Organic Sulfides Research Articles

Infrequent Cubane-Like Chromium Sulfide Cluster with σ-Donor Ligands with Efficient Electrocatalytic Property Toward Hydrogen Evolution Reaction.

The exploitation of efficient and economical electrocatalysts for hydrogen evolution reaction (HER) is of exceeding interest in renewable clean-energy technologies. Herein, the facile solvothermal reaction of S and chromic acetate in ethylenediamine (en) achieved a novel organic hybrid chromium sulfide [Cr4(μ3-S)4(en)4(SH)4]·0.25H2O (1), which offers a new type of antiferromagnetic cubane-like chromium sulfide cluster with σ-donor en ligands. 1 was utilized in combination with Ni nanoparticles and porous Ni foam (NF) to fabricate a Ni/1/NF electrode as an efficient cathodic catalyst, indicating excellent electrocatalytic property toward HER.

Extreme eutrophication and salinisation in the Coorong estuarine-lagoon ecosystem of Australia's largest river basin (Murray-Darling)

Estuaries in rainfall poor regions are highly susceptible to climatic and hydrological changes. The Coorong, a Ramsar-listed estuarine-coastal lagoon at the end of the Murray-Darling Basin (Australia), has experienced declining ecological health over recent decades. Twenty years of environmental data were analysed to assess patterns and drivers of water quality changes. Large areas of the Coorong are now persistently hyper-saline (salinity >80 psu) and hypereutrophic (total nitrogen, TN > 4 mg L−1, total phosphorus, TP > 0.2 mg L−1, chlorophyll a > 50 μg L−1) which coincided with reduced flushing due to diminished freshwater inflows and increasing evapo-concentration. Sediment quality also was related to flushing, with higher concentrations of organic carbon, TN, TP and sulfides as salinity increased. While total nutrient levels are very high, dissolved inorganic nutrients are generally low. Increased lagoonal flushing would be beneficial to reduce the hypersalinisation and hypereutrophication and improve ecosystem health.

Biosynthesis, behavior and fate of volatile organic sulfide in Lentinus edodes (Berk.) upon hot-air drying treatment

This study elucidated the biosynthesis and changing behaviors of organic sulfide in shiitake mushrooms upon hot-air drying treatment. The changes of aw, moisture migration, contours of taste and flavor, organic sulfide, and 4 key enzyme activities were monitored throughout three drying procedures (CT/ST1/ST2). Results showed that drying rate was related to the moisture migration. Key enzymes of γ-GTase, ASFase and CS lyase were heat-resistant proteases, while C-Dase exhibited low thermal stability with the activity decreased during treatment. A total of 17 organic sulfides were identified and PLS analyses suggested 6 cyclic polysulfides were formed by C-Dase desulfurization, while 5 thioethers generation were related to the thermal cleavage of direct precursors (straight-chain di/tris/tetrasulfonyl esters) and Maillard reaction. These results indicated that ST2 drying procedures had a positive effect on the formation of cyclic polysulfides at the end of drying pried and the achievement of premium flavor qualities.

Woodchip bioreactors for saline leachates denitrification can mitigate agricultural impacts in mediterranean areas: The Campo de Cartagena-Mar Menor environmental issue

Leachates from intensive agriculture containing high nitrate have been identified as a major cause of the severe eutrophication crisis that impacts Mar Menor (SE Spain), the largest hypersaline coastal lagoon in the Mediterranean basin. A best management practice for removing NO3−-N is denitrifying bioreactors. This is the first study to assess the efficiency of citrus woodchips bioreactors in treating agricultural leachates that flow to the Mar Menor via surface discharges. Denitrification capacity, woodchip degradation (by weight loss), formation of potentially harmful compounds, and greenhouse gas (GHG) emissions were assessed. Three bioreactors (6 m × 0.98 m x 1.2 m) filled with citrus woodchips (3 m3 d−1 per bioreactor) through which the untreated ditch water over 1.5 years. Bioreactors were operated at 8 h, 16 h, and 24 h hydraulic residence time respectively, in each bioreactor. The main characteristics of the ditch water were: pH ≈ 7.5–8.0, electrical conductivity ≈ 5–8 dS m−1, dissolved organic carbon ≈6–10 mg L−1, and NO3−-N ≈ 22–45 mg L−1. Bioreactors were highly efficient in reducing NO3−-N. The average RNO3 in effluents was for the complete experimental period 8 g N m−3 d−1, 10.9 g N m−3 d−1, and 12.6 g N m−3 d−1 for 8, 16 and 24 h residence time, respectively. Nitrate reduction efficiency was modulated by seasonal changes in temperature, with an increasing efficiency in warmer periods (maximum ≈ 85–90% for all hydraulic residence time) and decreasing in colder ones (minimum ≈ 12%, 23% and 41% for hydraulic residence time 8, 16 and 24 h respectively). Woodchips degradation was greatest during the first six months (average ≈ 29% weight loss) in the material above the water level, attributable to aerobic mineralization of the organic carbon, while weight loss was ≈11% in woodchip media continuously below the water level. Dissolved organic carbon, sulfide, ammonium, and soluble phosphorus concentrations in the effluents were mostly low, although some peaks in concentrations occurred. Design consideration must be taken to avoid environmental impacts due to the occasional presence of harmful compounds in the effluents.

Variation and Correlation Analysis of Flavour and Bacterial Diversity of Low-Salt Hotpot Sauce during Storage.

Culinary circles have experienced a recent trend towards low-salt hotpot sauces. Here, changes in the physicochemical quality, flavour, and bacterial diversity of hotpot sauces with different salt concentrations were studied during storage. The results indicated that the peroxide and acid values of hotpot sauce increased gradually and that the quality began to deteriorate with storage. A storage temperature of 4 °C and salt concentration above 4.4% significantly reduced spoilage. The salt concentration had no significant effect on the flavour but extended storage resulted in significant differences in flavour reflected in the changes of sweet, sour, bitter, umami, aftertaste-A, abundance, organic sulphide, and alkanes. Significant differences were found in the bacterial composition between samples stored at different temperatures. Norank-f-o-Chloroplast was the main bacterium in the samples stored at low temperatures, which was beneficial for preservation. Bacillus was detected in 4.1% NaCl samples stored at 25 °C, directly promoting sauce spoilage and an unpleasant flavour. This bacterium signalled the spoilage of low-salt hotpot sauce stored at room temperature.

Simulating fish farm enrichment and fallowing impacts reveals unequal biogeochemical recovery of benthic variables

Finfish aquaculture is playing an increasing role in global food provision, with accompanying increases in benthic impacts under intensive pen production systems. Deposited faeces under and near fish pens affect the seafloor environment and biogeochemical functioning. To maintain healthy coastal environments, many fish farms operate by alternating input and fallowing periods to allow benthic coastal receiving environments to recover from excess organic matter inputs. Here, we used flow-through annular flume mesocosms to simulate sustained organic matter inputs to the benthos with a subsequent fallowing period of no inputs. To quantify the effects of excess organic matter loading on benthic receiving environments, we carried out repeated closed-system flux studies to quantify the benthic carbon mineralisation processes, with a focus on benthic oxygen, inorganic and organic carbon, nitrogen, phosphate, and sulphide fluxes, along with the redox state throughout the input and recovery period. We found that recovery periods were input-dependent, with parameters requiring longer fallowing periods to recover following larger inputs. While some benthic parameter fluxes such as dissolved organic carbon, sulphide, and ammonium returned to their pre-input state relatively rapidly (1-2 mo) following cessation of inputs, others such as sediment oxygen demand, ammonium, and redox required longer (>7 mo) to recover. Our results suggest that in situations where the benthic macrofaunal community has been severely impaired, extended fallowing periods may be required in order to permit the biogeochemical composition of the seabed to return to a more natural state, with implications for farm-consenting permits and planning as well as operational fallowing practices.

A density functional theory study on the adsorption of different organic sulfides on boron nitride nanosheet.

The adsorption of methanethiol (MT), thiophene (T), benzothiophene (BT), dibenzothiophene (DBT) on hexagonal boron nitride (h-BN) has been investigated by the framework of the density functional theory (DFT) calculations in this work. The prefer adsorption sites and interfacial angles of different sulfur compounds on the surface of the h-BN are investigated and analyzed. The adsorption energy results indicated that the adsorption of MT (Ead ≈ -6 kcal mol-1), T (Ead ≈ -10 kcal mol-1), BT (Ead ≈ -15 kcal mol-1), and DBT (Ead ≈ -21 kcal mol-1) on monolayer h-BN is physical interaction, and the value of Ead on bilayer h-BN is more than that on monolayer h-BN 0.05%. Adsorptive conformations show that sulfides prefer to be adsorbed on center B atoms rather than N atoms. Meanwhile, thiophene and its analogues tend to be adsorbed parallel on h-BN plane. Energy decomposition, natural population analysis (NPA), and electrostatic potential (ESP) analysis used to better understand the nature of adsorption on h-BN. van der Waals force plays a dominant role in adsorption process. Due to the π-π interactions, T, BT, and DBT have larger van der Waals forces than MT and the value of adsorption energy is negative correlated to the number of benzene rings. These findings are helpful for deeper understanding the adsorptive desulfurization mechanism and help develop better adsorbents for desulfurization in the future.

Desulfurization of diesel via joint adsorption and extraction using a porous liquid derived from ZIF-8 and a phosphonium-type ionic liquid.

A type-III porous liquid based on zeolitic imidazolate framework-8 (ZIF-8) and an ionic liquid trihexyltetradecylphosphonium bis(trifluoromethylsulfonyl)imide ([THTDP][BTI]) was synthesized and used for the desulfurization of model diesel. The desulfurization effect by ZIF-8/[THTDP][BTI] combined both the adsorptive desulfurization by ZIF-8 and the extraction desulfurization by [THTDP][BTI]. The removal of the three chosen aromatic organic sulfides by the ZIF-8/[THTDP][BTI] porous liquid followed the order of dibenzothiophene (73.1%) > benzothiophene (70.0%) > thiophene (61.5%). It was further found that deep desulfurization could be realized by ZIF-8/[THTDP][BTI] through triple desulfurization cycles and ZIF-8/[THTDP][BTI] can be regenerated readily. The desulfurization mechanism was explored further in detail by conformation search and density functional theory calculations. Calculations supported that the large molecular volume of [THTDP][BTI] excluded itself from the cavities of ZIF-8, making the pores of ZIF-8 in the porous liquid unoccupied and accessible by other guest species, here the studied organic sulfides. These calculations indicate that the van der Waals interactions were the main interactions between ZIF-8/[THTDP][BTI] and specifically benzothiophene. This work supports that the porous liquid ZIF-8/[THTDP][BTI] could potentially be used for desulfurization of diesel in industry.

An investigation into arsenic speciation in a wetland impacted by acid mine drainage

The formation of acid mine drainage (AMD) and release of toxic contaminants, such as arsenic (As), is a serious environmental problem encountered worldwide. In this study, we investigate the crucial role the Klip River wetland system plays in attenuating As arising from gold mining activities within the Witwatersrand Basin in Johannesburg, South Africa. Mining operations in the region commenced over 130 years ago and have been associated with the widespread pollution of water resources by AMD. We investigated As concentrations, bioavailability and speciation in a peat core from the Klip River wetland as well as in samples from the main tributaries and tailing storage facilities (TSFs) in the upper catchment. Total As concentrations in tributary and TSFs samples ranged between 10.1-89.9 mgkg-1 and 77.4-106 mg kg-1, respectively, with concentrations in the wetland varying between 1.91-73.8 mg kg-1. In general, As bioavailability was low in both catchment (19%) and wetland (4%) samples, with elemental associations suggesting the majority is bound in an immobile form to organic matter and sulfide. As(v) was the predominant species detected in all samples (0.0901-16.6 mg kg-1), with As(m), MMA and DMA present in lower concentrations. Strong correlations between As and S suggest that speciation and methylation are dependent on both chemical and microbial activity. The study highlights the vital role that wetlands can play in sequestering As in the environment.

Removal of volatile organic compounds and hydrogen sulfide in biological wastewater treatment plant using the compact trickle-bed bioreactor

Removal of volatile organic compounds and hydrogen sulfide in biological wastewater treatment plant using the compact trickle-bed bioreactor

The synergy between a benzoselenadiazole covalent organic framework and TEMPO for selective photocatalytic aerobic oxidation of organic sulfides

A benzoselenadiazole covalent organic framework works in synergy with TEMPO for selective photocatalysis in aerobic oxidation of organic sulfides.

Cooperative photocatalysis of dye-Ti-MCM-41 with trimethylamine for selective aerobic oxidation of sulfides illuminated by blue light.

Ti-incorporated mesoporous materials have widespread applications in photocatalysis. Their adjustable pores could accommodate dyes like alizarin red S (ARS) to circumvent the lack of visible light response. Herein, Ti-MCM-41 was obtained to anchor visible light-capturing ARS, forming ARS-Ti-MCM-41. The ARS-Ti-MCM-41 was screened for the selective photocatalytic oxidation of organic sulfides. To improve the stability of the anchored ARS, electron transfer was orchestrated by a mediator trimethylamine (TMA, 2mol%) illuminated by blue LEDs. Phenyl methyl sulfide could be almost entirely converted into phenyl methyl sulfoxide with 99% of selectivity within 18min. In addition, Ti-MCM-41 was beneficial for the anchored ARS, which in turn guaranteed good recycling performance of ARS-Ti-MCM-41. The solvent trifluoroethanol enabled the stability of TMA and facilitated the highly selective formation of the target sulfoxides. This work sheds light on the vast possibility for visible light photocatalysis of dye-mesoporous materials.

Chalcogen atom abstraction from NCE− (E = O, S, Se) and i-Pr2S by the excited state of a luminescent tricyano osmium(vi) nitride

The unprecedented chalcogen atom abstraction from stable inorganic anions NCE− and organic sulphide i-Pr2S was developed by the excited state osmium nitride complex (OsN*).

Fabrication of dianthracene-based hyper-cross-linked polymers for selective photocatalytic oxidation of organic sulfides

Two dianthracene-based hyper-cross-linked polymers are developed as photocatalysts for selective photocatalytic oxidation of organic sulfides for the first time.

Diallyl trisulfide ameliorates bone loss and alters specific gut microbiota and serum metabolites in natural aging mice.

Aging is a major cause of bone loss and osteoporosis. Diallyl trisulfide (DATS), one of the main organic sulfides in garlic oil, has been shown to alleviate arthritis in mice. However, further research is still needed to determine how DATS affects bone formation and bone loss in aging mice. Here, we established a mouse model of natural aging for dietary DATS intervention. DATS treatment improved the bone microstructure, including the disorganized arrangement of bone trabeculae and promoted collagen synthesis, as confirmed by micro-CT and histological analyses. The abundance of beneficial bacteria for bone formation, such as Clostridiaceae and Erysipelotrichaceae, and the microbial diversity and community richness were all altered by DATS, according to 16S rRNA sequencing data. 14 potential biomarkers and 9 important metabolic pathways were examined using serum metabolomics analysis. Additionally, there has been a significant reduction in sphingosine, which is directly associated with bone metabolism. The level of sphingosine and relative abundance of Clostridium were found to be negatively correlated by correlation analysis, indicating that bacteria may regulate bone reconstruction via influencing metabolites. Furthermore, Runx2 and β-catenin gene expression levels increased in bones, which may be related to the ameliorative mechanism of DATS. Our results suggested that DATS may prevent age-related bone loss by upregulating osteogenic gene expression through altering gut microbes and serum metabolism.

2D β-ketoenamine-linked triazine covalent organic framework photocatalysis for selective oxidation of sulfides

Blue light-powered aerobic oxidation of organic sulfides sufficiently yields sulfoxides over TpTAPT-COF.

In Vitro and In Situ Characterization of Psychrotrophic Spoilage Bacteria Recovered from Chilled Chicken

Spoilage bacteria play a remarkable role in the spoilage of chilled chicken. In this paper, a total of 42 isolates belonging to 16 species of four genera were isolated from chilled chicken and displayed different characterizations of psychrotrophic spoilage. Six isolates of J7, J8, Q20, Q23, R1, and R9 with differences in proteolytic capabilities were further characterized for in situ spoilage potential evaluation. Pseudomonas lundensis J8 exhibited the strongest spoilage potential in situ, displaying a fast growth rate, increased pH velocity, high total volatile basic nitrogen, and high peptide content in the chicken samples. The volatile flavor analysis of chicken samples via electronic nose indicated that the content of characteristic odors representing spoilage, including sulfides, organic sulfide, and hydride, increased during storage. Additionally, the principle component and correlation analyses revealed that the spoilage odors produced by different species of bacteria were significantly different and positively correlated with the results of protease activity in vitro. The characteristics of spoilage bacteria in chilled chicken provided a comprehensive insight into microbial assessment during storage.

Dynamics of organic matter in the changing environment of a stratified marine lake over two decades

The marine lake (Rogoznica Lake), which fluctuates between stratified and holomictic conditions, is a unique environment on the eastern Adriatic coast affected by environmental changes. These changes are reflected in the warming of the water column, the apparent deoxygenation of the epilimnion, and the accumulation of organic matter (OM), toxic sulfide, and ammonium in the anoxic hypolimnion. Since the early 1990s, the volume of anoxic water has increased as the chemocline has moved to the surface water layer. A trend toward enrichment of refractory dissolved organic carbon (DOC) was observed in the anoxic hypolimnion, while a decreasing trend was observed in the oxic epilimnion in the spring DOC. At the same time, the most reactive surface-active fraction of DOC showed the opposite trend. In addition, there is evidence of accumulation of particulate organic carbon (POC) in the water column, followed by an increase in the fraction of POC in total organic carbon (TOC).On a multi-year scale (1996–2020), this work presents a unique time series of the dynamics of OM in the stratified marine system, showing a significant change in its quantity and quality due to climate and environmental variability. DOC-normalized surfactant activity is shown to be a good indicator of environmental change.

Evaluation of the tribological and anticorrosive properties of triazine derivatives in emulsion

Four triazine mantic acid derivative additives were synthesized, and their tribological properties in rapeseed oil (RSO) were investigated with a four-ball tester. The results showed that the emulsions prepared with thiotriazine derivatives had excellent tribological properties. For the same S content, the antiwear performance was enhanced by increasing the carbon chain length at low load and deduced by increasing the carbon chain length at high load. The superior antiwear performance was attributed to forming the organic sulfide and nitrogen adhering layer, moreover, under low load, the thiotriazine xanthate derivatives containing a longer substituent chain would be hardly damaged during sliding, and the branch chain on the substituent group would be beneficial to enhance the tribological properties of triazine xanthine derivatives. Sulfur-containing triazine derivatives have a good corrosion inhibition effect for Q235 steel because they contain N, O, S, and other active sites. These heteroatoms have unshared lone pair electrons, which can coordinate with the unoccupied orbital of Fe atoms to form covalent bonds and prohibit the corrosive media from contacting the surface of the Q235 steel, thus inhibiting the corrosion processes.

The Use of Polydialkylsiloxanes/Triflic Acid as Derivatization Agents in the Analysis of Sulfur-Containing Aromatics by “Soft”-Ionization Mass Spectrometry

Polycyclic aromatic sulfur-containing compounds are widely distributed in oil, especially in its low-volatile and heavy fractions (resins, asphaltenes), and this dictates the need for their determination when reliable methods for sulfur removing, cleaning and processing oil are developed. In these cases, "soft" ionization mass spectrometry methods, based on electrospray ionization (ESI) and matrix-assisted laser desorption/ionization (MALDI), are particularly effective. However, aromatic sulfur-containing compounds have low polarity and cannot be readily ionized by these methods. To overcome the problem, their preliminary conversion into sulfonium salts by the action of alkyl iodides and a silver-containing agent is widely used. In the process of developing more economical derivatization methods, we found a rather unexpected possibility of implementing S-alkylation of organic sulfides with commercial polydialkylsiloxanes (alkyl = CH3 or C2H5) in the presence of triflic acid (CF3SO3H) as a superacid co-alkylating agent. For homologous dibenzothiophenes as a typical model representative of petroleum sulfur-containing aromatic compounds, ESI and MALDI mass spectra exhibited the signals of corresponding S-alkylsulfonium salts with a high signal-to-noise ratio. A rational mechanism for the described chemical transformation is proposed, including the indispensable activation by triflic acid and the cleavage of the Si-C bond. Specific collision-induced dissociation of corresponding S-alkylated sulfonium cations is considered. The applicability of the derivatization approach to the analysis of petroleum products by high-resolution mass spectrometry is demonstrated.