The N-H methylsulfoxidation of sulfoximines using DMso as a methylsulfinyl source,induced by electrochemistry,has been developed.This method is the first example of an electrochemical reaction in which DMso serves as ...The N-H methylsulfoxidation of sulfoximines using DMso as a methylsulfinyl source,induced by electrochemistry,has been developed.This method is the first example of an electrochemical reaction in which DMso serves as a methylsulfinyl source.Unlike previous electrochemical reactions involving DMsO as a substrate,which exclusively proceed via radical mechanisms,this reaction follows an S-cation pathway.A wide range of N-methylsulfinyl sulfoximines were successfully obtained.展开更多
Sperm cryopreservation is an essential technique for male fertility preservation,especially in men who are undergoing medical treatment.Conventional cryopreservation methods face limitations such as oxidative stress,D...Sperm cryopreservation is an essential technique for male fertility preservation,especially in men who are undergoing medical treatment.Conventional cryopreservation methods face limitations such as oxidative stress,DNA fragmentation,and cytotoxicity associated with traditional cryoprotectants like dimethyl sulfoxide(DMSO).Recent breakthroughs have focused on improving post-thaw sperm viability with novel cryoprotectants and innovative freezing strategies.Prospective approaches include the use of amino acid-based cryoprotectants,deep eutectic solvents,and antioxidants that have been described to prevent oxidative damage and maintain DNA integrity.Vitrification,a high-speed freezing technique that prevents ice crystal formation,has demonstrated superior outcomes compared to conventional slow freezing.Moreover,the Direct Dropping Method,a cryoprotectant-free approach,has been introduced as a contamination-minimizing technique that preserves sperm functionality.Multiomics tools are also utilized to determine biomarkers for protocol optimization.Despite these advancements,cryoprotectant toxicity is a central challenge,emphasizing the necessity for safer agents.Future research must focus on long-term sperm functionality and individualized cryopreservation strategies to maximize reproductive outcomes.The current review highlights the challenges associated with sperm cryopreservation,explores innovative strategies and novel cryoprotectants,underscores the significance of maintaining DNA integrity,and proposes future research directions to improve fertility preservation outcomes.展开更多
N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-prop...N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(2+),which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.展开更多
Compared with organic electrolytes,aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features,showcasing unique advantages in supercapacitors.However,challenges remain fo...Compared with organic electrolytes,aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features,showcasing unique advantages in supercapacitors.However,challenges remain for low-salt aqueous electrolytes operating at high voltage and low temperature.Herein,we report a low-salt(0.87 m,m means mol kg^(-1))'salt in dimethyl sulfoxide/water'hybrid electrolyte with non-flammability via hybridizing aqueous electrolyte with an organic co-solvent of dimethyl sulfoxide(hydrogen bond acceptor).As a result,the 0.87 m hybrid electrolyte exhibits enhanced electrochemical stability,a freezing temperature below-50℃,and an outstanding ionic conductivity of 0.52mS cm~(-1)at-50℃.Dimethyl sulfoxide can anchor water molecules through intermolecular hydrogen bond interaction,effectively reinforcing the stability of water in the hybrid electrolyte.Furthermore,the interaction between dimethyl sulfoxide and water molecules diminishes the involvement of water in the generation of ordered ice crystals,finally facilitating the low-temperature performance of the hybrid electrolyte.When paired with the 0.87 m'salt in dimethyl sulfoxide/water'hybrid electrolyte,the symmetric supercapacitor presents a 2.0 V high operating voltage at 25℃,and can operate stably at-50℃.Importantly,the suppressed electrochemical reaction of water at-50℃further leads to the symmetric supercapacitor operated at a higher voltage of 2.6 V.This modification strategy opens an effective avenue to develop low-salt electrolytes for high-voltage and low-temperature aqueous supercapacitors.展开更多
VOSO4 immobilized within nanoreactors of Al-MCM-41 (VO2+/Al-MCM-41) was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption, and chemical analysi...VOSO4 immobilized within nanoreactors of Al-MCM-41 (VO2+/Al-MCM-41) was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption, and chemical analysis techniques. The prepared VO2+/Al-MCM-41 successfully catalyzes the oxidation of aryl alkyl sulfides and up to 99% conversion and 90% selectivity for the corresponding sulfoxides were obtained with H2O2 as oxidant in acetonitrile at room temperature in 30 min.展开更多
The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to hig...The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to high chemical yields and moderate enantioselectivities were obtained.展开更多
Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1＇-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti（O^ipr）...Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1＇-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti（O^ipr）4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity （over 99%ee） in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioseleetivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.展开更多
Chemotherapy extravasation remains an accidental complication of chemotherapy administration and may result in serious damage to patients. We review in this article the clinical aspects of chemotherapy extravasation a...Chemotherapy extravasation remains an accidental complication of chemotherapy administration and may result in serious damage to patients. We review in this article the clinical aspects of chemotherapy extravasation and latest advances in definitions, classification, pre-vention, management and guidelines. We review the grading of extravasation and tissue damage according to various chemotherapeutic drugs and present an update on treatment and new antidotes including dexrazoxane for anthracyclines extravasation. We highlight the importance of education and training of the oncology team for prevention and prompt pharmacological and non-pharmacological management and stress the availability of new antidotes like dexrazoxane wherever anthracyclines are being infused.展开更多
Osteochondral allografting has been proved to be a useful method to treat diseased or damaged areas of joint surfaces. Operational long-term stocks of grafts which supply a buffer between procurement and utilization w...Osteochondral allografting has been proved to be a useful method to treat diseased or damaged areas of joint surfaces. Operational long-term stocks of grafts which supply a buffer between procurement and utilization would contribute to the commercialization or industrialization of this technology. Vitrification has been thought to be a promising method for successful preservation of articular cartilage （AC）, but high concentration cryoprotectants （CPAs） are used which may cause high cellular toxicity. An effective way to reduce CPA toxioity is to increase CPA concen- tration gradually while the temperature is lowered. Understanding the mechanism of （31~A permeation at subzero temperatures is important for designing the cryopreservation protocol. In this research, the permeation of dimethyl sulfoxide （MezSO） in ovine AC at subzero temperatures was studied experimentally. Pretreated AC discs were ex- posed in Me2SO solutions for different time （0, 5, 15, 30, 50, 80, and 120 min） at three temperature levels （-10, -20, and -30℃）. The Me2SO concentration within the tissue was determined by ultraviolet （UV） spectrophotometry. The diffusion coefficients were estimated to be 0.85×10-6, 0.48×10-8, and 0.27×10-6 cm2/s at -10, -20, and -,30℃, respectively, and the corresponding activation energy was 29.23 kJ/mol. Numerical simulation was performed to com- pare two Me2SO addition protocols, and the results demonstrated that the total loading duration could be effectively reduced with the knowledge of permeation kinetics.展开更多
AIM: To investigate whether dimethyl sulfoxide(DMSO) inhibits gut inflammation and barrier dysfunction following zymosan-induced systemic inflammatoryresponse syndrome and multiple organ dysfunction syndrome.METHODS: ...AIM: To investigate whether dimethyl sulfoxide(DMSO) inhibits gut inflammation and barrier dysfunction following zymosan-induced systemic inflammatoryresponse syndrome and multiple organ dysfunction syndrome.METHODS: Sprague-Dawley rats were randomly divided into four groups: sham with administration of normal saline(SS group); sham with administration of DMSO(SD group); zymosan with administration of normal saline(ZS group); and zymosan with administration of DMSO(ZD group). Each group contained three subgroups according to 4 h,8 h,and 24 h after surgery. At 4 h,8 h,and 24 h after intraperitoneal injection of zymosan(750 mg/kg),the levels of intestinal inflammatory cytokines [tumor necrosis factor-alpha(TNF-α) and interleukin(IL)-10] and oxides(myeloperoxidase,malonaldehyde,and superoxide dismutase) were examined. The levels of diamine oxidase(DAO) in plasma and intestinal mucosal blood flow(IMBF) were determined. Intestinal injury was also evaluated using an intestinal histological score and apoptosis of intestinal epithelial cells was determined by deoxynucleotidyl transferase d UTP nick end labeling(TUNEL) assay. The intestinal epithelial tight junction protein,ZO-1,was observed by immunofluorescence.RESULTS: DMSO decreased TNF-α and increased IL-10 levels in the intestine compared with the ZS group at the corresponding time points. The activity of intestinal myeloperoxidase in the ZS group was higher than that in the ZD group 24 h after zymosan administration(P < 0.05). DMSO decreased the content of malondialdehyde(MDA) and increased the activity of superoxide dehydrogenase(SOD) 24 h after zymosan administration. The IMBF was lowest at 24 h and was 49.34% and 58.26% in the ZS group and ZD group,respectively(P < 0.05). DMSO alleviated injury in intestinal villi,and the gut injury score was significantly lower than the ZS group(3.6 ± 0.2 vs 4.2 ± 0.3,P < 0.05). DMSO decreased the level of DAO in plasma compared with the ZS group(65.1 ± 4.7 U/L vs 81.1 ± 5.0 U/L,P < 0.05). DMSO significantly preserved ZO-1 protein expression and localization 24 h after zymosan administration. The TUNEL analysis indicated that the number of apoptotic intestinal cells in the ZS group was much higher than the ZD group(P < 0.05).CONCLUSION: DMSO inhibited intestinal cytokines and protected against zymosan-induced gut barrier dysfunction.展开更多
Upon extractive desulfurization of sulfur-rich oil obtained after recycling raffinate,the effects of single and compound extractants,temperature,and extractant/oil ratio on desulfurization rate,oil loss rate,extractan...Upon extractive desulfurization of sulfur-rich oil obtained after recycling raffinate,the effects of single and compound extractants,temperature,and extractant/oil ratio on desulfurization rate,oil loss rate,extractant loss rate,and selectivity coefficient were investigated.The results showed that the thiophene existing in the simulated sulfur-rich oil could be further removed by extraction.The single-stage desulfurization rates achieved by dimethyl sulfoxide(DMSO)and sulfolane(SF)were 53.51%and 47.36%,respectively,while the selectivity coefficient of SF was 1.13,which was higher than that of DMSO(with a selectivity coefficient of 1.04).For the compound extractant,a single-stage desulfurization rate of 49.59%and a selectivity coefficient of 1.40 were obtained by using DMSO+10%MEA as the extractant,which was higher than that of SF.Upon using 50%SF+50%DMSO as the extractant,the single-stage desulfurization rate reached 50.92%with a selectivity coefficient of 1.32.Based on the comprehensive consideration,the DMSO+10%MEA extractant was selected as the best extractant for treating the sulfur-rich oil.展开更多
The oxidation of organic compounds by sulfonated porous carbon and H2O2 was studied at room temperature. Alkyl and aryl sulfides were oxidized to the corresponding sulfoxides or sulfones in excellent yields. Secondary...The oxidation of organic compounds by sulfonated porous carbon and H2O2 was studied at room temperature. Alkyl and aryl sulfides were oxidized to the corresponding sulfoxides or sulfones in excellent yields. Secondary alcohols were also converted to the corresponding esters/lactones and aldehydes to methyl esters in good yields. Moreover,aliphatic tertiary amines and substituted pyridines were oxidized to N-oxides.展开更多
Phenylcarboxymethyl Sulfoxide, PhSOCH 2COOH(LH), complexes of six lanthanide nitrates: Ln 2L 2(NO 3) 4·2LH· n H 2O(where Ln=La, Ce, Pr, Nd, Sm, Eu) were synthesized. Elemental analyses, molar conduc...Phenylcarboxymethyl Sulfoxide, PhSOCH 2COOH(LH), complexes of six lanthanide nitrates: Ln 2L 2(NO 3) 4·2LH· n H 2O(where Ln=La, Ce, Pr, Nd, Sm, Eu) were synthesized. Elemental analyses, molar conductivities, IR, 1HNMR and TG DTA measurements were used to characterize the complexes. The results show that the ligand(L) is coordinated to metal ions through two oxygen atoms of the carboxyl group and one oxygen atom of the sulfoxide moieties. Neutral ligang (LH)is coordinated to two metal ions through two oxygen atoms of carboxyl group as an asymmetrical bridging bidentate. The fluorescence spectra of Eu 3+ complex indicates that there is no inversion symmetry at the site of Eu 3+ ion, but the emission intensity of fluorescence is quite good.The solubility of the complexes is very good in water.展开更多
Feasible and effective cell models for hepatitis B virus(HBV) infection are required for investigating the complete lifecycle of this virus, including the early steps of viral entry. Resistance to dimethyl sulfoxide/p...Feasible and effective cell models for hepatitis B virus(HBV) infection are required for investigating the complete lifecycle of this virus, including the early steps of viral entry. Resistance to dimethyl sulfoxide/polyethylene glycol(DMSO/PEG), h NTCP expression, and a differentiated state are the limiting factors for successful HBV infection models. In the present study, we used a hepatoma cell line(Hu7^(hDNTCPh)) to overcome these limiting factors so that it exhibits excellent susceptibility to HBV infection. To achieve this goal, different hepatoma cell lines were tested with 2.5% DMSO/4%PEG8000, and one resistant cell line(Huh7 D) was used to construct a stable h NTCP-expressing cell line(Hu7^(hDNTCPh)) using a recombinant lentivirus system. Then, the morphological characteristics and differentiation molecular markers of Hu7^(hDNTCPh) cells with or without DMSO treatment were characterized. Finally, the susceptibility of Hu7^(hDNTCPh) cells to HBV infection was assessed. Our results showed that Huh7 D cells were resistant to 2.5% DMSO/4% PEG8000, whereas the others were not. Hu7^(hDNTCPh) cells were established to express a high level of h NTCP compared to liver extracts, and Hu7^(hDNTCPh) cells rapidly transformed into a non-dividing, well-differentiated polarized phenotype under DMSO treatment. Hu7^(hDNTCPh) cells fully supported the entire lifecycle of HBV infection. This cell culture system will be useful for the analysis of host-virus interactions, which should facilitate the discovery of antiviral drugs and vaccines.展开更多
Platinum, palladium and rhodium of the raw feeds extracted and separated with a new sulfoxide extractant （MSO） were studied in the paper. The pilot test results showed that the percentage extractions are more than 9...Platinum, palladium and rhodium of the raw feeds extracted and separated with a new sulfoxide extractant （MSO） were studied in the paper. The pilot test results showed that the percentage extractions are more than 99% for platinum and palladium in Pt-Pd feed, and the percentage strippings are 100% and 99.2% with HCl and ammonia, respectively. The ratio of palladium to platinum is 0.0016 in stripping platinum solution, and the ratio of platinum to palladium is 0.0020 in stripping palladium solution. The percentage extraction of platinum is 99% in Pt-Rh feed, and the percentage stripping is 100%. The ratio of rhodium to platinum is 0.0002 in stripping platinum solution. Therefore, platinum, palladium, and rhodium feeds are separated effectively with MSO.展开更多
The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-h...The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.展开更多
DBUH-Br_3 catalyzed selective conversion of sulfides to sulfoxides in the presence of H_2O_2 as oxidizing agent is described.The reaction was performed selectively at room temperature and relatively short reaction times.
The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ethe...The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.展开更多
N,N-Diallyl methionine ethyl ester hydrochloride 5 underwent alternating copolymerization with SO_2 via the Butler cyclopolymerization protocol in dimethyl sulfoxide(DMSO) to give water-soluble cycloterpolymer 6 with...N,N-Diallyl methionine ethyl ester hydrochloride 5 underwent alternating copolymerization with SO_2 via the Butler cyclopolymerization protocol in dimethyl sulfoxide(DMSO) to give water-soluble cycloterpolymer 6 with a ～1:1 molar ratio of sulfide and sulfoxide groups as a result of oxygen transfer from DMSO. Half of the sulfide groups in 6, upon oxidation with H_2O_2, afforded polymer sulfoxide 7 and polymer sulfone 8. The solution properties of these polymers were determined via a viscometric technique. The thermal stability of these polymers was determined by thermogravimetric analysis. The inhibition efficiency obtained from gravimetric mass loss, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques agreed well with each other. The corrosion efficiencies increase with increasing concentration of the polymers. At a polymer concentration of 175 mM, the maximum inhibition efficiency of copolymer compounds 6–8 was determined to be 92%, 97%, and 95%, respectively. The synthesized polymer compounds acted as mixed-type inhibitors. Polymer compound 7 adsorbed onto the metal surface via chemisorption and physisorption and obeyed Langmuir, Temkin, and Freundlich adsorption isotherms. Analyses by X-ray photoelectron spectroscopy and scanning electron microscopy–energy-dispersive X-ray spectroscopy indicated that the adsorbed polymers formed a thin film on the metal surface and prevented further corrosive attack.展开更多
The composition and structure of cyclic sulfoxide derivative Pd(IT) complexwere investigated. The coordinated number was studied with slope method. The coordination number is2 in lower acidity, but it is 3 in higher a...The composition and structure of cyclic sulfoxide derivative Pd(IT) complexwere investigated. The coordinated number was studied with slope method. The coordination number is2 in lower acidity, but it is 3 in higher acidity. Four methods, UV (ultraviolet) spectra, FUR(Fourier transform infrared) spectra, ~1H-NMR (nuclear magnetic resonance) spectra, and ^(13)C-NMRspectra, were used to determine the coordinated atom in complex. Pd is coordinated with O and S atomin S=O group in lower acidity media. The conversion of coordination bond appears with an increasingtime. Pd is coordinated with S atom in S=O group in higher acidity media, and inter-ligand-transferreaction occurs.展开更多
基金the Key Project of Provincial Natural Science Research Foundation of Anhui Universities,China(Nos.2022AH050406,2023AH050346)Anhui Province Research Funding for Outstanding Young Talents in Colleges and Universities,China(No.gxyq2022021)+3 种基金the Autonomous Project of Key Laboratory of Green and Precise Synthetic Chemistry and Applications,Ministry of Education(KLGPSCA202307,KLGPSCA202111)the Project of Graduate Innovation Fund(CX2024016)the Laboratory Open Project of Huaibei Normal University(Nos.2023syskf017,2023syskf027)the Industry-University-Research Horizontal Project(Nos.2023340603000039,22100370)forfinancial support.
文摘The N-H methylsulfoxidation of sulfoximines using DMso as a methylsulfinyl source,induced by electrochemistry,has been developed.This method is the first example of an electrochemical reaction in which DMso serves as a methylsulfinyl source.Unlike previous electrochemical reactions involving DMsO as a substrate,which exclusively proceed via radical mechanisms,this reaction follows an S-cation pathway.A wide range of N-methylsulfinyl sulfoximines were successfully obtained.
文摘Sperm cryopreservation is an essential technique for male fertility preservation,especially in men who are undergoing medical treatment.Conventional cryopreservation methods face limitations such as oxidative stress,DNA fragmentation,and cytotoxicity associated with traditional cryoprotectants like dimethyl sulfoxide(DMSO).Recent breakthroughs have focused on improving post-thaw sperm viability with novel cryoprotectants and innovative freezing strategies.Prospective approaches include the use of amino acid-based cryoprotectants,deep eutectic solvents,and antioxidants that have been described to prevent oxidative damage and maintain DNA integrity.Vitrification,a high-speed freezing technique that prevents ice crystal formation,has demonstrated superior outcomes compared to conventional slow freezing.Moreover,the Direct Dropping Method,a cryoprotectant-free approach,has been introduced as a contamination-minimizing technique that preserves sperm functionality.Multiomics tools are also utilized to determine biomarkers for protocol optimization.Despite these advancements,cryoprotectant toxicity is a central challenge,emphasizing the necessity for safer agents.Future research must focus on long-term sperm functionality and individualized cryopreservation strategies to maximize reproductive outcomes.The current review highlights the challenges associated with sperm cryopreservation,explores innovative strategies and novel cryoprotectants,underscores the significance of maintaining DNA integrity,and proposes future research directions to improve fertility preservation outcomes.
基金financially supported by the National Natural Science Foundation of China(Nos.21901037,21901038 and 92161111)the Program for Professor of Special Appointment(Eastern Scholar)at Shanghai Institutions of Higher Learning+1 种基金the Fundamental Research Funds for the Central Universities(No.2232019G-07)the International Cooperation Fund of Science and Technology Commission of Shanghai Municipality(No.21130750100)。
文摘N-doping has significant influence in manipulating the properties of TiO_(2),and this has stimulated the development of N-donor-functionalized titanium-oxo clusters(TOCs)as molecular models to study the structure-property relationship.However,the structural type and photoresponsive application are still limited for such TOCs,especially regarding the high-nuclearity TOCs that contain structure unit of TiO_(2)for photocatalysis.Herein,we showed the synthesis of a series of high-nuclearity TOCs 1-3 compounds usingπ-conjugated 1,10-phenanthroline(phen)as chromophore and N-donor functional ligand.Compound 1 features cocrystal structure composed of one[Ti_(26)]~(2+)and half[Ti_(22)]~(2+),which renders it as the first cocrystallized TOC containing two positively charged species and phen-functionalized TOC showing the highest nuclearity up to 37 Ti centers.By adjusting the synthetic conditions,the individual{Ti_(22)}and{Ti_(26)}clusters can also be isolated as Compounds 2 and 3,respectively.The core structure of{Ti_(22)}is mainly constructed from four lacunary{Ti_(4)}derived from pentagonal{Ti(Ti)_5}unit,while{Ti_(26)}is built from four complete{Ti(Ti)_5}unit.Notably,a{Ti_8O_(14)}structure unit of anatase TiO_(2)can be identified in{Ti_(26)}.Based on the unique structural features and proper photophysical and photochemical properties of Compounds 1-3,they are applied for photocatalytic sulfoxidation.Owing to the presence of anatase structure unit in{Ti_(26)}and the synergistic effect from{Ti_(22)}and{Ti_(26)},the catalytic performance presents in the order of Compound 1>Compound 3>Compound 2.This work provides excellent models to understand the structureproperty relationship from the perspective of cocrystallization and Ti-O binding model and will further promote the application of TOCs as functional catalysts for organic transformation.
基金partly supported by the National Key R&D Program of China(2022YFB4101602)the National Natural Science Foundation of China(22078052)the Fundamental Research Funds for the Central Universities(DUT22ZD207)。
文摘Compared with organic electrolytes,aqueous electrolytes exhibit significantly higher ionic conductivity and possess inherent safety features,showcasing unique advantages in supercapacitors.However,challenges remain for low-salt aqueous electrolytes operating at high voltage and low temperature.Herein,we report a low-salt(0.87 m,m means mol kg^(-1))'salt in dimethyl sulfoxide/water'hybrid electrolyte with non-flammability via hybridizing aqueous electrolyte with an organic co-solvent of dimethyl sulfoxide(hydrogen bond acceptor).As a result,the 0.87 m hybrid electrolyte exhibits enhanced electrochemical stability,a freezing temperature below-50℃,and an outstanding ionic conductivity of 0.52mS cm~(-1)at-50℃.Dimethyl sulfoxide can anchor water molecules through intermolecular hydrogen bond interaction,effectively reinforcing the stability of water in the hybrid electrolyte.Furthermore,the interaction between dimethyl sulfoxide and water molecules diminishes the involvement of water in the generation of ordered ice crystals,finally facilitating the low-temperature performance of the hybrid electrolyte.When paired with the 0.87 m'salt in dimethyl sulfoxide/water'hybrid electrolyte,the symmetric supercapacitor presents a 2.0 V high operating voltage at 25℃,and can operate stably at-50℃.Importantly,the suppressed electrochemical reaction of water at-50℃further leads to the symmetric supercapacitor operated at a higher voltage of 2.6 V.This modification strategy opens an effective avenue to develop low-salt electrolytes for high-voltage and low-temperature aqueous supercapacitors.
基金Supported by the Research Council of the University of Alzahra, Iran
文摘VOSO4 immobilized within nanoreactors of Al-MCM-41 (VO2+/Al-MCM-41) was synthesized and characterized by X-ray diffraction, Fourier transform infrared spectroscopy, nitrogen adsorption-desorption, and chemical analysis techniques. The prepared VO2+/Al-MCM-41 successfully catalyzes the oxidation of aryl alkyl sulfides and up to 99% conversion and 90% selectivity for the corresponding sulfoxides were obtained with H2O2 as oxidant in acetonitrile at room temperature in 30 min.
基金National Natural Science Foundation of China(No.20102002,20472028)Science Foundation of Jiangsu Province for their financial support(No.20332050).
文摘The asymmetric oxidation of sulfides catalyzed by WO3 and 30% H2O2 in the presence of salan as chiral ligands under heterogeneous conditions is described. The reaction system is very easily to be operated. Mild to high chemical yields and moderate enantioselectivities were obtained.
基金the Natural Science Foundation of Chongqing Science and Technology Committee (No.2007BB4442)the Science and Technology Research Project of Chongqing Education Commission (No.KJ070402)
文摘Polymer-immobilized catalysis has many advantages such as easy recovery and reuse of catalyst. We prepared three novel chiral 1,1＇-bi-2-naphthol-Ti coordination polymers with properly designed ligands and Ti（O^ipr）4 under mild conditions. The prepared polymers exhibited good activity and excellent enantioselectivity （over 99%ee） in catalyzing the asymmetric oxidation of sulfides. The bridge linker in the polymer and the reaction solvent noticeably affected the enantioseleetivity. The chiral coordination polymer was very stable and easy to separate from catalyzed reaction systems, with no significant loss of activity or enantioselectivity after reuse for at least ten times. These findings suggest a promising type of catalysts for synthesizing the widely used sulfoxides by asymmetrically oxidizing sulfides.
文摘Chemotherapy extravasation remains an accidental complication of chemotherapy administration and may result in serious damage to patients. We review in this article the clinical aspects of chemotherapy extravasation and latest advances in definitions, classification, pre-vention, management and guidelines. We review the grading of extravasation and tissue damage according to various chemotherapeutic drugs and present an update on treatment and new antidotes including dexrazoxane for anthracyclines extravasation. We highlight the importance of education and training of the oncology team for prevention and prompt pharmacological and non-pharmacological management and stress the availability of new antidotes like dexrazoxane wherever anthracyclines are being infused.
基金supported by the National Natural Science Foundation of China (No. 50606032)the Graduate Innovation Research Program of Zhejiang Province (No. YK2008020), China
文摘Osteochondral allografting has been proved to be a useful method to treat diseased or damaged areas of joint surfaces. Operational long-term stocks of grafts which supply a buffer between procurement and utilization would contribute to the commercialization or industrialization of this technology. Vitrification has been thought to be a promising method for successful preservation of articular cartilage （AC）, but high concentration cryoprotectants （CPAs） are used which may cause high cellular toxicity. An effective way to reduce CPA toxioity is to increase CPA concen- tration gradually while the temperature is lowered. Understanding the mechanism of （31~A permeation at subzero temperatures is important for designing the cryopreservation protocol. In this research, the permeation of dimethyl sulfoxide （MezSO） in ovine AC at subzero temperatures was studied experimentally. Pretreated AC discs were ex- posed in Me2SO solutions for different time （0, 5, 15, 30, 50, 80, and 120 min） at three temperature levels （-10, -20, and -30℃）. The Me2SO concentration within the tissue was determined by ultraviolet （UV） spectrophotometry. The diffusion coefficients were estimated to be 0.85×10-6, 0.48×10-8, and 0.27×10-6 cm2/s at -10, -20, and -,30℃, respectively, and the corresponding activation energy was 29.23 kJ/mol. Numerical simulation was performed to com- pare two Me2SO addition protocols, and the results demonstrated that the total loading duration could be effectively reduced with the knowledge of permeation kinetics.
基金Supported by National 11th Five-Year Plan of China for Military Medical Projects,No.06Z055the National Natural Science Foundation of China,No.81301607
文摘AIM: To investigate whether dimethyl sulfoxide(DMSO) inhibits gut inflammation and barrier dysfunction following zymosan-induced systemic inflammatoryresponse syndrome and multiple organ dysfunction syndrome.METHODS: Sprague-Dawley rats were randomly divided into four groups: sham with administration of normal saline(SS group); sham with administration of DMSO(SD group); zymosan with administration of normal saline(ZS group); and zymosan with administration of DMSO(ZD group). Each group contained three subgroups according to 4 h,8 h,and 24 h after surgery. At 4 h,8 h,and 24 h after intraperitoneal injection of zymosan(750 mg/kg),the levels of intestinal inflammatory cytokines [tumor necrosis factor-alpha(TNF-α) and interleukin(IL)-10] and oxides(myeloperoxidase,malonaldehyde,and superoxide dismutase) were examined. The levels of diamine oxidase(DAO) in plasma and intestinal mucosal blood flow(IMBF) were determined. Intestinal injury was also evaluated using an intestinal histological score and apoptosis of intestinal epithelial cells was determined by deoxynucleotidyl transferase d UTP nick end labeling(TUNEL) assay. The intestinal epithelial tight junction protein,ZO-1,was observed by immunofluorescence.RESULTS: DMSO decreased TNF-α and increased IL-10 levels in the intestine compared with the ZS group at the corresponding time points. The activity of intestinal myeloperoxidase in the ZS group was higher than that in the ZD group 24 h after zymosan administration(P < 0.05). DMSO decreased the content of malondialdehyde(MDA) and increased the activity of superoxide dehydrogenase(SOD) 24 h after zymosan administration. The IMBF was lowest at 24 h and was 49.34% and 58.26% in the ZS group and ZD group,respectively(P < 0.05). DMSO alleviated injury in intestinal villi,and the gut injury score was significantly lower than the ZS group(3.6 ± 0.2 vs 4.2 ± 0.3,P < 0.05). DMSO decreased the level of DAO in plasma compared with the ZS group(65.1 ± 4.7 U/L vs 81.1 ± 5.0 U/L,P < 0.05). DMSO significantly preserved ZO-1 protein expression and localization 24 h after zymosan administration. The TUNEL analysis indicated that the number of apoptotic intestinal cells in the ZS group was much higher than the ZD group(P < 0.05).CONCLUSION: DMSO inhibited intestinal cytokines and protected against zymosan-induced gut barrier dysfunction.
文摘Upon extractive desulfurization of sulfur-rich oil obtained after recycling raffinate,the effects of single and compound extractants,temperature,and extractant/oil ratio on desulfurization rate,oil loss rate,extractant loss rate,and selectivity coefficient were investigated.The results showed that the thiophene existing in the simulated sulfur-rich oil could be further removed by extraction.The single-stage desulfurization rates achieved by dimethyl sulfoxide(DMSO)and sulfolane(SF)were 53.51%and 47.36%,respectively,while the selectivity coefficient of SF was 1.13,which was higher than that of DMSO(with a selectivity coefficient of 1.04).For the compound extractant,a single-stage desulfurization rate of 49.59%and a selectivity coefficient of 1.40 were obtained by using DMSO+10%MEA as the extractant,which was higher than that of SF.Upon using 50%SF+50%DMSO as the extractant,the single-stage desulfurization rate reached 50.92%with a selectivity coefficient of 1.32.Based on the comprehensive consideration,the DMSO+10%MEA extractant was selected as the best extractant for treating the sulfur-rich oil.
基金Supported by the Malek-Ashtar University of Technology
文摘The oxidation of organic compounds by sulfonated porous carbon and H2O2 was studied at room temperature. Alkyl and aryl sulfides were oxidized to the corresponding sulfoxides or sulfones in excellent yields. Secondary alcohols were also converted to the corresponding esters/lactones and aldehydes to methyl esters in good yields. Moreover,aliphatic tertiary amines and substituted pyridines were oxidized to N-oxides.
文摘Phenylcarboxymethyl Sulfoxide, PhSOCH 2COOH(LH), complexes of six lanthanide nitrates: Ln 2L 2(NO 3) 4·2LH· n H 2O(where Ln=La, Ce, Pr, Nd, Sm, Eu) were synthesized. Elemental analyses, molar conductivities, IR, 1HNMR and TG DTA measurements were used to characterize the complexes. The results show that the ligand(L) is coordinated to metal ions through two oxygen atoms of the carboxyl group and one oxygen atom of the sulfoxide moieties. Neutral ligang (LH)is coordinated to two metal ions through two oxygen atoms of carboxyl group as an asymmetrical bridging bidentate. The fluorescence spectra of Eu 3+ complex indicates that there is no inversion symmetry at the site of Eu 3+ ion, but the emission intensity of fluorescence is quite good.The solubility of the complexes is very good in water.
基金supported by the National Natural Science Foundation of China (Grant number: 81601760, 31621061 and 81461130019)General Financial Grant from the China Postdoctoral Science Foundation (Grant number: 2016M602587)+1 种基金the Shenzhen Foundation of Science and Technology (Grant number: JCYJ20160425 104534335)supported by the Youth Innovation Promotion Association CAS (No.201603)
文摘Feasible and effective cell models for hepatitis B virus(HBV) infection are required for investigating the complete lifecycle of this virus, including the early steps of viral entry. Resistance to dimethyl sulfoxide/polyethylene glycol(DMSO/PEG), h NTCP expression, and a differentiated state are the limiting factors for successful HBV infection models. In the present study, we used a hepatoma cell line(Hu7^(hDNTCPh)) to overcome these limiting factors so that it exhibits excellent susceptibility to HBV infection. To achieve this goal, different hepatoma cell lines were tested with 2.5% DMSO/4%PEG8000, and one resistant cell line(Huh7 D) was used to construct a stable h NTCP-expressing cell line(Hu7^(hDNTCPh)) using a recombinant lentivirus system. Then, the morphological characteristics and differentiation molecular markers of Hu7^(hDNTCPh) cells with or without DMSO treatment were characterized. Finally, the susceptibility of Hu7^(hDNTCPh) cells to HBV infection was assessed. Our results showed that Huh7 D cells were resistant to 2.5% DMSO/4% PEG8000, whereas the others were not. Hu7^(hDNTCPh) cells were established to express a high level of h NTCP compared to liver extracts, and Hu7^(hDNTCPh) cells rapidly transformed into a non-dividing, well-differentiated polarized phenotype under DMSO treatment. Hu7^(hDNTCPh) cells fully supported the entire lifecycle of HBV infection. This cell culture system will be useful for the analysis of host-virus interactions, which should facilitate the discovery of antiviral drugs and vaccines.
文摘Platinum, palladium and rhodium of the raw feeds extracted and separated with a new sulfoxide extractant （MSO） were studied in the paper. The pilot test results showed that the percentage extractions are more than 99% for platinum and palladium in Pt-Pd feed, and the percentage strippings are 100% and 99.2% with HCl and ammonia, respectively. The ratio of palladium to platinum is 0.0016 in stripping platinum solution, and the ratio of platinum to palladium is 0.0020 in stripping palladium solution. The percentage extraction of platinum is 99% in Pt-Rh feed, and the percentage stripping is 100%. The ratio of rhodium to platinum is 0.0002 in stripping platinum solution. Therefore, platinum, palladium, and rhodium feeds are separated effectively with MSO.
基金This work was supported by the NNSFC (20332030, 20572027), Research Grants Council of Hong Kong and SRF for ROCS, State Education Ministry
文摘The substituent effect of sulfoxides in solvent extraction of palladium is investigated theoretically by using di-n-hexyl and diphenyl sulfoxide-palladium （Ⅱ） adducts as model complexes. RHF, DFT and two half-and-half functional （BHandHLYP and BHandH） methods have been applied in the geometry optimization, and BHandH method at the 6-31G^＊ level （Pd, 3-21G^＊） can give adequate accuracy for both free sulfoxides and their Pd （Ⅱ） complexes. As compared to diphenyl sulfoxide （DPSO）, the better affinity of di-n-hexyl sulfoxide （DHSO） towards Pd（Ⅱ） has been reasonably explained by a stronger electronic transfer, shorter Pd-S bond length and a larger binding energy in its Pd （Ⅱ） complex.
文摘DBUH-Br_3 catalyzed selective conversion of sulfides to sulfoxides in the presence of H_2O_2 as oxidizing agent is described.The reaction was performed selectively at room temperature and relatively short reaction times.
文摘The recent development of selective oxidation of aromatic sulfides with molecular oxygen was highlighted.The sulfoxides and sulfones could be obtained by simply switching the reaction media,i.e.,bis(2-butoxyethyl)ether(BBE)or poly(ethylene glycol)dimethyl ether(PEGDME).The application of the high-boiling-point polyether as an initiator and green media can eliminate the need of large quantities of additives and volatile solvents.This strategy represents an economic and eco-friendly method that could find potential applications.
基金financial assistance of the Deanship of Scientific Research, KFUPM, Saudi Arabia through Internal project # IN131047
文摘N,N-Diallyl methionine ethyl ester hydrochloride 5 underwent alternating copolymerization with SO_2 via the Butler cyclopolymerization protocol in dimethyl sulfoxide(DMSO) to give water-soluble cycloterpolymer 6 with a ～1:1 molar ratio of sulfide and sulfoxide groups as a result of oxygen transfer from DMSO. Half of the sulfide groups in 6, upon oxidation with H_2O_2, afforded polymer sulfoxide 7 and polymer sulfone 8. The solution properties of these polymers were determined via a viscometric technique. The thermal stability of these polymers was determined by thermogravimetric analysis. The inhibition efficiency obtained from gravimetric mass loss, potentiodynamic polarization, and electrochemical impedance spectroscopy techniques agreed well with each other. The corrosion efficiencies increase with increasing concentration of the polymers. At a polymer concentration of 175 mM, the maximum inhibition efficiency of copolymer compounds 6–8 was determined to be 92%, 97%, and 95%, respectively. The synthesized polymer compounds acted as mixed-type inhibitors. Polymer compound 7 adsorbed onto the metal surface via chemisorption and physisorption and obeyed Langmuir, Temkin, and Freundlich adsorption isotherms. Analyses by X-ray photoelectron spectroscopy and scanning electron microscopy–energy-dispersive X-ray spectroscopy indicated that the adsorbed polymers formed a thin film on the metal surface and prevented further corrosive attack.
文摘The composition and structure of cyclic sulfoxide derivative Pd(IT) complexwere investigated. The coordinated number was studied with slope method. The coordination number is2 in lower acidity, but it is 3 in higher acidity. Four methods, UV (ultraviolet) spectra, FUR(Fourier transform infrared) spectra, ~1H-NMR (nuclear magnetic resonance) spectra, and ^(13)C-NMRspectra, were used to determine the coordinated atom in complex. Pd is coordinated with O and S atomin S=O group in lower acidity media. The conversion of coordination bond appears with an increasingtime. Pd is coordinated with S atom in S=O group in higher acidity media, and inter-ligand-transferreaction occurs.
