selected, including Enterobacterales, A. baumannii and P. aeruginosa. The antibiotic susceptibility of all isolates was assessed using the microdilution and Kirby-Bauer methods for PTS, PTSO, amoxicillin/clavulanate, piperacillin/tazobactam, cefotaxime, ceftazidime, cefepime, imipenem, ciprofloxacin, and amikacin. Both PTS and PTSO demonstrated in vitro bactericidal activity against CAR-R Enterobacteriaceae and A. baumannii, with no significant difference in activity compared to their response against CAR-S isolates. However, both compounds were less active against P. aeruginosa than against any of the other bacteria, regardless of their resistance to carbapenems. In all cases, the minimum inhibitory concentration values of PTSO were significantly lower than those of PTS. These findings offer valuable information about the potential antibacterial use of these substances, particularly against infections that currently have limited therapeutic options.

Deactivating Effect of Hydroxyl Radicals Reactivity by Sulfate and Sulfite Functional Groups in Aqueous Phase─Atmospheric Implications for Small Organosulfur Compounds

Deactivating Effect of Hydroxyl Radicals Reactivity by Sulfate and Sulfite Functional Groups in Aqueous Phase─Atmospheric Implications for Small Organosulfur Compounds

Finding the Ajoene Sweet-Spot: Structure-Activity Relations that Govern its Blood Stability and Cancer Cytotoxicity.

Ajoene is an organosulfur compound found in crushed garlic that exerts its anti-cancer activity by S-thiolating cysteine residues on proteins. Its development is hampered due to limited bioavailability, so in this study, we synthesised analogues of ajoene to probe the significance of the ajoene vinyl disulfide/sulfoxide core with respect to cytotoxicity and blood stability. Polar side groups were also incorporated to improve aqueous solubility. It was found that derivatives containing a vinyl disulfide functional group (4-7, as in ajoene), were more cytotoxic compared to analogues in which the double bond was removed, although the latter showed superior blood stability. It was also found that the allyl-S sulfur of the disulfide was more electrophilic to S-thiolysis based on the global electrophilicity index (ω) and the condensed electrophilic Fukui function . S-Thiolysis was found to be exergonic for the vinyl disulfides based on entropy and enthalpy computations with a deprotonated thiolate. Derivatisation to the dihydro (10, 12) and deoxydihydroajoenes (9, 11) produced analogues that were slightly less potent but with greatly improved blood stability. Taken together, the deoxydihydroajoenes present themselves as good candidates for further therapeutic development.

Quantitative analysis of organosulphur compounds in crude oil samples using magnetic solid phase extraction based on Au-Fe3O4 adsorbent and gas chromatography with time-of-flight mass spectrometry

This study focused on the development of a magnetic solid phase extraction (m-SPE) method using Au-Fe3O4 as an adsorbent followed by GC-ToFMS analysis for the determination of organosulphur compounds (OSCs) in fuel samples. The m-SPE using Au-Fe3O4 NPs was preferred because of the low toxicity of the adsorbent1, high separation efficiency using external magnet2 and greater extraction selectivity between sulphur and Au atom3. The Au-Fe3O4 NPs were characterized using XRD, UV–Vis, TEM, SEM and FTIR. This method was optimized using multivariate analysis based on a two-level full factorial and central composite designs. The conditions which produced optimum efficiency were found to be 150 mg mass of sorbent, 100 µL eluent volume, 50 min extraction time and 6,5 pH of the sample. These optimum conditions showed a relatively low limit of detection in the range of 0.02–0.199nµg/g and limit of quantification of 0.08–0.602 µg/g. Furthermore, a relative standard deviation of triplicates analysis was between 0.8 and 2.3% with good linearity of 0.9816–0.9961. The percentage recovery for thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene ranged from 76 to 95% for the spiked samples. The optimized m-SPE method was then applied in real fuel oil samples. The concentration of thiophene, 3-methylthiophene, benzothiophene and dibenzothiophene in crude oil, gasoline, diesel and kerosene ranged from 0.43–1.94 µg/g, 0.78–1.63 µg/g, 0.95–4.31 µg/g to 1.55–2.09 µg/g, respectively. The m-SPE, followed by GC-ToFMS method, proved to be efficient, inexpensive and an alternative method for OSCs analysis in fuel oils.

Organosulfur Cathodes in Lithium Metal Batteries: Bridging the Gap between Fundamentals and Practical Applications

AbstractHigh‐specific energy sulfur‐based cathodes have attracted considerable interest in lithium batteries. Organosulfur cathodes offer inherent advantages of high element abundance and an extended cycling life, aligning with the evolving requirements of future energy storage devices. Over the past decade, research efforts have been devoted to optimizing electrochemical performance through the rich and tunable molecular structures of organosulfur compounds. To further advance the fundamental research and practical application of lithium‐organosulfur batteries, a systematical analysis of the correlation between the molecular structures and electrochemical mechanisms of organosulfur cathodes is imperative. This involves deriving the key parameters at the cell level and investigating the feasibility. In this review, the thermodynamics, reaction processes, and electrochemical kinetics of organosulfur cathodes, grounded in fundamental theories of electrochemistry and materials science are discussed. Expanding the insights, comparisons among elemental sulfur, organosulfur, and n‐type organic cathodes (e.g., carbonyl cathodes) are drawn. The gap between fundamentals and practical applications targeting 500 Wh kg−1 lithium organosulfur batteries is highlighted through energy density calculations and identification of key factors affecting pouch cells. Finally, potential strategies and prospects for the overall design of advanced lithium‐organosulfur batteries are proposed, considering both theoretical foundations and practical implementations.

Dimethyl Sulfoxide (DMSO) as a Potential Source of Interference in Research Related to Sulfur Metabolism-A Preliminary Study.

Dimethyl sulfoxide (DMSO), an organosulfur compound, is widely used as the gold standard solvent in biological research. It is used in cell culture experiments and as a component of formulations in in vivo studies. Unfortunately, parameters related to sulfur metabolism are often not taken into account when using DMSO. Therefore, in this work we aim to show that the addition of DMSO to the culture medium (even in amounts commonly considered acceptable) alters some parameters of sulfur metabolism. For this study, we used three cell lines: a commercially available Caco-2 line (HTB-37, ATCC) and two lines created as part of our early studies (likewise previously described in the literature) to investigate the anomalies of sulfur metabolism in mucopolysaccharidosis. As the negative effects of DMSO on the cell membrane are well known, additional experiments with the partial loading of DMSO into polymerosomes (poly(ethylene glycol) methyl ether-block-poly(lactide-co-glycolide), PEG-PLGA) were performed to eliminate these potentially disruptive effects. The results show that DMSO is a source of interference in studies related to sulfur metabolism and that there are not just simple effects that can be corrected in the final result by subtracting control values, since complex synergisms are also observed.

Porphyrin Aluminum Metal-Organic Framework in Liquid Water, its Interaction with the Oxidized Organosulfur Compound Diethyl Sulfoxide, and its Sorption from Aqueous Solution.

Oxidized organosulfur compounds and, in particular, sulfoxides are of interest as solvents in the semiconductor and pharmaceutical industry, environmental contaminants, and simulants in deactivation of chemical warfare agents. An experimental study is reported of the interaction of porphyrin aluminum metal-organic framework Al-MOF-TCPPH2 (Compound 2) with diethyl sulfoxide (DESO) in pure form and in aqueous solution. First, the suitability of Compound 2 as sorbent in aqueous solution was assessed; namely, its long-term stability (up to 15 days) in liquid water has been investigated at room temperature and under stirring. Here, a novel facile spectroscopic method has been used, a periodic micro-sampling of sorbent from suspension, followed by vacuum mini-filtration and an ex situ time-dependent attenuated total reflection Fourier transform infrared spectroscopy (ATR FT-IR) analysis. Next, the interaction of Compound 2 with pure liquid DESO under ambient conditions was investigated, which yields the stoichiometric adsorption complex (Al-MOF-TCPPH2)1(DESO)2 denoted Compound 3. In this adsorption complex, molecules of DESO interact with the OH group and carboxylate group of the sorbent. Then, the removal of DESO from Compound 3 was assessed, using facile treatment with warm water in the micro Soxhlet apparatus followed by the ATR FT-IR analysis. Finally, Compound 2 was tested in sorption of DESO from diluted aqueous solution. In the initial step, the sorption proceeds very quickly (in <1 min the concentration of DESO decreases by about 20%) followed by a much slower step. The maximum amount of adsorbed DESO corresponds to half of the amount adsorbed from pure DESO as found by the high-performance liquid chromatography-ultraviolet detection method. This adsorbed amount corresponds to 1 mol DESO adsorbate per mol of sorbent. Porphyrin aluminum metal-organic framework Compound 2 is promising for the removal of DESO from diluted aqueous solution, and it is of interest for the removal of similar oxidized organosulfur compounds.

Exposure of polyethylene microplastics affects sulfur migration and transformation in anaerobic system

Polyethylene (PE) microplastic, which is detected in various environmental media worldwide, also inevitably enters wastewater treatment plants, which may have an impact on anaerobic processes in wastewater treatment. In this work, the effect of PE microplastics on anaerobic sulfur transformation was explored. Experimental results showed that PE microplastics addition at 0.1%− 0.5% w/w promoted H2S production by 14.8%−27.4%. PE microplastics enhanced the release of soluble organic sulfur and inorganic sulfate, and promoted the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Mechanism analysis showed that PE microplastics increased the content of electroactive components (e.g., protein and humic acids) contained in extracellular polymeric substances (EPS). In particular, PE microplastics increased the proportion and the dipole moment of α-helix, an important component involved in electron transfer contained in extracelluar protein, which provided more electron transfer sites and promoted the α-helix mediated electron transfer. These enhanced the direct electron transfer ability of EPSs, which might explain why PE microplastics facilitated the bioprocesses of organosulfur compounds hydrolysis and sulfate reduction. Correspondingly, metagenomic analysis revealed that PE microplastics increased the relative abundance of S2- producers (e.g., Desulfobacula and Desulfonema) and the relative abundance of functional genes involved in anaerobic sulfur transformation (e.g., PepD and cysD), which were beneficial to H2S production in anaerobic system.

Enhancing high-density microalgae cultivation via exogenous supplementation of biostimulant derived from onion peel waste for sustainable biodiesel production

Microalgae demonstrate significant potential as a source of liquid-based biofuels. However, increasing biomass productivity in existing cultivation systems is a critical prerequisite for their successful integration into large-scale operations. Thus, the current work aimed to accelerate the growth of C. vulgaris via exogenous supplementation of biostimulant derived from onion peel waste. Under the optimal growth conditions, which entailed a biostimulant dosage of 37.5% v/v, a pH of 3, an air flow rate of 0.4 L/min, and a 2% v/v inoculum harvested during the mid-log phase, yielded a maximum biomass concentration of 1.865 g/L. Under the arbitrarily optimized parameters, a comparable growth pattern was evident in the upscaled cultivation of C. vulgaris, underscoring the potential commercial viability of the biostimulant. The biostimulant, characterized through gas chromatography-mass spectrometry (GC-MS) analysis, revealed a composition rich in polyphenolic and organo-sulphur compounds, notably including allyl trisulfide (28.13%), methyl allyl trisulfide (23.04%), and allyl disulfide (20.78%), showcasing potent antioxidant properties. Additionally, microalgae treated with the biostimulant consistently retained their lipid content at 18.44% without any significant reduction. Furthermore, a significant rise in saturated fatty acid (SFA) content was observed, with C16:0 and C18:1 dominating both bench-scale (44.08% and 14.01%) and upscaled (51.12% and 13.07%) microalgae cultures, in contrast to the control group where C18:2 was prevalent. Consequently, SFA contents reached 54.35% and 65.43% in bench-scale and upscaled samples respectively, compared to 33.73% in the control culture. These compositional characteristics align well with the requirements for producing high-quality crude biodiesel.