Search results for "Fides"

Palladium-catalyzed heteroaryl thioethers synthesis overcoming palladium dithiolate resting states inertness: Practical road to sulfones and NH-sulfo…

2018

International audience; We provide efficient synthetic access to heteroaryl sulfones in two-steps using a simple palladium-1,1'-bis [(diphenyl)phosphanyl]ferrocene catalyst to form in high yields variously functionalized heteroaromatic thioethers. Pyridinyl-containing substrates can be subsequently selectively oxidized into sulfones and NH-sulfoximines by using very mild oxidation conditions with a high functional group tolerance. In the palladium catalyzed C-S coupling of heteroaromatic thiols, reactivity limitation is attached with electron-deficient thiols. We show that this limitation can be resolved by the successful use of 2-bromoheteroarenes in the C-S coupling. We established herein…

Supramolecular organic-inorganic hybrid assemblies with tunable particle size: interplay of three noncovalent interactions.

2013

Degradable cationic nanohydrogel particles for stimuli-responsive release of siRNA.

2014

Well-defined nanogels have become quite attractive as safe and stable carriers for siRNA delivery. However, to avoid nanoparticle accumulation, they need to provide a stimuli-responsive degradation mechanism that can be activated at the payload's site of action. In this work, the synthetic concept for generating well-defined nanohydrogel particles is extended to incorporate disulfide cross-linkers into a cationic nanonetwork for redox-triggered release of oligonucleotide payload as well as nanoparticle degradation under reductive conditions of the cytoplasm. Therefore, a novel disulfide-modified spermine cross-linker is designed that both allows disassembly of the nanogel as well as removal…

Mechanism of the Oxidation of Sulfides by Dioxiranes. 1. Intermediacy of a 10-S-4 Hypervalent Sulfur Adduct

2002

Earlier studies established that dimethyldioxirane (1a) reacts with sulfides 2 in two consecutive concerted electrophilic oxygen-transfer steps to give first sulfoxides 3 and then sulfones 4. The same sequential electrophilic oxidation model was assumed for the reaction of sulfides 2 with the strongly electrophilic methyl(trifluoromethyl)dioxirane (1b). In this paper we report on a systematic and general study on the mechanism of the reaction of simple sulfides 2 with DMDO (1a) and TFDO (1b) which provides clear evidence for the involvement of hypervalent sulfur species in the oxidation process. In the oxidation of sulfides 2a-c, diphenyl sulfide (2d), para-substituted aryl methyl sulfides …

Heterogeneous oxidation of pyrimidine and alkyl thioethers in ionic liquids over mesoporous Ti or Ti/Ge catalysts.

2004

Heterogeneous catalytic oxidation of a series of thioethers (2-thiomethylpyrimidine, 2-thiomethyl-4,6-dimethyl-pyrimidine, 2-thiobenzylpyrimidine, 2-thiobenzyl-4,6-dimethylpyrimidine, thioanisole, and n-heptyl methyl sulfide) was performed in ionic liquids by using MCM-41 and UVM-type mesoporous catalysts containing Ti, or Ti and Ge. A range of triflate, tetrafluoroborate, trifluoroacetate, lactate and bis(trifluoromethanesulfonyl)-imide-based ionic liquids were used. The oxidations were carried out by using anhydrous hydrogen peroxide or the urea-hydrogen peroxide adduct and showed that ionic liquids are very effective solvents, achieving greater reactivity and selectivity than reactions p…

La fides e la promessa: forme di reciprocità tra dèi e uomini nella riscrittura di Ovidio

2017

Nelle rielaborazioni ovidiane dei racconti mitici greci, emergono diversi casi in cui la relazione tra esseri umani e divinità è riscritta alla luce della nozione romana di fides. Ma se la quasi totalità di questi miti, in cui il dio promette all’interagente mortale un pegno, un dono o un privilegio, è giustificata dalla presenza di vincoli di tipo amoroso, parentale o devozionale, un caso a parte rappresenta il racconto di Numa Pompilio e Giove (Fast. 3. 285-392) – un racconto Romano – in cui l’agente umano merita i pignora certa del dio e instaura con lui un rapporto di reciprocità. Il contributo si propone di esaminare questa rappresentazione della fides pollicita attraverso un confronto…

Thieme Chemistry Journals Awardees – Where Are They Now? Molybdenum(V)-Mediated Synthesis of Nonsymmetric Diaryl and Aryl Alkyl Chalcogenides

2017

Oxidative chalcogenation reaction using molybdenum(V) reagents provides fast access to a wide range of nonsymmetric aryl sulfides and selenides. The established protocol is tolerated by a variety of labile functions, protecting groups, and aromatic heterocycles. In particular, when labile moieties are present, the use of molybdenum(V) reagents provides superior yields compared to other oxidants.

Chemically Selective Imaging of Individual Bonds through Scanning Electron Energy-Loss Spectroscopy : Disulfide Bridges Linking Gold Nanoclusters

2020

As proof-of-principle of chemically selective, spatially resolved imaging of individual bonds, we carry out electron energy-loss spectroscopy in a scanning transmission electron microscopy instrument on atomically precise, thiolate-coated gold nanoclusters linked with 5,5′-bis(mercaptomethyl)-2,2′-bipyridine dithiol ligands. The images allow the identification of bridging disulfide bonds (R–S–S–R) between clusters, and X-ray photoelectron spectra support the finding. peerReviewed

Oktakarboksyftalocyjaniny jako katalizatory utleniania związków siarki

2007

Zbadano aktywność katalityczną oktakarboksyftalocyjaniny kobaltu (CoPcOC), żelaza (FePcOC) i miedzi (CuPcOC) w aerobowym utlenianiu 2-tioetanolu, siarczku sodu i L-cysteiny. Kompleksy kobaltu i żelaza okazały się efektywnymi katalizatorami homofazowymi tych reakcji. Na aktywność katalityczną wpływ mają takie czynniki, jak rodzaj skompleksowanego metalu, pH, asocjacja ftalocyjanin w roztworze.

Titanocene Selenide Sulfides Revisited: Formation, Stabilities, and NMR Spectroscopic Properties

2019

[TiCp2S5] (phase A), [TiCp2Se5] (phase F), and five solid solutions of mixed titanocene selenide sulfides [TiCp2SexS5−x] (Cp = C5H5−) with the initial Se:S ranging from 1:4 to 4:1 (phases B–E) were prepared by reduction of elemental sulfur or selenium or their mixtures by lithium triethylhydridoborate in thf followed by the treatment with titanocene dichloride [TiCp2Cl2]. Their 77Se and 13C NMR spectra were recorded from the CS2 solution. The definite assignment of the 77Se NMR spectra was based on the PBE0/def2-TZVPP calculations of the 77Se chemical shifts and is supported by 13C NMR spectra of the samples. The following complexes in varying ratios were identified in the CS2 solutions of …