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Introduction: Distinguishing and categorizing the origin of garlic are highly significant, considering its widespread use as a flavoring agent. With billions of dollars annually in global trade, garlic is frequently susceptible to fraudulent practices. Methodology: Paper spray ionization mass spectrometry (PS‐MS) was employed to quickly analyze garlic samples from distinct geographic origins: China and Brazil. The so‐generated PS‐MS data were treated with metabolomic multivariate approaches, and the garlic samples from these different geographic regions were easily discriminated. Results: Brazilian garlic was characterized to contain higher levels of amino acids, such as arginine, proline, and valine, and organosulfur compounds, such as allicin, alliin, and l‐γ‐glutamil‐S‐allyl‐l‐cysteine, compared to Chinese garlic. The PS‐MS data were treated employing multivariate approaches, typically used in the metabolomics field, and this protocol was promptly able to discern among both types of samples. Conclusion: Hence, this combined strategy holds promise not only as an effective tool for the authentication of the geographical origin of garlic but also as a powerful means for biomarker discovery. [ABSTRACT FROM AUTHOR]

Introduction: Garlic (Allium sativum) is a popular food spice worldwide with many health benefits. Garlic and its products have been used to treat various infections in traditional medicine in India, the Middle East, and Southeast Asia. Garlic and its organosulphur compounds have antibacterial properties against methicillin-resistant Staphylococcus aureus (MRSA), but the antibiofilm property and interaction with methicillin have been relatively unexplored. Biofilm formation is crucial in MRSA infections, one of the most common nosocomial infections. Method: The antibacterial activity fresh garlic extract (FGE) against MRSA was evaluated by determining the minimum inhibitory concentration (MIC) and zone of inhibition using microdilution and well diffusion assays respectively. Microtiter plate crystal violet assay and scanning electron microscopy was use to evaluate the antibiofilm activity of FGE against MRSA. Results: Sub-MIC concentrations of FGE significantly reduce methicillin-susceptible S. aureus (MSSA) and MRSA biofilm formation. Scanning electron microscopy analysis suggests that FGE reduces the attachment of MSSA and MRSA. Diallyl sulphide, one of the organosulphur compounds of garlic, inhibited the biofilm formation of MSSA and MRSA. Sub-MIC concentration of FGE also sensitized MRSA to methicillin, completely inhibiting MRSA growth when used in combination. Similar effects were noticed when FGE was combined with other β-lactam antibiotics to which MRSA was resistant. Conclusions: The study validates garlic as an antibacterial agent in ethnomedicine through scientific evidence. Garlic and its organosulphur compounds are potential antibiofilm agents against MRSA. Moreover, garlic could be potentially used as a complementary or alternative medicine to treat infections caused by drug-resistant bacteria such as MRSA. [ABSTRACT FROM AUTHOR]

This article discusses the use of photocatalysis in [2,3]-sigmatropic rearrangement reactions of diazo compounds. Metal catalysts are commonly used to access the carbene fragment necessary for these reactions, but visible-light-mediated transformations have gained interest for their green and sustainable synthesis potential. The authors explore the use of heavy atoms and organosulfur compounds as catalysts in these reactions, and optimize the conditions using ruthenium catalysts. The photocatalytic rearrangement reactions are found to be efficient and yield moderate to high yields of the desired products. [Extracted from the article]

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. [ABSTRACT FROM AUTHOR]

Cyclopropylmethyl sulfides react with N‐fluorosulfonimide (NFSI) or molecular iodine, enabling C−S cleavage to generate cyclopropylcarbinyl cations, which evolve through cyclopropane ring‐opening reactions into homoallyl cations suitable to react with nucleophiles present in the reaction media. This desulfurative cleavage of cyclopropylmethyl thioethers under non‐acidic conditions facilitates homoallylation of N‐based nucleophiles such as alkyl or aryl amines as well as sulfonimides through a one‐pot protocol in one or two steps depending on the nucleophile. The reaction is initiated by a halogen‐sulfur bond that causes C−S bond cleavage. Moreover, the reaction with iodine proceeds through homoallyl iodide intermediates. [ABSTRACT FROM AUTHOR]

In light of the important biological activities and widespread applications of organic disulfides, dithiocarbamates, xanthates, thiocarbamates and thiocarbonates, the continual persuit of efficient methods for their synthesis remains crucial. Traditionally, the preparation of such compounds heavily relied on intricate multi‐step syntheses and the use of highly prefunctionalized starting materials. Over the past two decades, the direct sulfuration of C−H bonds has evolved into a straightforward, atom‐ and step‐economical method for the preparation of organosulfur compounds. This review aims to provide an up‐to‐date discussion on direct C−H disulfuration, dithiocarbamation, xanthylation, thiocarbamation and thiocarbonation, with a special focus on describing scopes and mechanistic aspects. Moreover, the synthetic limitations and applications of some of these methodologies, along with the key unsolved challenges to be addressed in the future are also discussed. The majority of examples covered in this review are accomplished via metal‐free, photochemical or electrochemical approaches, which are in alignment with the overraching objectives of green and sustainable chemistry. This comprehensive review aims to consolidate recent advancements, providing valuable insights into the dynamic landscape of efficient and sustainable synthetic strategies for these crucial classes of organosulfur compounds. [ABSTRACT FROM AUTHOR]

A binuclear dioxomolybdenum catalyst [(MoO2Cl2)2(L)] (1) (with L (1S,2S)-N,N′-bis(2-pyridinecarboxamide)-1,2-cyclohexane) was prepared and used as catalyst for the desulfurization of a multicomponent model fuel containing the most refractory sulfur compounds in real fuels. This complex was shown to have a high efficiency to oxidize the aromatic benzothiophene derivative compounds present in fuels, mainly using a biphasic 1:1 model fuel/MeOH system. This process conciliates catalytic oxidative and extractive desulfurization, resulting in the oxidation of the sulfur compounds in the polar organic solvent. The oxidative catalytic performance of (1) was shown to be influenced by the presence of water in the system. Using 50% aq. H2O2, it was possible to reuse the catalyst and the extraction solvent, MeOH, during ten consecutive cycles without loss of desulfurization efficiency. [ABSTRACT FROM AUTHOR]

Catalytic oxidative desulfurization (ODS) using titanium silicate catalysts has emerged as an efficient technique for the complete removal of organosulfur compounds from automotive fuels. However, the precise control of highly accessible and stable-framework Ti active sites remains highly challenging. Here we reveal for the first time by using density functional theory calculations that framework hexa-coordinated Ti (TiO6) species of mesoporous titanium silicates are the most active sites for ODS and lead to a lower-energy pathway of ODS. A novel method to achieve highly accessible and homogeneously distributed framework TiO6 active single sites at the mesoporous surface has been developed. Such surface framework TiO6 species exhibit an exceptional ODS performance. A removal of 920 ppm of benzothiophene is achieved at 60°C in 60 min, which is 1.67 times that of the best catalyst reported so far. For bulky molecules such as 4,6-dimethyldibenzothiophene (DMDBT), it takes only 3 min to remove 500 ppm of DMDBT at 60°C with our catalyst, which is five times faster than that with the current best catalyst. Such a catalyst can be easily upscaled and could be used for concrete industrial application in the ODS of bulky organosulfur compounds with minimized energy consumption and high reaction efficiency. [ABSTRACT FROM AUTHOR]

HKUST-1 is a well-known copper-based metal-organic framework (MOF), promising to be used in separation processes, however its industrial usage remains confined due to its difficult handling and low mechanical stability when in powder form. In this work, we have synthesized and analyzed the mechanical properties of novel HKUST-1 shaped composites based on methylcellulose (MC) and poly(vinyl formal) (PVMF), using a simple and inexpensive extrusion technique. The composites were characterized using different techniques, such as Fourier transform infrared (FTIR) spectroscopy and powder X-ray diffraction (PXRD) analysis, which demonstrated that their structure and crystallinity were not compromised by the shaping process. Their mechanical properties were investigated by compressive strength measurements and scanning electron microscopy (SEM). The composite with methyl cellulose showed good mechanical resistance, with an average crushing strength value of 40 N. Nitrogen sorption measurements showed that the specific surface area reduction due to the shaping process for HKUST@MC was only 8.6%. The greater hydrolytic stability after heat activation of HKUST@MC compared to that of the pure MOF was also verified. The adsorptive capacity of HKUST@MC towards organosulfur compounds found in sour gas was evaluated in a desulfurization test using a realistic multicomponent gas mixture. HKUST@MC exhibiting a high efficiency to adsorb organosulfur outperformed the benchmark sulfur adsorbent Norit RGM 3 in the adsorption of ethanethiol and dimethyl disulfide. Therefore, in this work we present a technically feasible and cost-effective method to produce a novel HKUST-1 shaped composite with good mechanical and water resistance properties preserving the MOF porosity and gas adsorption properties. [ABSTRACT FROM AUTHOR]

This article discusses a new method for synthesizing diaryl disulfides and arylthio acetic acids using thioglycolic acid and copper catalysts. Traditional methods for synthesizing these compounds can be challenging, but this new method offers a more accessible approach. The article provides optimized reaction conditions and explores the substrate scope of the method, demonstrating its applicability to a variety of aryl iodides. The synthesized compounds can be used as intermediates for the synthesis of asymmetric sulfides. Overall, this method offers a cost-effective and readily available solution for the synthesis of these important compounds. [Extracted from the article]

Optically pure sulfoxides are valuable organosulfur compounds extensively employed in medicinal and organic synthesis. In this study, we present a biocatalytic oxidation‐reduction cascade system designed for the preparation of enantiopure sulfoxides. The system involves the cooperation of a low‐enantioselective chimeric oxidase SMO (styrene monooxygenase) with a high‐enantioselective reductase MsrA (methionine sulfoxide reductase A), facilitating "non‐selective oxidation and selective reduction" cycles for prochiral sulfide oxidation. The regeneration of requisite cofactors for MsrA and SMO was achieved via a cascade catalysis process involving three auxiliary enzymes, sustained by cost‐effective D‐glucose. Under the optimal reaction conditions, a series of heteroaryl alkyl, aryl alkyl and dialkyl sulfoxides in R configuration were synthesized through this "one‐pot, one step" cascade reaction. The obtained compounds exhibited high yields of >90 % and demonstrated enantiomeric excess (ee) values exceeding 90 %. This study represents an unconventional and efficient biocatalytic way in utilizing the low‐enantioselective oxidase for the synthesis of enantiopure sulfoxides. [ABSTRACT FROM AUTHOR]

Sulfenamides are organosulfur compounds that contain a single bond between nitrogen and sulfur in their structures. Sulfur can react with nucleophiles to yield new compounds. The compounds having nitrogen–sulfur bonds are used in polymers for a variety of purposes, including medicines, agrochemicals, veterinary medications, and environmental studies. This review will examine several chemical reactions that lead to sulfenamide production as well as how they are used in cell biology and biochemical applications. [ABSTRACT FROM AUTHOR]

Allium species have been recommended in traditional medicine for its efficacy in treating a variety of diseases such as arthritis, cardiovascular and kidney diseases, diabetes, colds, flu, headache, cough, hemorrhage, atherosclerosis, asthma, cancer, colic and skin problems Notably, it has shown promise in mitigating inflammation, regulating blood sugar levels and reducing oxidative damage. Metabolic syndrome, a cardiovascular risk factor characterized by a cluster of metabolic irregularities, including obesity, dyslipidemia, hypertension, and type 2 diabetes mellitus, often precipitates insulin resistance and development of cardiovascular disease or diabetes. This review endeavors to explore the role of various Allium species on different aspect of metabolic syndrome. Bibliographic databases, including PubMed and Scopus, Science Direct and Google Scholar databases were searched for the collection of relevant information. The abundant biological benefits of Allium species against the metabolic syndrome can be attributed to compounds such as flavonoids, steroidal saponins, stilbenoids and organosulfur compounds (OSCs). Both extracts and isolated compounds have exhibited efficacy in reducing internal mediator of hypertension, cholesterol, triglycerides and low-density lipoprotein, showcasing favorable attributes in weight management and type 2 diabetes control. Organosulfur compounds, steroidal saponins and phenolics are among the large number of active components of the genus Allium, displaying multiple pharmacological actions, which are supported by in vitro, in vivo and clinical studies. Nevertheless, while the existing body of evidence underscores the potential of Allium genus and its active components in managing complications associated with metabolic syndrome, further clinical trials are warranted to support their efficacy and safety for clinical application. [Display omitted] • This review presents role of different species belongs to the genus Allium on different aspect of the metabolic syndrome. • The abundant biological benefits of Allium species is dominated by flavonoids, steroidal saponins, stilbenoids and OSCs. • The biological benefits of extracts and pure compounds (in vitro, in vivo and clinical studies) against the metabolic syndrome is comprehensively discussed. • Detailed molecular pathways affected by Allium species are discussed in detail. [ABSTRACT FROM AUTHOR]

Dibenzothiophene (DBT) is a major form of organo-sulfur compound chiefly found in coal. Acidithiobacillus ferrooxidans cells played the role of catalyst in degrading DBT to 2-hydroxy biphenyl (2HBP) through the formation of dibenzothiophene-sulfone and releasing the sulfur present in it. Experiments on the biodegradation of DBT by A. ferrooxidans bacterium using 9K medium with DBT at 3 g/L in a 500 mL shake flask scale achieved degradation of DBT up to 95% in 12 days. The A. ferrooxidans cells degrade DBT to 2-hydroxy biphenyl and release the sulfur atom in DBT through the formation of the intermediate dibenzothiophene-sulfone. The formation of 2HBP from microbial degradation of DBT followed the chemical control model of shrinking core reactions model in solid-liquid interactions. The kinetics of the DBT degradation by A. ferrooxidans followed first-order for a low initial concentration of DBT (3 g/L), and the kinetics were shifted to second-order with an increase in DBT concentration to 5 g/L. [ABSTRACT FROM AUTHOR]

We report a versatile, Et3N-mediated thia-Michael addition–elimination reaction for producing a series of novel heteroaromatic thiol-based 2H-chromenes in good to excellent yields (59–94%). The protocol involves a one-pot reaction with mild conditions, short reaction period, simple workup procedure, and scalability. The synthesized compounds were screened with different bases and characterized by 1H NMR, 13C NMR, and HRMS. The compounds were assessed for their in vitro antibacterial activities against two pathogenic bacterial strains, E. coli and S. aureus. Among all the tested compounds, 17f and 17t exhibited the most excellent potency against both bacterial strains relative to the standard antibiotic, gentamicin, with corresponding MIC values of 12.5 (μg mL−1) and 6.25 (μg mL−1). In the SARs, the compounds 17t and 17f, having –Cl and –Br groups, respectively, showed the highest substantial antibacterial activity. The results revealed a promising lead organosulfur compound for future drug discovery. [ABSTRACT FROM AUTHOR]

Water-soluble ligands based on a 1,10-phenanthroline core are relatively poorly studied compounds. Developing efficient and convenient syntheses of them would result in new interesting applications because of the importance of 1,10-phenanthrolines. In this manuscript, we describe novel and practical ways to introduce a carboxyl and, for the first time, a phenol and dithiocarboxyl group under mild reaction conditions. This strategy enables highly efficient and practical synthesis of suitable organosulfur compounds with high added value, high chemoselectivity, and a broad substrate range. We present the selective conversion of a hydroxydialdehyde in the form of 10-hydroxybenzo[h]quinoline-7,9-dicarbaldehyde into its derivative, unique hydroxydicarboxylic acid, by an oxidation procedure, giving 10-hydroxybenzo[h]quinoline-7,9-dicarboxylic acid. A similar procedure resulted in the formation of 9-methyl-1,10-phenanthroline-2-carboxylic acid by oxidation of commercially available neocuproine. An alternative method of obtaining 1,10-phenanthroline derivatives possessing carboxylic acid group can be based on the hydrolysis of ester or nitrile groups; however, this synthesis leads to unexpected products. Moreover, we apply Perkin condensation to synthesize a vinyl (or styryl) analog of 1,10-phenanthroline derivatives with phenol function. This reaction also demonstrates a new, simple, and efficient strategy for converting methyl derivatives of 1,10-phenanthroline. We anticipate that the new way of converting methyl will find wide application in chemical synthesis. [ABSTRACT FROM AUTHOR]

Certain factors hinder the commercialization of biodesulfurization process, including low substrate-specificity of the currently reported desulfurizing bacteria and restricted mass transfer of organic-sulfur compounds in biphasic systems. These obstacles must be addressed to clean organic-sulfur rich petro-fuels that pose serious environmental and health challenges. In current study, a dibenzothiophene desulfurizing strain, Gordonia rubripertincta W3S5 (source: oil contaminated soil) was systematically evaluated for its potential to remove sulfur from individual compounds and mixture of organic-sulfur compounds. Metabolic and genetic analyses confirmed that strain W3S5 desulfurized dibenzothiophene to 2-hydroxybiphenyl, suggesting that it follows the sulfur specific 4 S pathway. Furthermore, this strain demonstrated the ability to produce trehalose biosurfactants (with an EI24 of 53%) in the presence of dibenzothiophene, as confirmed by TLC and FTIR analyses. Various genome annotation tools, such as ClassicRAST, BlastKOALA, BV-BRC, and NCBI-PGAP, predicted the presence of otsA, otsB, treY, treZ, treP, and Trehalose-monomycolate lipid synthesis genes in the genomic pool of strain W3S5, confirming the existence of the OtsAB, TreYZ, and TreP pathways. Overall, these results underscore the potential of strain W3S5 as a valuable candidate for enhancing desulfurization efficiency and addressing the mass transfer challenges essential for achieving a scaled-up scenario. [ABSTRACT FROM AUTHOR]

Over the past few years, the biological properties of garlic have been utilized as an attractive natural alternative to many therapeutic drugs. The biological effects of garlic have been ascribed to organosulfur compounds, secondary metabolites derived from amino acids. The present study aimed to investigate the extracts of a novel garlic variety (Hisar garlic 17) after processing it as fresh, dry, heated, and aged in different solvents and then analyzed with highly sensitive and rapid technique i.e., High resolution liquid chromatograph mass spectrometer quadrupole time of flight (HR-LCMS-QTOF) Mass spectrometer to study the amino acids and organosulfur compounds. 47 amino acids and 11 organosulfur compounds were detected out of which 8 organosulfur compounds were found as secondary metabolites of amino acids. Among the 22 crucial a-amino acids, garlic extracts revealed the presence of 18 amino acids, either in their native state or associated with various complex compounds. The study reported major organosulfur compounds, including Alliin, S-allyl cysteine, S-methyl cysteine, N-gamma-Glutamyl-Sallylcysteine, and 2-Propenyl 1-(2-propenylsulfinyl)propyl disulfide. This study demonstrated that HG17 garlic is abundant in amino acids and organosulfur compounds, suggesting its potential utilization as a supplement in nutraceuticals. [ABSTRACT FROM AUTHOR]

Garlic (Allium sativum L.), a member of the Alliaceae family, has been widely used in cuisine and traditional medicine since ancient times. Black garlic is produced by fermentation of fresh garlic under controlled conditions for a certain period at high temperature (60-90°C) and high humidity (70-90%). According to the Turkish Statistical Institute (TURKSTAT) data, Kastamonu and Gaziantep garlic varieties are the most cultivated garlic varieties in our country. Changes in protein, sugar content, antioxidant capacity (DPPH and ABTS methods), total phenolic content, 5-hydroxymethylfurfural (HMF) content, and organosulfur compound profiles were investigated in samples taken from Kastamonu and Gaziantep fresh garlic at 7, 14, 21, and 28 days of black garlic production under 65°C temperature and 70% humidity conditions. With these analyses, the differences between black garlic and fresh garlic and the changes in black garlic during the production process were revealed in detail. It was determined that the amount of total phenolic content and antioxidant capacities increased in the black garlic production processes of both regions compared to fresh garlic. While sucrose was fresh garlic's dominant sugar, fructose was black garlic's dominant sugar. Among the organosulfur compounds, allicin was dominant in fresh garlic and SAC in black garlic. It was determined that SAC was formed after the enzymatic conversion of ɣ-glutamyl-S-alk(en)yl-L-cysteine and ɣ-glutamyl and the temperature and fermentation time used in black garlic production increased the formation of SAC. The protein content ranging between 5.8%-7.3% in fresh garlic was 13.1-14.2% in black garlic. Fresh and black garlic from the Gaziantep region was determined to have higher total phenolic content, antioxidant capacity, and organosulfur compound contents. [ABSTRACT FROM AUTHOR]

Garlic is in the family Liliaceae and has many different constituents such as organic sulfur compounds, amino acids, carbohydrates, minerals, and vitamins. In this work, a simple, sensitive, and accurate analytical method was developed for the determination of selected organosulfur compounds (OSCs) in garlic bulbs using reversed phase-high performance liquid chromatography (RP-HPLC). Oil-soluble and water-soluble OSCs were extracted from the garlic samples via acetonitrile and deionized water, respectively. The OSCs were separated on a Phenomenex C18 (250 mm, 4 mm, 5mm) column and the monitoring was performed with a UV detector at 220 nm. An isocratic mobile phase comprising of 0.10 M trifluoroacetic acid (TFA) in 85% acetonitrile (ACN) and 0.10 M TFA in distilled water (DW) (90: 10% v/v) was used to elute the analytes. Under optimum experimental conditions, the limits of detection (LOD) for the analytes were calculated in the range of 0.09 to 0.17 mg/kg. For the garlic sample extracts analyzed under optimal instrumental conditions, DAS (diallyl sulfide), DADS (diallyl disulfide), and DATS (diallyl trisulfide) were detected in the ranges of 8.0 to 32.5 mg/ kg, 20.4 to 67.3 mg/kg, and 60.7 to 356.6 mg/kg, respectively. Spiked recovery experiments were conducted on the garlic samples to confirm the method's applicability and accuracy. The recovery results ranged between 39.0% and 90.9% for the garlic samples extracted with deionized water. The developed method is simple, precise, accurate, reliable, and time-effective for the determination of OSCs. Additionally, the green profile of the developed method was investigated by using AGREEprep software and the greenness score was recorded as 0.65, indicating that the method developed is environmentally friendly. [ABSTRACT FROM AUTHOR]

Dearomative intramolecular Diels–Alder/sulfur extrusion reaction of thiophenes with alkynes successfully afforded fluoranthenes in moderate to excellent yields. The proximity of both reactive sites fixed at the peri‐position of naphthalene would play an important role in the progress of this reaction. Tri(o‐tolyl)phosphine effectively suppressed the side reactions as a sulfur scavenger. [ABSTRACT FROM AUTHOR]

The presence of organic molecules containing sulfur-sulfur bonds was documented in the water columns and sediments of the natural aquatic systems as well as in fossil fuels. These compounds range from small molecules of volatile organic compounds to polysulfide cross-linked macromolecules in the sediments. While processes leading to formation of these compounds were intensively studied during the last decades, kinetics and mechanisms of reactions which lead to their decomposition are poorly understood. In this work, the kinetics and products of the reactions of dimethyl disulfide, dimethyl trisulfide, and cyclic polysulfide lenthionine (1,2,3,5,6-pentathiepane) with hydrogen sulfide at the environmental pH and temperature ranges were studied. It was shown that at pH ≥ 5, the reaction of bisulfide anion (HS–) rather than that of hydrogen sulfide controls the overall reaction rates. The activation energy and the order of the reaction with respect to bisulfide anion is dimethyl disulfide– < dimethyl trisulfide < lenthionine, while the order of the reaction with respect to organosulfur compounds is lenthionine < dimethyl trisulfide < dimethyl disulfide. The obtained results suggest that bisulfide anion is responsible for fast decomposition of organosulfur compounds in aphotic natural aquatic systems. This observation leads to the conclusion that sulfurization of sedimentary organic matter during the early diagenesis is not an unidirectional but a dynamic process, and concentrations of organic compounds with sulfur-sulfur bonds are controlled by the polysulfide to sulfide sulfur concentrations ratio in the sedimentary pore waters. In addition, the cyclic polysulfides were shown to be more stable than their linear analogs that results in preferential preservation of these compounds during the maturation process. [ABSTRACT FROM AUTHOR]

Chemoselective transformations of functionalized sulfonyl fluorides and chlorides are surveyed comprehensively. It is shown that sulfonyl fluorides provide an excellent selectivity control in their reactions. Thus, numerous conditions are tolerated by the SO2F group – from amide and ester formation to directed ortho‐lithiation and transition‐metal‐catalyzed cross‐couplings. Meanwhile, sulfur (VI) fluoride exchange (SuFEx) is also compatible with numerous functional groups, thus confirming its title of "another click reaction". On the contrary, with a few exceptions, most transformations of functionalized sulfonyl chlorides typically occur at the SO2Cl moiety. [ABSTRACT FROM AUTHOR]

This review disclosed synthetic approaches to sulfonyl amides from non‐sulfonyl halogenated precursors. Known methods were systematized into groups and subgroups according to the type of starting organosulfur compound. Thiols, disulfides, and sulfonamides form a group of S(II)‐containing precursors, which are used in oxidative amination reactions. An important and versatile group for oxidative amination is represented with S(IV)‐containing compounds, i. e., sufinates, sulfinamides, DMSO, N‐sulfinyl‐O‐(tert‐butyl)hydroxylamine, etc. A series of S(VI)‐containing precursors for amination reactions (except sulfonyl halides) include sulfonic acids, sulfonyl azides, thiosulfonates, and sulfones. All approaches are represented with the most prominent examples of the resulting sulfonamides, which could be obtained in high yields mostly via short reaction sequences. Promising electrochemical methods for the preparation of sulfonamides from thiols, disulfides, sulfonamides, sulfinic acid derivatives, and dimethyl sulfoxide under mild and green conditions are also highlighted. [ABSTRACT FROM AUTHOR]

Black garlic is a fermented product from garlic (Allium sativum L.) that is processed by heating fresh garlic at a certain temperature and humidity for several days. Black garlic has higher antioxidant activity and is rich in organosulfur compounds. Therefore, black garlic has an unpleasant taste and odor. Spray drying of black garlic extract is important for wider application, preservation and prolongation of its shelflife. Black garlic powders were produced using SD-18A mini spray dryer. The purpose of this research was to evaluate the effect of inlet temperatures on the physical properties and antioxidant activity of aqueous black garlic powder. The inlet temperatures ranged from 165 to 225 °C, whereas other conditions were kept constant such as maltodextrin concentration (8 %) and feed flow rate (4.5 mL/min). The black garlic powders were examined for powder yield, moisture content, hygroscopicity, bulk density, wettability, antioxidant activity and total phenolic and flavonoid content. The optimal conditions for the drying process were achieved with an inlet temperature of 225 °C. An increase in the inlet temperature of the spray dryer has increased the powder yield, hygroscopicity, antioxidant activity and total phenolic and flavonoid content of the black garlic powder, but reduced the water content, bulk density and wettability of the spraydried product. [ABSTRACT FROM AUTHOR]

Inflammatory diseases are strongly associated with global morbidity and mortality. Several mediators are involved in this process, including proinflammatory interleukins and cytokines produced by damaged tissues that, somehow, act as initiators of the autoreactive immune response. Bioactive compounds present in plant-based foods and byproducts have been largely considered active agents with the potential to treat or prevent inflammatory diseases, being a valuable alternative to traditional therapeutic agents used nowadays, which present several side effects. In this regard, the present research uncovers the anti-inflammatory activity of the bioaccessible fraction of broccoli stalks processed, by applying different conditions that render specific concentrations of bioactive sulforaphane (SFN). The raw materials' extracts exhibited significantly different contents of total glucosinolates (GSLs) that ranged between 3993.29 and 12,296.48 mg/kg dry weight (dw), with glucoraphanin as the most abundant one, followed by GI and GE. The indolic GSLs were represented by hydroxy-glucobrassicin, glucobrassicin, methoxy-glucobrassicin, and neo-glucobrassicin, with the two latter as the most abundant. Additionally, SFN and indole-3-carbinol were found in lower concentrations than the corresponding GSL precursors in the raw materials. When exploring the bioaccessibility of these organosulfur compounds, the GSL of all matrices remained at levels lower than the limit of detection, while SFN was the only breakdown product that remained stable and at quantifiable concentrations. The highest concentration of bioaccessible SFN was provided by the high-ITC materials (~4.00 mg/kg dw). The results retrieved on the cytotoxicity of the referred extracts evidenced that the range of supplementation of growth media tested (0.002–430.400 µg of organosulfur compounds/mL) did not display cytotoxic effects on Caco-2 cells. The obtained extracts were assessed based on their capacity to reduce the production of key proinflammatory cytokines (interleukin 6 (IL-6), IL-8, and TNF-α) by the intestinal epithelium. Most of the tested processing conditions provided plant material with significant anti-inflammatory activity and the absence of cytotoxic effects. These data confirm that SFN from broccoli stalks, processed to optimize the bioaccessible concentration of SFN, may be potential therapeutic leads to treat or prevent human intestinal inflammation. [ABSTRACT FROM AUTHOR]

Sideritis scardica Griseb, also known as "mountain tea" and "Olympus tea" (Lamiaceae family) is an endemic plant from the mountainous regions of the Balkan Peninsula. In this study, we focused on an in-depth phytochemical analysis of S. scardica infusion using ultra-high-performance liquid chromatography hyphenated with high-resolution mass spectrometry (UHPLC–HRMS). Quantitative determination of the main secondary metabolites was carried out by UHPLC–HRMS analyses using the external standard method. The results revealed more than 100 metabolites, including five sugar acids and saccharides, 21 carboxylic, hydroxybenzoic, hydroxycinnamic acids, and derivatives, 15 acylquinic acids, 10 phenylpropanoid glycosides, four iridoid glycosides, 28 flavonoids, seven fatty acids, and four organosulfur compounds. Furthermore, a dereplication and fragmentation patterns of five caffeic acids oligomers and four acylhexaric acids was performed for the first time in S. scardica. Regarding the quantitative analysis, the phenylethanoid verbascoside (53) (151.54 ± 10.86 mg/g lyophilized infusion, li), the glycosides of isoscutellarein (78) (151.70 ± 14.78 mg/g li), methylisoscutelarein (82) (107.4 ± 9.07 mg/g li), and hypolaetin (79) (78.33 ± 3.29 mg/g li), as well as caffeic acid (20) (87.25 ± 6.54 mg/g li), were found to be the major compounds in S. scardica infusion. The performed state-of-the-art phytochemical analysis of S. scardica provides additional knowledge for the chemical constituents and usage of this valuable medicinal plant. [ABSTRACT FROM AUTHOR]

Thioureas and their derivatives are organosulfur compounds having excellent biological and non-biological applications. These compounds contain S- and N-, which are nucleophilic and allow for establishing inter-and intramolecular hydrogen bonding. These characteristics make thiourea moiety a very important chemosensor to detect various environmental pollutants. This article covers a broad range of thioureas and their derivatives that are used for highly sensitive, selective, and simple fluorimetric (turn-off and turn-on), and colorimetric chemosensors for the detection and determination of different types of anions, such as CN-, AcO-, F-, ClO- and citrate ions, etc., and neutral analytes such as ATP, DCP, and Amlodipine, etc., in biological, environmental, and agriculture samples. Further, the sensing performances of thioureas-based chemosensors have been compared and discussed, which could help the readers for the future design of organic fluorescent and colorimetric sensors to detect anions and neutral analytes. We hope this study will support the new thoughts to design highly efficient, selective, and sensitive chemosensors to detect different analytes in biological, environmental, and agricultural samples. [ABSTRACT FROM AUTHOR]

The Meloidogyne genus is widely recognized for its significant economic and scientific importance within the group of plant-parasitic nematodes. The chemical management of nematodes presents its challenges and heavily depends on employing soil fumigants containing toxic and costly nematicides. However, plant-derived essential oils offer promising alternatives, demonstrating a wide range of biological activities that affect nematodes through a range of mechanisms, including disrupting their nervous systems, inducing detrimental effects on plasma membrane permeability, penetrating the gelatinous matrix of nematode eggs, and disturbing intracellular redox status. Most of the extracted essential oils were predominantly sourced from the Lamiaceae family (32%), followed by Asteraceae (11%), Apiaceae (9%), and Poaceae (8%), and with genera Thymus, Mentha, Ocimum, Artemisia, Cymbopogon being the most common. The nematicidal activity of EOs primarily arises from their chemical groups, such as terpenes, phenylpropanoids, and organosulfur compounds. Among these, geraniol, carvacrol, limonene, eugenol, thymol, and pinene demonstrate the strongest nematicidal potential. The assessed EO efficacy was evaluated against 6 species belonging to the genus Meloidogyne. This review also provides knowledge of synergistic and antagonistic interactions of EO components. Synergistic interactions were identified between carvacrol and geraniol, as well as geraniol and eugenol, whereas binary combinations of carvacrol, γ-terpinene, and o-cymene exhibited reduced efficacy. Understanding how specific compounds interact can lead to the development of more potent and effective final products. [ABSTRACT FROM AUTHOR]

This article explores the field of organosulfur chemistry and its applications in various industries. The authors specifically discuss their research on aryne chemistry and its interaction with organosulfur compounds. They detail their efforts in developing synthetic methodologies using sulfonium zwitterions and the unique reactivities of the resulting S(IV) intermediates. The article highlights their recent achievements in sigmatropic rearrangement, ring-opening reactions of cyclic sulfides, and selective arylation of thio-oxindoles. The authors aim to advance zwitterion chemistry and expand its applications through selectivity control and diversity-oriented synthesis. [Extracted from the article]

The protection of carbonyl functional groups via dithioacetalization with thiols or dithiols plays a significant role in multi-step organic syntheses, such as natural products and drug synthesis. Therefore, dithioacetalization has always been cherished as one of the most important organic transformations in both academic and industrial research. Numerous synthetic strategies for the dithioacetalization of carbonyl compounds have been reported in the literature for the synthesis of industrially valuable organosulfur compounds or precursors like acyclic dithioacetals, dithiolanes, and dithianes. Regardless of having many conventional efficient synthetic protocols, greener approaches have been recognized as a viable alternative due to environmental and health concerns. Consequently, the growing trend of developing greener methods stimulated by the green chemistry concept for dithioacetalization is inevitable. The present review is aimed to highlight the recent advances in the greener and convenient synthetic approaches employed for the dithioacetalization of carbonyl compounds. [ABSTRACT FROM AUTHOR]

We herein report a protocol for the α‐thio‐ and α‐seleno‐cyanation of different cyclic β‐ketoesters and oxindoles by using NaSCN or KSeCN as easily accessible inorganic nucleophilic S(e)CN sources under oxidative conditions. Key to success for both transformations is the use of dibenzoylperoxide as an oxidant allowing for the coupling of two inherently nucleophilic species under operationally simple conditions in high yields and with broad functional group tolerance. [ABSTRACT FROM AUTHOR]

The mechanism of biological activity of various sulfur-containing compounds and sulfur fragments of both natural and synthetic origins is presented. Unique characteristics of organosulfur compounds that are present in natural plant products are considered to reveal the most efficient sulfur components of the natural origin. An insufficient efficiency of the pharmacological action of plant raw materials and undesirable effects indisputably confirm the topical character of research on the preparation of modified analogs of natural biologically active sulfur-containing compounds. The modern data on the development of new polytopic organosulfur compounds combining different redox-active functional groups in the structure, which should favor their efficiency and a decrease in side manifestations, are reviewed. Sulfur-containing metal complexes with antimicrobial, antiviral, and anticancer properties are among the most promising pharmacologically active compounds. In spite of the success achieved in this field of chemistry, the preparation of new target-oriented biodrugs based on bioessential metals (Cu, Zn, Se) and biomimetic organosulfur fragments remains to be an urgent problem. The developments in this direction should favor to understand mechanisms of the therapeutic action of new drugs and to prepare drugs of the new generation followed by their implementation in clinical practice. [ABSTRACT FROM AUTHOR]

Nowadays, organosulfur compounds provide new options in the development of full organic ion batteries. However, many drawbacks (such as kinetics limitations during the reversible oxidation of disulfides with cleavage of S–S bond, as well as solubility in non-aqueous electrolytes) make their commercialization difficult. Herein, a new concept for the design of organosulfur compounds with regulated redox properties and limited solubility is proposed. As a proof-of-concept, we designed peri-disulfo-substituted 1,8-naphthalimide derivatives, in which the alkyl chain length and halogen substituents (Cl or Br) at positions 3 and 6 are varied. The compounds were synthesized by an originally developed procedure starting from tetrahalonaphthalic anhydride via nucleophilic substitution at both peri-positions in the respective imide. Using ionic liquid electrolyte, it was found that the new peri-dithiolo-1,8-naphthalimides can participate in n- and p-type redox reactions at about 2.0 V and above 4.0 V vs. Li/Li+, respectively. The redox potentials are sensitive mainly to whether Cl or Br substituents are available in the molecule architecture, while the alkyl chain length determines the kinetics of the redox reactions. Among all compounds, the chloro-substituted compound with the shorter alkyl chain displays the best kinetics for both low- and high-voltage redox reactions. [ABSTRACT FROM AUTHOR]

The organic compound imidazole has the chemical formula C3N2H4. Numerous significant biological compounds contain imidazole. The amino acid histidine is the most prevalent. The substituted imidazole derivatives have great potential for treating a variety of systemic fungi infections. Thiourea is an organosulfur compound with the formula SC(NH2)2. It is a reagent in organic synthesis. In this paper, some new imidazole and thiourea derivatives are synthesized, characterized, and studied for their biological activity. These new compounds were synthesized from the starting material terephthalic acid, which was transformed to corresponding ester [I] by the refluxing of diacid with methanol in the presence of H2SO4 as a catalyst, compound [I] condensation with hydrazine hydrate 80% to yielded acid hydrazide [II], which was refluxed with 2 moles of various aromatic aldehydes in the presence of few drops of glacial acetic acid as a catalyst to yielded Schiff bases [IIIa-d]. Refluxing of chosen derivative [IIIa-d] with acetyl chloride in dry benzene gave new acetyl compounds [IVa-a] which were reacted with thiourea and anhydrous sodium carbonate with acetone as a solvent to give new thiourea derivatives [Va-d]. Compounds [Va-d] were used to synthesize new imidazole derivatives [VIa-d] by the reaction of appropriate compound [Va-d] with 2 moles of benzoin in dry DMF under cyclization reaction. FTIR, HNMR, and mass spectroscopy are used to characterize the synthesized compounds. [ABSTRACT FROM AUTHOR]

Sulfur‐centered radicals have a key role in a plethora of synthetic organic transformations, whose scope has been further expanded thanks to the possibility to generate such species under visible light photocatalytic conditions. This review focuses on those transformations involving isocyanides and sulfur‐centered radicals with the aim to highlight the chemical space accessible, both in terms of complexity and diversity, and the mechanistic rational underpinning the current and future development of such chemical methodologies. [ABSTRACT FROM AUTHOR]

Aims: Sugarcane plants infected with Leifsonia xyli subsp. xyli (Lxx) have their primary metabolism affected with decreased levels of sugars and amino acids. Cysteine and methionine are sulfur-containing essential amino acids used for bacterial growth and the Lxx titer in sugar cane leaves could affect the animo acid concentrations. The goal of this study was to evaluate how the increase in Lxx titer affects the nutritional status and sulfur metabolism in sugar cane leaves. Methods: Susceptible sugar cane (Saccharum officinarum) genotype: CB49260 was used in this study with low (256 cells) and high (2090 cells) Lxx titers and macronutrients and primary metabolites assessed from leaves and culms. Results: Plants with high Lxx titers accumulated more biomass in the main culm, leaves, and shoots than plants with low Lxx titers. Additionally, plants with high Lxx titers had 26% more sulfur content in leaves than plants with low Lxx titers. Higher levels of sulfate, sucrose, maltose, raffinose, shikimic acid, malate, putrescine, glycerol, and, erythritol were also present in plants with high Lxx titers; but decreased levels of methionine and glutathione in leaves. In the culm, plants with high Lxx titers also had increased levels of maltose; but decreased levels of threonine, ornithine, phenylalanine and myo-inositol when compared with plants with low Lxx titers. Conclusions: This study demonstrated that high bacterial titers increase sulfur demand in sugar cane; however, the increased S content in the leaf did not result in higher sulfur assimilation, verified by increased sulfate but decreased methionine and glutathione levels. Therefore, our study showed that lower methionine availability, and methionine catabolism to putrescine in the leaves may fail to meet the increased sulfur organic compound demand of Lxx. The decrease in glutathione biosynthesis may reflect impaired biosynthesis or a drain on this antioxidant resulting from oxidative stresss by pathogenesis of Lxx. [ABSTRACT FROM AUTHOR]

The addition of heteroatom compounds to alkynes and alkenes is an atom‐efficient method of carbon‐heteroatom bond formation and is widely used as a fundamental synthetic method for the construction of functional molecules. Nevertheless, examples of transition‐metal‐catalyzed addition reactions of group 16 heteroatom compounds to carbon‐carbon unsaturated bonds have been limited due to the widespread belief that organic sulfur and selenium compounds are representative catalyst poisons. In recent decades, however, several seminal catalytic reactions of sulfur compounds have been developed, providing important insights into catalysis and poisons. Therefore, this paper focuses on the transition‐metal‐catalyzed addition of organosulfur compounds to alkynes and alkenes, gains comprehensive insights into the catalysis and catalyst poisons, and proposes concepts for the development of transition‐metal‐catalyzed reactions of group 16 heteroatom compounds. [ABSTRACT FROM AUTHOR]

Volatile organic compound (VOC) emissions and subsequent oxidation contribute to the formation of secondary pollutants and poor air quality in general. As more VOCs at lower mixing ratios have become the target of air quality investigations, their quantification has been aided by technological advancements in proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOF-MS). However, such quantification requires appropriate instrument background measurements and calibrations, particularly for VOCs without calibration standards. This study utilized a Vocus PTR-TOF-MS coupled with a gas chromatograph for real-time and speciated measurements of ambient VOCs in Boulder, Colorado, during spring 2021. The aim of these measurements was to understand and characterize instrument response and temporal variability as to inform the quantification of a broader range of detected VOCs. Fast, frequent calibrations were made every 2 h in addition to daily multipoint calibrations. Sensitivities derived from the fast calibrations were 5 ± 6 % (average and 1 standard deviation) lower than those derived from the multipoint calibrations due to an offset between the calibrations and instrument background measurement. This offset was caused, in part, by incomplete mixing of the standard with diluent. These fast calibrations were used in place of a normalization correction to account for variability in instrument response and accounted for non-constant reactor conditions caused by a gradual obstruction of the sample inlet. One symptom of these non-constant conditions was a trend in fragmentation, although the greatest observed variability was 6 % (1 relative standard deviation) for isoprene. A PTR Data Toolkit (PTR-DT) was developed to assess instrument performance and rapidly estimate the sensitivities of VOCs which could not be directly calibrated on the timescale of the fast calibrations using the measured sensitivities of standards, molecular properties, and simple reaction kinetics. Through this toolkit, the standards' sensitivities were recreated within 1 ± 8 % of the measured values. Three clean-air sources were compared: a hydrocarbon trap, zero-grade air and ultra-high purity nitrogen, and a catalytic zero-air generator. The catalytic zero-air generator yielded the lowest instrument background signals for the majority of ions, followed by the hydrocarbon trap. Depending on the ionization efficiency, product ion fragmentation, ion transmission, and instrument background, standards' limits of detection (5 s measurement integration) derived from the catalytic zero-air generator and the fast calibration sensitivities ranged from 2 ppbv (methanol) to 1 pptv (decamethylcyclopentasiloxane; D5 siloxane) with most standards having detection limits below 20 pptv. Finally, applications of measurements with low detection limits are considered for a few low-signal species including sub-parts-per-trillion by volume (pptv) enhancements of icosanal (and isomers; 1 min average) in a plume of cooking emissions, and sub-parts-per-trillion by volume enhancements in dimethyl disulfide in plumes containing other organosulfur compounds. Additionally, chromatograms of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane (D3, D4, and D5 siloxanes, respectively), combined with high sensitivity, suggest that online measurements can reasonably be associated with the individual isomers. [ABSTRACT FROM AUTHOR]

The synthesis of organosulfur compounds gained specific interest in the interference of organic chemistry and chemical biology. Copper chlorophyllin (CC) is a bio‐based copper complex that facilitates the synthesis of organosulfur compounds through the thioetherification reaction. The current paper deals with the immobilization of CC on the ZrO2 nanoparticles (CC@ZrO2) and its application in the one‐pot thioetherification of alkyl and aryl halides using thiourea, an alternative to the bad‐smelling thiols. After the characterization of CC@ZrO2 with different analytical techniques such as FT‐IR, TGA, XPS, N2 adsorption/desorption, XRD, ICP, and FESEM, the catalytic activity of the prepared CC@ZrO2 was evaluated in the synthesis of different types of thioether derivatives. Good to excellent yields, high reusability, and reproducibility made this cost‐effective approach a benchmark in C–S cross‐coupling reactions. [ABSTRACT FROM AUTHOR]

The global sulphur cycle has implications for human health, climate change, biogeochemistry and bioremediation. The organosulphur compounds that participate in this cycle not only represent a vast reservoir of sulphur but are also used by prokaryotes as sources of energy and/or carbon. Closely linked to the inorganic sulphur cycle, it involves the interaction of prokaryotes, eukaryotes and chemical processes. However, ecological and evolutionary studies of the conversion of organic sulphur compounds are hampered by the poor conservation of the relevant pathways and their variation even within strains of the same species. In addition, several proteins involved in the conversion of sulphonated compounds are related to proteins involved in sulphur dissimilation or turnover of other compounds. Therefore, the enzymes involved in the metabolism of organic sulphur compounds are usually not correctly annotated in public databases. To address this challenge, we have developed HMSS2, a profiled Hidden Markov Model‐based tool for rapid annotation and synteny analysis of organic and inorganic sulphur cycle proteins in prokaryotic genomes. Compared to its previous version (HMS‐S‐S), HMSS2 includes several new features. HMM‐based annotation is now supported by nonhomology criteria and covers the metabolic pathways of important organosulphur compounds, including dimethylsulphoniopropionate, taurine, isethionate, and sulphoquinovose. In addition, the calculation speed has been increased by a factor of four and the available output formats have been extended to include iTol compatible data sets, and customized sequence FASTA files. [ABSTRACT FROM AUTHOR]

Various organosulfur compounds, such as dimethyl trisulfide (DMTS), display anti-inflammatory properties. We aimed to examine the effects of DMTS on acute pancreatitis (AP) and its mechanism of action in both in vivo and in vitro studies. AP was induced in FVB/n mice or Wistar rats by caerulein, ethanol-palmitoleic acid, or L-ornithine-HCl. DMTS treatments were administered subcutaneously. AP severity was assessed by pancreatic histological scoring, pancreatic water content, and myeloperoxidase activity measurements. The behaviour of animals was followed. Pancreatic heat shock protein 72 (HSP72) expression, sulfide, and protein persulfidation were measured. In vitro acinar viability, intracellular Ca2+ concentration, and reactive oxygen species production were determined. DMTS dose-dependently decreased the severity of AP. It declined the pancreatic infiltration of leukocytes and cellular damage in mice. DMTS upregulated the HSP72 expression during AP and elevated serum sulfide and low molecular weight persulfide levels. DMTS exhibited cytoprotection against hydrogen peroxide and AP-inducing agents. It has antioxidant properties and modulates physiological but not pathophysiological Ca2+ signalling. Generally, DMTS ameliorated AP severity and protected pancreatic acinar cells. Our findings indicate that DMTS is a sulfur donor with anti-inflammatory and antioxidant effects, and organosulfur compounds require further investigation into this potentially lethal disease. [ABSTRACT FROM AUTHOR]

N‐Heteroaryl sulfonamides are an extremely significant variety of organosulfur compounds that are present in many significant FDA‐approved drugs and therapeutic agents. Therefore, synthesis of these N‐heteroaryl sulfonamides is one of the most interesting topics among the synthetic organic chemists. Among the various synthetic methodologies, direct C−N bond formation through N‐heteroarylation of sulfonamides has emerged as a procedure continued of choice as it bypasses the genotoxicity common in the traditional methods. This review encompasses and summarizes the progress and development in this subject with literature coverage up to June 2023. [ABSTRACT FROM AUTHOR]

First, the iodide anion is oxidized to molecular iodine at the anode, and then sulfonyl hydrazides B 13 b are utilized to generate sulfonyl radicals B I b for subsequent reactions. A possible reaction mechanism was proposed in which oxidation of the starting materials by bromine species (molecular bromine, hypobromite, bromate, perbromate and tribromide anions), generated by the anodic oxidation of the bromine anion, produced radical intermediates, the coupling of which led to the final products. Keywords: organosulfur compounds; electrosynthesis; halogen-mediated; eco-friendly; sulfonyl compounds; organic thiocyanates EN organosulfur compounds electrosynthesis halogen-mediated eco-friendly sulfonyl compounds organic thiocyanates 2799 2816 18 08/31/23 20230915 NES 230915 Graph 1 Introduction The significant influence of sulfur atoms on the electronic and physical properties of organic compounds has led to the widespread occurrence of sulfur functional groups in natural products, pharmaceuticals, and other biologically active compounds. The sulfonyl radical B I b is obtained by the oxidation of B 37a b with the iodine species obtained by oxidation of iodide at the anode. [Extracted from the article]

Polystyrene (PS) is one of the least recycled large‐volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of "degradation‐upcycling" to synthesize a library of high‐value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value‐added chemicals. [ABSTRACT FROM AUTHOR]

Polystyrene (PS) is one of the least recycled large‐volume commodity plastics due to bulkiness of foam products and associated contaminants. PS recycling is also severely hampered by the lack of financial incentive, limited versatility, and poor selectivity of existing methods. To this end, herein we report a thermochemical recycling strategy of "degradation‐upcycling" to synthesize a library of high‐value aromatic chemicals from PS wastes with high versatility and selectivity. Two cascade reactions are selected to first degrade PS to benzene under mild temperatures, followed by the derivatization thereof utilizing a variety of acyl/alkyl and sulfinyl chloride additives. To demonstrate the versatility, nine ketones and sulfides of cosmetic and pharmaceutical relevance were prepared, including propiophenone, benzophenone, and diphenyl sulfide. The approach is also amenable to sophisticated upcycling reaction designs and can produce desired products stepwise. The facile and versatile approach will provide a scalable and profitable methodology for upcycling PS waste into value‐added chemicals. [ABSTRACT FROM AUTHOR]