- Inorganic Mediator toward Organosulfide Active Material: Anchoring and Electrocatalysis
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Organosulfides are promising high-capacity cathode materials for rechargeable lithium batteries. However, they are hindered by several key challenges including the electronic/ionic insulation and solubility issues of the discharged products. Herein, TiS2 nanosheets@carbon nanotubes (TiS2 NSs@MWCNT) are proposed as a promoter and booster toward phenyl tetrasulfide (PTS). It serves as a bifunctional mediator, not only anchoring active materials in the cathode through chemical adsorption but also facilitating the reaction kinetics. The Li-organosulfide cell yields a reversible discharge capacity of 467.6 mAh g?1 and a high capacity retention of 81.9% after 200 cycles at 0.5 C rate. When the PTS areal mass loading is 5.8 mg cm?2 and the electrolyte/PTS ratio is 3.8 μL mg?1, a high specific capacity of 444 mAh g?1 at 0.5 C rate can still be achieved. The strong anchoring and electrocatalysis effects of TiS2 toward PhSLi and polysulfide are revealed using experimental and computational approaches. The study sheds light on metal sulfides as mediators to improve the cycling life of Li-organosulfide batteries and provides deep comprehension of the instinct interaction evolution at molecular level, which is invaluable for fabrication of electrode materials.
- Fan, Qianqian,Guo, Wei,Si, Yubing,Wang, Xin,Wang, Bo,Fu, Yongzhu
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- Electrochemical Synthesis of Organic Polysulfides from Disulfides by Sulfur Insertion from S8 and an Unexpected Solvent Effect on the Product Distribution
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An electrochemical synthesis of organic polysulfides through sulfur insertion from elemental sulfur to disulfides or thiols is introduced. The highly economic, low-sensitive and low-priced reaction gives a mixture of polysulfides, whose distribution can be influenced by the addition of different amounts of carbon disulfide as co-solvent. To describe the variable distribution function of the polysulfides, a novel parameter, the “absorbance average sulfur amount in polysulfides” (SAP) was introduced and defined on the basis of the “number average molar mass” used in polymer chemistry. Various organic polysulfides were synthesized with variable volume fractions of carbon disulfide, and the yield of each polysulfide was determined by quantitative 13C NMR. Moreover, by using two symmetrical disulfides or a disulfide and a thiol as starting materials, a mixture of symmetrical and asymmetrical polysulfides could be obtained.
- F?hrmann, Jan,Hilt, Gerhard
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p. 11141 - 11149
(2021/06/09)
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- Redox Activation of Hydrogen Sulfide, Thiols, and Sulfur in Electrosynthesis of Organic Di- and Polysulfides
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A novel and efficient method for the synthesis of biologically active organic di-, tri- and tetrasulfides has been proposed. Different methods of redox activation of sulfur, hydrogen sulfide, and thiols in the reactions with organic compounds have been considered. Electrochemical initiation of the reactions of the mediator–H2S–S8 system with cyclohexane, methylcyclohexane, and benzene has occurred to the formation of polysulfides R2Sn (n = 2–4). The application of tetrabutylammonium bromide as a mediator of H2S oxidation has allowed to decrease the anodic overpotential of electrosynthesis. Di- and tetrasulfides have been obtained under anodic activation of the cycloalkanethiols (C5, C6) or thiophenol in the reaction with sulfur. Electroreduction of S8 in the presence of the same thiols has favored the formation of di- and trisulfides. The yield and the ratio of the R5Sn (n = 2–4) depend on the method of redox activation of the thiolating reagent.
- Shinkar’,Smolyaninov,Kuzmin,Berberova
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p. 689 - 696
(2019/06/05)
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- Applications of Synthetic Organic Tetrasulfides as H2S Donors
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In an effort to expand the availability of simple polysulfides for H2S donation, we report here the synthesis and H2S release profiles of bis(aryl) and bis(alkyl) tetrasulfides. The tetrasulfide donors release H2S in a first-order dependence on reduced glutathione (GSH) and release more H2S than the commonly used trisulfide DATS.
- Cerda, Matthew M.,Hammers, Matthew D.,Earp, Mary S.,Zakharov, Lev N.,Pluth, Michael D.
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supporting information
p. 2314 - 2317
(2017/05/12)
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- Synthesis and antimicrobial activities of structurally novel S,S′-bis(heterosubstituted) disulfides
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The central focus of this study is on the antibacterial and antifungal properties of synthetically produced S,S′-bis(heterosubstituted) disulfides as a means to control the growth of various infection-causing pathogens. Staphylococcus aureus, Francisella tularensis and Candida albicans were each found to be highly susceptible to several of these compounds by agar or broth dilution and Kirby-Bauer diffusion assays. These structurally simple, low molecular weight disulfides have shown promising bioactivities and may serve as leads to the development of effective new antibacterials for pathogenic bacteria such as methicillin-resistant S. aureus and F. tularensis.
- Ramaraju, Praveen,Gergeres, Danielle,Turos, Edward,Dickey, Sonja,Lim, Daniel V.,Thomas, John,Anderson, Burt
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experimental part
p. 3623 - 3631
(2012/07/16)
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- COMPOSITIONS AND METHODS FOR TREATING OR PREVENTING HYPOXIC OR ISCHEMIC INJURY
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A method for treating or preventing injury of a biological material exposed to hypoxic or ischemic conditions comprising contacting the biological material with an effective amount of a compound is disclosed. The compound has the following structure (I):
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Page/Page column 40-41
(2010/04/30)
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- ANTIBACTERIAL S-HETEROSUBSTITUTED DISULFIDES
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Synthetically-derived S,S-heterodisubstituted disulfides that exhibit potent in vitro antibacterial activity against a variety of bacteria, including Staphylococcus aureus, methicillin-resistant Staphylococcus aureus and Francisella tularensis. The present invention provides compounds, methods and compositions effective to treat microbial/bacterial infections, and, especially, infections arising from bacteria which have developed resistance to conventional antibiotics.
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Page/Page column 13; 16
(2009/05/30)
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- Rhodium-catalyzed sulfur atom exchange reaction between organic polysulfides and sulfur
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RhH(PPh3)4 and cis-1,2-bis(diphenylphosphino)ethylene (dppv) catalyze the exchange of sulfur atoms between sulfur and organic polysulfides. The exchange of dialkyl trisulfides with sulfur proceeds at a high efficiency within 5 min at room temperature yielding a mixture of organic polysulfides.
- Arisawa, Mieko,Tanaka, Ken,Yamaguchi, Masahiko
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p. 4797 - 4800
(2007/10/03)
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- Optimization of the synthesis of symmetric aromatic tri- and tetrasulfides
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The reaction of aromatic thiols with sulfur dichloride and sulfur monochloride to form the corresponding aromatic trisulfides, 2a-d, and tetrasulfides, 3a-d, has been optimized with respect to yield and purity. The use of pyridine as an amine base and the
- Zysman-Colman, Eli,Harpp, David N.
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p. 2487 - 2489
(2007/10/03)
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- Use of a sacriflcial-sulfur electrode in electroorganic chemistry. V. Formation of the sequence CSSSC from S and thiols or thiolates
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At a working potential of about +2.0 V (vs SCE) the carbon-sulfur electrode is a source of the electrogenerated cation S2+. In organic media, this electrophile reacts with thiols (or thiolates) to give a mixture of polysulfides of which the trisulfide is the main product. The reaction between electrogenerated Sy2- and alkyl halides is less selective. Elsevier,.
- Do, Quang Tho,Elothmani, Driss,Simonet, Jacques,Guillanton, Georges Le
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p. 273 - 281
(2007/10/03)
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- THE REACTION OF t-BUTYL HYPOCHLORITE WITH THIOCARBONYL COMPOUND - A CONVENIENT METHOD FOR THE TRANSFORMATION
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The reaction of t-butyl hypochlorite with different thiocarbonyl compounds has been studied.Primary thioamides 1a-c give 1,2,4-thiadiazole derivatives.N-Phenylthiourea 4a gives 5-imino-4-phenyl-3-phenylamino-4,5-dihydro-1,2,4-thiadiazoline 15.Secondary and tertiary thioamides 2a-d, N-methyl-2-thiopyrrolidinone 3, N,N'-dicyclohexylthiourea 4b, N,N,N'-trimethylthiourea 4c, 5-ethyl-5-phenylthiobarbituric acid 5, xanthione 7a, Mischler's thioketone 7b, thiocoumarin 8, O-ethylthiobenzoate 9, O,O-diphenylthiocarbonate 10, di-p-tolyl and o-phenylene trithiocarbonates 11 and 12 have all afforded the oxigen analogues.N,N-Dimethyl-S-phenyldithiocarbonate 6 produces a mixture of di-, tri-, and tetrasulfides.A mechanism for the transformation is suggested in accordance with the Hard and Soft Acids and Bases (HSAB) principle.
- El-Wassimy, M.T.M.,Jorgensen, K.A.,Lawesson, S.-O.
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p. 1729 - 1734
(2007/10/02)
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