Methyl Sulfone Research Articles

Comparative Study of High Voltage Spinel∥Lithium Titanate Lithium‐ion Batteries in Ethylene Carbonate Free Electrolytes

AbstractA persistent obstacle towards the realization of high voltage cathodes is electrolyte instability where oxidation and transition metal dissolution manifest in rapid capacity failure with both issues connected to the presence of ethylene carbonate in the electrolyte. Here, alternative electrolyte co‐solvents are investigated and compared, where the cyclic carbonate is replaced with sulfones ethyl methyl sulfone (EMS) and tetra methylene sulfone (TMS) and fluoroethylene carbonate (FEC). The best full cell performance was observed for cells cycled in a FEC/EMC (3/7) and FEC/EMC (1/1) electrolytes which exhibited 84–85 % capacity retention after 500 cycles. TMS/EMC (3/7), was determined to be the best performing sulfone electrolyte and maintained 71 % capacity after 500 cycles. Post‐mortem XPS analysis indicated different film forming mechanisms for the respective co‐solvent. A thicker cathode electrolyte interphase (CEI) on the LNMO was observed for the FEC containing electrolytes (relative to when TMS was used as the co‐solvent) indicating more effective passivation of the reactive cathode surface which correlated well with the enhanced cycling stability observed. For LTO, more evidence of transition metal migration and a thicker solid electrolyte interphase (SEI) layer was observed for the sulfone electrolyte suggesting more parasitic anode‐electrolyte interactions and an inability to mitigate Mn2+/Ni2+ crosstalk.

Nonsolvating Fluoroaromatic Cosolvent Enabled Long-Term Cycling of High-Voltage Lithium-Ion Batteries with Organosulfur Electrolytes.

The structure-activity relationships of nonsolvating cosolvents for organosulfur-based electrolyte systems were revealed. The performance of nonsolvating dilutant fluorobenzene (FB) was compared to various fluorinated ether dilutants in high-voltage electrolytes containing a concentration of 1.2 M LiPF6 dissolved in fluoroethylene carbonate (FEC), ethyl methyl sulfone (EMS), and the dilutant. In a high-voltage and high-loading LiNi0.8Mn0.1Co0.1O2 (NMC811) full cell configuration, the organosulfur-based electrolyte containing FB dilutant enabled superior electrochemical performance compared to the electrolytes using other nonsolvating fluorinated ether formulations. Moreover, the FB-containing electrolyte exhibited the highest ionic conductivity and lowest viscosity among all organosulfur-based electrolytes containing nonsolvating dilutant. These improvements are attributed to the enhanced physical properties of electrolyte and lithium-ion mobility. Furthermore, by employing first-principles simulations, the observed suppression of side reactions at high voltage is linked to FB's lower reactivity toward singlet dioxygen, which is likely produced at the NMC interface. Overall, FB is considered an excellent diluent that does not impede cell operation by mass decomposition at the cathode.

Constructing stable electrode–electrolyte interfaces by sulfone-based additive to improve the high-voltage performance of LiCoO2

LiCoO2 battery can provide high reversible capacity at a high voltage of 4.6 V, however, maintaining its stability at high voltages remains a major challenge. To address this issue, ethyl methyl sulfone (EMS) is employed as an electrolyte additive to construct stable interfaces between the electrode and electrolyte under high-voltage condition. The characterization results indicate that the addition of EMS can inhibit the decomposition of the standard electrolyte (STD) and the dissolution of Co2+ from cathode, as well as the formation of lithium dendrites on the Li anode, thereby enhancing the stability of both cathode/electrolyte and anode/electrolyte interfaces. Consequently, the cycling performance of LiCoO2 battery using STD+3 %EMS is augmented by 16.9 % at 1 C under a cut-off voltage of 4.6 V over 100 cycles, delivering a specific capacity of 137 mA h g−1. This research provides novel insights into the design of electrolyte additives for high-voltage LiCoO2 batteries and contributes to the further development of high-voltage lithium-ion batteries.

Nickel‐Catalyzed Microwave‐Mediated Methylsulfonylation of Alkyl Halides

AbstractThe direct nickel‐catalyzed methylsulfonylation of alkyl and aryl halides using dimethyl sulfite as the sulfur dioxide surrogate as well as the source of methyl has been achieved. This protocol provides a robust method for the synthesis of methyl sulfone derivatives under microwave irradiation in moderate to excellent yields within 60 minutes and shows excellent functional group tolerance.

A point mutation in the meiotic crossover formation gene HEI10/TFS2 leads to thermosensitive genic sterility in rice.

Thermosensitive genic female sterility (TGFS) is a promising property to be utilized for hybrid breeding. Here, we identified a rice TGFS line, tfs2, through an ethyl methyl sulfone (EMS) mutagenesis strategy. This line showed sterility under high temperature and became fertile under low temperature. Few seeds were produced when the tfs2 stigma was pollinated, indicating that tfs2 is female sterile. Gene cloning and genetic complementation showed that a point mutation from leucine to phenylalanine in HEI10 (HEI10tfs2), a crossover formation protein, caused the TGFS trait of tfs2. Under high temperature, abnormal univalents were formed, and the chromosomes were unequally segregated during meiosis, similar to the reported meiotic defects in oshei10. Under low temperature, the number of univalents was largely reduced, and the chromosomes segregated equally, suggesting that crossover formation was restored in tfs2. Yeast two-hybrid assays showed that HEI10 interacted with two putative protein degradation-related proteins, RPT4 and SRFP1. Through transient expression in tobacco leaves, HEI10 were found to spontaneously aggregate into dot-like foci in the nucleus under high temperature, but HEI10tfs2 failed to aggregate. In contrast, low temperature promoted HEI10tfs2 aggregation. This result suggests that protein aggregation at the crossover position contributes to the fertility restoration of tfs2 under low temperature. In addition, RPT4 and SRFP1 also aggregated into dot-like foci, and these aggregations depend on the presence of HEI10. These findings reveal a novel mechanism of fertility restoration and facilitate further understanding of HEI10 in meiotic crossover formation.

Covalent functionalization by using blue light activated radicals: on the reaction mechanisms of arylazo sulfone binding on graphene.

Covalent functionalization of graphene presents a pivotal strategy to enhance its surface properties and overcome inherent chemical inertness. While diazonium salts have been extensively utilized for this purpose, their limitations necessitate exploration of alternative approaches. Arylazo sulfones, such as diazonium salt derivatives serving as chromophores, offer a promising solution, enabling photochemical reactions under visible light. Here, we propose a novel method for rapid covalent photofunctionalization of chemical vapor deposition (CVD) graphene on copper substrates using arylazo sulfones. The generation of aryl radicals - chlorobenzene in this case - was achieved through blue light LED irradiation of 4-chlorophenylazo methyl sulfone solution in acetonitrile. Efficient surface covalent modification of graphene was verified by observing (i) the photogeneration of radicals with a decrease in the π-π* band absorbance and an increase in the n-π* of arylazosulfone solution by UV-Vis spectroscopy; (ii) an increase in C sp3 defects on graphene from the Raman D band, the Auger C KLL signal and graphene C 1s X-ray photoelectron spectroscopy (XPS); and (iii) the presence of the chlorobenzene XPS Cl 2p signal. The aryl radical generation was enhanced by the copper substrate during irradiation, with a possible double path reaction mechanism. This approach highlights the versatility of arylazo sulfones in covalently patterning graphene surfaces, thus unlocking opportunities by overcoming the current approach consisting of the deposition of resist materials with successive cycles of lithography and electrochemistry.

Diallyl trisulfide and its active metabolite allyl methyl sulfone attenuate cisplatin-induced nephrotoxicity by inhibiting the ROS/MAPK/NF-κB pathway

Cisplatin, a chemotherapy medication employed in the treatment of various solid tumors, is constrained in its clinical application due to nephrotoxicity. Diallyl trisulfide (DATS), a compound derived from garlic that possessed anticancer and antioxidant properties, can be combined with cisplatin without hindering its antitumor effects. The present investigation examined the defensive properties of DATS and its active metabolites against renal dysfunction caused by cisplatin. We created a mouse model to study renal injury caused by cisplatin and assessed kidney histology, immunochemistry, and serum cytokines. DATS treatment effectively reduced the pathological changes caused by cisplatin by decreasing the levels of renal function markers BUN, CRE, cystatin C, NGAL, inflammatory factors TNF-α, IL-6, and the protein expression of α-SMA, NF-κB, KIM-1. A pharmacokinetic evaluation of DATS found that allyl methyl sulfone (AMSO2) was the most abundant and persistent metabolite of DATS in vivo. Then, we examined the impact of AMSO2 on cell viability, apoptosis, ROS generation, and MAPK/NF-κB pathways in HK-2 cells treated with cisplatin. Cotreatment with AMSO2 effectively hindered the HK-2 cells alterations induced by cisplatin. Furthermore, AMSO2 mitigated oxidative stress through the modulation of MAPK and NF-κB pathways. Our findings indicated that DATS and its active derivative AMSO2 attenuated cisplatin-induced nephrotoxicity. DATS shows potential as a viable treatment for nephrotoxicity caused by cisplatin.

Synthesis of [28-13C]-24-methylenecholesterol using 1-tert-butyl-1H-tetrazol-5-yl [13C]-methyl sulfone to methylenate an isopropyl ketone intermediate

Synthesis of [28-13C]-24-methylenecholesterol using 1-tert-butyl-1H-tetrazol-5-yl [13C]-methyl sulfone to methylenate an isopropyl ketone intermediate

QUANTUM CHEMICAL CALCULATION OF STRUCTURAL AND THERMODYNAMIC PROPERTIES OF ETHYL METHYL SULFONE IN THE GAS PHASE

A detailed conformational analysis of ethyl methyl sulfone has been carried out using quantum chemical approaches, by revealing all stable conformers, their energy, structural parameters, relative population, and IR spectra at different levels of theory. Thermochemical parameters, such as energy, entropy and heat capacity of ethyl methyl sulfone stable conformers in the gas phase were calculated directly using the wB97XD/6-311++G(2df, 2pd) density functional theory method. Some correlation has been established between the structural characteristics of various conformers and their thermodynamic properties.

Synthesis of 3-Functionalized 4-Quinolones from Readily Available Anthranilic Acids.

We report herein an efficient synthesis of 3-functionalized 4-quinolones, a class of privileged pharmacophores found in numerous biologically and pharmaceutically active compounds. Our synthetic strategy features a telescoped two-step sequence starting from readily available anthranilic acids and functionalized methane derivatives bearing an electron-withdrawing group, such as methyl sulfones, methyl ketones, and acetonitrile. The method delivers good to excellent yields for a variety of structurally diverse substrates, showing good functional group tolerability. We believe that the disclosed method offers a highly efficient and practical entry to functionalized 4-quinolones under mild conditions that is amenable to preparative-scale synthesis.

Continuous-Flow Synthesis of Methyl Sulfone with Microchannel Reactors: A Safer and Efficient Production Strategy

Continuous-Flow Synthesis of Methyl Sulfone with Microchannel Reactors: A Safer and Efficient Production Strategy

Oxidation State Tuning of Room Temperature Phosphorescence and Delayed Fluorescence in Phenothiazine and Phenothiazine-5,5-dioxide Dimers.

Heterocyclic dimers consisting of combinations of butterfly-shaped phenothiazine (PTZ) and its chemically oxidized form phenothiazine-5,5-dioxide (PTZ(SO2 )) have been synthesized. A twist is imposed across the dimers by ortho-substituents including methyl ethers, sulfides and sulfones. X-ray crystallography, cyclic voltammetry and optical spectroscopy, underpinned by computational studies, have been employed to study the interplay between the oxidation state, conformational restriction, and emission mechanisms including thermally activated delayed fluorescence (TADF) and room temperature phosphorescence (RTP). While the PTZ(SO2 ) dimers are simple fluorophores, the presence of PTZ induces triplet-mediated emission with a mixed PTZ-PTZ(SO2 ) dimer displaying concentration dependent hallmarks of both TADF and RTP.

Reaction of FeaqII with Peroxymonosulfate and Peroxydisulfate in the Presence of Bicarbonate: Formation of FeaqIV and Carbonate Radical Anions.

Many advanced oxidation processes (AOPs) use Fenton-like reactions to degrade organic pollutants by activating peroxymonosulfate (HSO5-, PMS) or peroxydisulfate (S2O82-, PDS) with Fe(H2O)62+ (FeaqII). This paper presents results on the kinetics and mechanisms of reactions between FeaqII and PMS or PDS in the absence and presence of bicarbonate (HCO3-) at different pH. In the absence of HCO3-, FeaqIV, rather than the commonly assumed SO4•-, is the dominant oxidizing species. Multianalytical methods verified the selective conversion of dimethyl sulfoxide (DMSO) and phenyl methyl sulfoxide (PMSO) to dimethyl sulfone (DMSO2) and phenyl methyl sulfone (PMSO2), respectively, confirming the generation of FeaqIV by the FeaqII-PMS/PDS systems without HCO3-. Significantly, in the presence of environmentally relevant concentrations of HCO3-, a carbonate radical anion (CO3•-) becomes the dominant reactive species as confirmed by the electron paramagnetic resonance (EPR) analysis. The new findings suggest that the mechanisms of the persulfate-based Fenton-like reactions in natural environments might differ remarkably from those obtained in ideal conditions. Using sulfonamide antibiotics (sulfamethoxazole (SMX) and sulfadimethoxine (SDM)) as model contaminants, our study further demonstrated the different reactivities of FeaqIV and CO3•- in the FeaqII-PMS/PDS systems. The results shed significant light on advancing the persulfate-based AOPs to oxidize pollutants in natural water.

Phase Behaviors and Ion Transport Properties of LiN(SO<sub>2</sub>CF<sub>3</sub>)<sub>2</sub>/Sulfone Binary Mixtures

Highly concentrated Li salt/aprotic solvent solutions are promising electrolytes for next-generation batteries. Understanding the Li+ ion transport process is crucial for designing novel battery electrolytes. In this study, we systematically investigated the phase behavior, solvate structures, and Li+ transport properties of binary mixtures comprising lithium bis(trifluoromethanesulfonyl)amide (LiTFSA) and various sulfones, such as sulfolane (SL), 3-methyl sulfolane (MSL), dimethyl sulfone (DMS), ethyl methyl sulfone (EMS), and ethyl isopropyl sulfone (EiPS). Except for the MSL system, the [LiTFSA]/[sulfone] = 1/2 mixtures remained in a liquid state at room temperature, thus enabling a systematic comparison of the Li+ transport properties in the highly concentrated electrolytes. In highly concentrated liquid electrolytes, Li+ ions diffuse by exchanging ligands (sulfone and TFSA). Li+ ions diffuse faster than TFSA in all electrolytes except the EiPS-based electrolyte at a composition of [LiTFSA]/[sulfone] = 1/2, resulting in high Li+ transference numbers. SL-based electrolytes show higher ionic conductivity and Li+ transference numbers than other sulfone-based electrolytes. Consequently, sulfone solvents with compact molecular sizes and low energy barriers of conformational change are favorable for enhancing the Li+ ion transport in the electrolytes.

General Strategy To Improve the Photon Budget of Thiol-Conjugated Cyanine Dyes.

Maleimide-cysteine chemistry has been a routine practice for the site-specific labeling of fluorophores to proteins since the 1950s. This approach, however, cannot bring out the best photon budget of fluorophores. Here, we systematically measured the Cyanine3/5 dye conjugates via maleimide-thiol and amide linkages by counting the total emitted photons at the single-molecule level. While brightness and signal-to-noise ratios do not change significantly, dyes with thioether linkages exhibit more severe photobleaching than amide linkers. We then screened modern arylation-type bioconjugation strategies to alleviate this damage. Labeling thiols with phenyloxadiazole (POD) methyl sulfone, p-chloronitrobenzene, and fluorobenzene probes gave rise to electron-deficient aryl thioethers, effectively increasing the total emitted photons by 1.5-3 fold. Among the linkers, POD maintains labeling efficiency and specificity that are comparable to maleimide. Such an increase has proved to be universal among bulk and single-molecule assays, with or without triplet-state quenchers and oxygen scavengers, and on conformationally unrestricted or restricted cyanines. We demonstrated that cyanine-POD conjugates are general and superior fluorophores for thiol labeling in single-molecule FRET measurements of biomolecular conformational dynamics and in two-color STED nanoscopy using site-selectively labeled nanobodies. This work sheds light on the photobleaching mechanism of cyanines under single-molecule imaging while highlighting the interplay between the protein microenvironment, bioconjugation chemistry, and fluorophore photochemistry.

High-concentration LiPF6/sulfone electrolytes: structure, transport properties, and battery application.

Non-flammable and oxidatively stable sulfones are promising electrolyte solvents for thermally stable high-voltage Li batteries. In addition, sulfolane-based high-concentration electrolytes (HCEs) show high Li+ ion transference numbers. However, LiPF6 has not yet been investigated as the main salt in sulfone-based HCEs for Li batteries. In this study, we investigated the phase behaviors, solvate structures, and transport properties of binary and ternary mixtures of LiPF6 and the following sulfone solvents: sulfolane (SL), dimethyl sulfone (DMS), ethyl methyl sulfone (EMS), and 3-methyl sulfolane (MSL). The stable crystalline solvates Li(SL)4PF6 and Li(DMS)2.5PF6 with high melting points were formed in the LiPF6/SL and LiPF6/DMS mixtures, respectively. In contrast, LiPF6/EMS, LiPF6/MSL, and LiPF6/SL/another sulfone mixtures remained liquids over a wide temperature range. Raman spectroscopy revealed that SL and another sulfone are competitively coordinated to Li+ ions to dissociate LiPF6 in the ternary mixtures. Although the ionic conductivity decreased with increasing LiPF6 concentration due to an increase in viscosity, Li+ ions diffused faster than PF6-via exchanging ligands in the HCE [LiPF6]/[SL]/[DMS] = 1/2/2, resulting in a higher Li ion transference number than that in conventional Li battery electrolytes.

Fluorophenyl methyl sulfone as an interface modifier for Ni-rich cathode materials of lithium-ion batteries

Nickel-rich lithium layered oxides are considered as the most addressing advanced cathode material for lithium-ion batteries, however, its low cycling performance at high temperature is considered the main bottleneck in expanding application areas. To improve poor surface stability of advanced cathode materials, fluorophenyl methyl sulfone is suggested as a surface modifier, which can make stable cathode-electrolyte interphases on the cathode via simple electrochemical oxidation. Electrochemical voltage spectroscopy indicates that the cell cycled with fluorophenyl methyl sulfone exhibits a higher amount of oxidation peaks corresponded to the formation of artificial interphases. In the cycling performance, the cell cycled with fluorophenyl methyl sulfone reveals improved cycling retention (81.7%) compared to that cycled with standard electrolyte (62.5%) at high temperature. Additional systematic analyses suggest that parasitic reaction associated with electrolyte decomposition is well suppressed in the cell controlled with fluorophenyl methyl sulfone because sulfone moiety of the additive participates to effective artificial interphases on the cathode.

Network Toxicology Guided Mechanism Study on the Association between Thyroid Function and Exposures to Polychlorinated Biphenyls Mixture.

Polychlorinated biphenyls (PCBs) are persistent and highly toxic pollutants, which can accumulate in organisms and produce toxic effects, especially damaging the function of thyroid hormones. So far, the molecular mechanism of PCBs mixture and their metabolites interfering with thyroid hormones has not been studied thoroughly except for individual compounds. In this study, PubMed, Web of Science, and STITCH databases were used to search PCBs and their corresponding target proteins. The intersection of PCBs and thyroid hormone dysfunction target proteins was obtained from GeneCards. The “compounds-targets-pathways” network was constructed by Cytoscape software. And KEGG and Go analyses were performed for key targets. Finally, molecular docking was used to verify the binding effect. Four major active components, five key targets, and 10 kernel pathways were successfully screened by constructing the network. Functional enrichment analysis showed that the interference was mediated by cancer, proteoglycans, PI3K-Akt, thyroid hormone, and FoxO signaling pathways. The molecular docking results showed that the binding energies were less than -5 kcal·mol−1. PCBs and their metabolites may act on the key targets of MAPK3, MAPK1, RXRA, PIK3R1, and TP53. The toxic effect of sulfated and methyl sulfone PCBs is greater. The method of screening targets based on the simultaneous action of multiple PCBs can provide a reference for other research. The targets were not found in previous metabolite toxicity studies. It also provides a bridge for the toxic effects and experimental research of PCBs and their metabolites in the future.

Genetic mapping and physiological analysis of chlorophyll-deficient mutant in Brassica napus L

BackgroundLeaf color mutants have reduced photosynthetic efficiency, which has severely negative impacts on crop growth and economic product yield. There are different chlorophyll mutants in Arabidopsis and crops that can be used for genetic control and molecular mechanism studies of chlorophyll biosynthesis, chloroplast development and photoefficiency. Chlorophyll mutants in Brassica napus are mostly used for mapping and location research but are rarely used for physiological research. The chlorophyll-deficient mutant in this experiment were both genetically mapped and physiologically analyzed.ResultsIn this study, yellow leaf mutant of Brassica napus L. mutated by ethyl methyl sulfone (EMS) had significantly lower chlorophyll a, b and carotenoid contents than the wild type, and the net photosynthetic efficiency, stomatal conductance and transpiration rate were all significantly reduced. The mutant had sparse chloroplast distribution and weak autofluorescence. The granule stacks were reduced, and the shape was extremely irregular, with more broken stromal lamella. Transcriptome data analysis enriched the differentially expressed genes mainly in phenylpropane and sugar metabolism. The mutant was mapped to a 2.72 Mb region on A01 by using BSA-Seq, and the region was validated by SSR markers.ConclusionsThe mutant chlorophyll content and photosynthetic efficiency were significantly reduced compared with those of the wild type. Abnormal chloroplasts and thylakoids less connected to the stroma lamella appeared in the mutant. This work on the mutant will facilitate the process of cloning the BnaA01.cd gene and provide more genetic and physiological information concerning chloroplast development in Brassica napus.

One-Pot Synthesis of Strain-Release Reagents from Methyl Sulfones.

Sulfone-substituted bicyclo[1.1.0]butanes and housanes have found widespread application in organic synthesis due to their bench stability and high reactivity in strain-releasing processes in the presence of nucleophiles or radical species. Despite their increasing utility, their preparation typically requires multiple steps in low overall yield. In this work, we report an expedient and general one-pot procedure for the synthesis of 1-sulfonylbicyclo[1.1.0]butanes from readily available methyl sulfones and inexpensive epichlorohydrin via the dialkylmagnesium-mediated formation of 3-sulfonylcyclobutanol intermediates. Furthermore, the process was extended to the formation of 1-sulfonylbicyclo[2.1.0]pentane (housane) analogues when 4-chloro-1,2-epoxybutane was used as the electrophile instead of epichlorohydrin. Both procedures could be applied on a gram scale with similar efficiency and are shown to be fully stereospecific in the case of housanes when an enantiopure epoxide was employed, leading to a streamlined access to highly valuable optically active strain-release reagents.