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2.
Protein S-nitrosation is an important post-translational modification. However, the detection of S-nitrosation is still problematic because S-nitrosation products, that is, S-nitrosothiols, are unstable species. Here a new reaction which can selectively convert unstable S-nitrosothiols to stable thioethers in one-pot under very mild conditions is reported. This reaction has the potential to be applied in the detection of protein S-nitrosation. 相似文献
3.
Abstract Two trithiamacrocycles have been designed by molecular modelling to have preorganised endodentate sulfur donor atoms. These new macrocycles have five- and six-membered saturated heterocycles inserted into 2,5,8-trithia[9]-m-benzenophane; molecular dynamics simulations suggest that the endo forms will be rigid on a nanosecond timescale. Optimum metal-sulfur distances which the new ligands will accommodate lie between 2.76 Å and 2.95 Å, suggesting they will be particularly suitable for a large soft metal ion such as silver(I). 相似文献
4.
Hermes JP Sander F Peterle T Urbani R Pfohl T Thompson D Mayor M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(48):13473-13481
Ligand-stabilized gold nanoparticles (Au NPs) are promising materials for nanotechnology with applications in electronics, catalysis, and sensors. These applications depend on the ability to synthesize stable and monodisperse NPs. Herein, the design and synthesis of two series of dendritic thioether ligands and their ability to stabilize Au NPs is presented. The dendrimers have 1,3,5-trisubstituted benzene branching units bridged by either meta-xylene or ethylene moieties. A comparison between the two ligands shows how both size control and the stability of the NPs are influenced by the nature of the ligand-NP wrapping interaction. The meta-xylene-bridged ligands provided NPs with a narrow size distribution centered around a diameter of 1.2 nm, whereas the NPs formed with ethylene-bridged dendrimers lack long-term stability with NP aggregation detected by UV/Vis spectroscopy and transmission electron microscopy. The bulkier tert-butyl-functionalized meta-xylene bridges form larger ligand shells that inhibit further growth of the NPs and thus provide a simple route to stable and monodisperse Au NPs that may find use as functional components in nanoelectronic devices. 相似文献
5.
Peterle T Leifert A Timper J Sologubenko A Simon U Mayor M 《Chemical communications (Cambridge, England)》2008,(29):3438-3440
The design and synthesis of oligomeric ligands based on benzylic thioethers is presented together with their ability to enwrap and stabilize gold nanoparticles with diameters below 2 nm, which become--with increasing length of the oligomer--more monodisperse and stable. 相似文献
6.
S. E. Mitrofanova E. N. Girfanova I. Yu. Averko-Antonovich E. N. Cherezova 《Russian Journal of Applied Chemistry》2006,79(1):137-141
Polyfunctional oligomeric antioxidants with a sterically hindered phenolic fragment were prepared. The influence of these antioxidants on oxidation and degradation of SKI-3 rubber was analyzed. 相似文献
7.
Jadranka ?ubrilo Ingo Hartenbach Thomas Schleid Rainer F. Winter 《Journal of organometallic chemistry》2007,692(7):1496-1504
Thioethers PhC2H4SMe, PhC3H6SiPr and MeSAllyl form substitutionally labile monomeric adducts (p-cymene)RuCl2(SRR′) (2a-c) upon treatment with the {(p-cymene)RuCl2}2 dimer (p-cymene = η6-MeC6H4iPr-1,4). Pure adducts were obtained by crystallization from CH2Cl2/Et2O, and 2a,c as well as the bis(thioether) complex (3) were studied by X-ray crystallography. The trichloro bridged diruthenium complex is formed as a byproduct in the preparation of 3 and was also crystallographically characterized. In solution, pure samples 2a-c equilibrate with free thioether and the dimeric starting complex 1. The amount of 1 present in these mixtures increases with increasing bulk of the thioether substituents. Attempts to thermally replace the cymene ligand by the dangling arene substituent of the thioether ligand of 2a,b failed. Complexes 2a-c as well as the dimethylsufide derivative 2d were studied by cyclic voltammetry and display a close to reversible (2a,c,d) or partially reversible (2b) oxidation near +0.85 V and an irreversible reduction at rather negative potential. New peaks observed after oxidation and reduction point to dissociation of the thioether ligand as the main decomposition pathway of the associated radical cations and anions. 相似文献
8.
Michael M. Pollard 《Tetrahedron》2006,62(51):11908-11915
This paper describes a convenient and high yielding three-step approach for the synthesis of trans-tetraphenylporphyrins possessing two thioethers in the ortho positions, which will facilitate the synthesis of more elaborate and complex porphyrin architectures. Their synthesis is realized by a double nucleophilic aromatic substitution of 2 equiv of a thiolate on 2,6-dichlorobenzaldehyde to generate a bis-thioether substituted benzaldehyde. This aldehyde is then condensed with 2 equiv of pyrrole to give a dipyrromethane, which in the final step reacts with an aromatic aldehyde to give a series of thioether-substituted trans-tetraphenylporphyrins. 相似文献
9.
V. R. Durvasula F. A. Stuber D. Bhattacharjee 《Journal of polymer science. Part A, Polymer chemistry》1989,27(2):661-669
The known polymerization of 4,4′-difluorobenzophenone (DFB) with the dianion of hydroquinone to poly(phenylene ether ether ketone) (PEEK) and polymerization of either DFB with the dianion of 4,4′-dihydroxybenzophenone or self polycondensation of the anion of 4-hydroxy-4′-fluoro-benzophenone to poly(phenylene ether ketone) (PEK) were studied in N-cyclohexyl-2-pyrrolidone (CHP), which is a high-boiling aprotic polar solvent. The formation of high-molecular weight PEEK and PEK in this solvent was very efficient. The reactivity in CHP can be ascribed to effective solvation of metal ions rendering the anion very reactive toward nucleophilic substitution. The polymerization was extended to 4,4′-bis(4-fluorobenzoyl)diphenyl ether and 1,4-bis[4-(4-fluorobenzoyl)phenoxy]benzene to give a high molecular weight polymer with PEK and PEEK repeating units and PEEK respectively. The polymerization of DFB with purified anhydrous sodium sulfide in CHP gave rapidly a high molecular weight poly(phenylene ketone sulfide) (PKS). In contrast, diphenyl sulfone (DPS) was not very effective in obtaining such a high molecular weight PKS even with prolonged heating, which suggests the uniqueness of CHP in promoting a high degree of polymerization. 相似文献
10.
《中国化学快报》2022,33(8):4021-4025
Dielectric elastomers (DEs) have drawn much attention owing to their application prospects in artificial muscles and soft robotics, it is still a big challenge to prepare DEs with high electromechanical performances. This work reports a highly stretchable poly(thioether)-b-polysiloxane-b-poly(thioether) triblock copolymer based homogenous DEs with high electromechanical properties. The triblock copolymer (PSiPGE) was synthesized through the ring-opening polymerization (ROP) of phenyl glycidyl ether (PGE) and carbonyl sulfide (COS) catalyzed by silicon alkoxides. The dipoles (benzene rings) on the side groups of PSiPGE improved the dipole polarizations and the phase separation structure of this triblock copolymer enhanced the interfacial polarizations between poly(thioether) and polysiloxane, and thus improving the dielectric constant (ε’, up to 5.8). In addition, the PSiPGE exhibited low elastic modulus (Y, 0.04 MPa), and thus possessed high electromechanical sensitivity (β, ~145 MPa?1) which is much higher than that of most homogenous DEs. This work provides a new strategy to construct homogenous DEs with excellent electromechanical performances, leading to a greater application aspect in the actuated devices. 相似文献
11.
Mitsuru Ueda Tetsuya Abe Mitsuo Oda 《Journal of polymer science. Part A, Polymer chemistry》1992,30(9):1993-1998
Aromatic poly(thioether ketone)s were prepared by the direct polycondensation of aromatic dicarboxylic acids with aryl compounds containing ether or sulfide structures using phosphorus pentoxide/methanesulfonic acid (PPMA) as a condensing agent and solvent. Polycondensation proceeded smoothly and produced aromatic poly(thioether ketone)s with inherent viscosities up to 0.73 dL/g. The synthesis of substituted aryl ketones by the reaction of substituted benzoic acids with aryl compounds in PMMA was studied in detail to demonstrate the feasibility of the reaction for polymer formation. The thermogravimetry of the aromatic poly(thioether ketone)s showed a 10% weight loss in air and nitrogen at around 450 and 460°C, respectively. © 1992 John Wiley & Sons, Inc. 相似文献
12.
Multimeric presentation, a rather effective way of enhancing peptide immunogenicity, is best exemplified by MAP (multiple antigenic peptide) dendrimers consisting of a branched Lys core on which several copies of the peptide epitope are displayed. While accessible by solid-phase synthesis, MAPs can also be conveniently made in solution, e.g., by linking the epitope (N-acetylated and with a C-terminal Cys) through a thioether bond onto the α and ε (haloacetyl-activated) positions of the Lys core. We now report the reverse version of this approach, whereby a chloroacetyl-derivatised epitope is tethered to a thiol-functionalised form of a Lys dendron core. This convergent approach can be carried out either in solution or in the solid phase and is advantageous because (i) in situ tris(2-carboxyethyl)phosphine (TCEP)-mediated reduction of disulfide bonds maintains the thiol platform reactive throughout the ligation process; (ii) the low amounts of TCEP used pose minimal risk to chloroacetyl groups in the peptide, resulting in (iii) significantly reduced byproduct formation, hence cleaner products. For the solid phase version of the method, an optimised procedure has been devised to convert the Lys core into a tetrathiol dendron. 相似文献
13.
《Journal of Inorganic and Nuclear Chemistry》1978,40(11):1957-1961
Four new chelating agents containing vicinal thioether groups have been prepared by the addition of the appropriate thiols to acetylenedicarboxylic acid. These new compounds are 4,5-Dicarboxy-3,6-dithiaoctanedioic acid, 2,9-Diamino-5,6-dicarboxy-4,7-dithiadecanedioic acid, 3,6-Dithiaoctanediamine-4,5-dicarboxylic acid dihydrochloride, and Disodium-3,6-dithia-1,8-octanediol-4,5-dicarboxylate. Reasonably stable complexes are formed with several divalent metal ions, through precipitation interfered with the complete characterization of the mercury(II) complexes in some cases. For all of these, the stability constants of the mercury(II) complexes were appreciably lower than the stability constants of structurally similar complexes containing vicinal mercaptal groups and the degree of selectivity for mercury(II) was also less. These chelating agents exhibit a very minimal tendency to bind calcium ions. 相似文献
14.
A. N. Tarasenkov E. V. Getmanova M. I. Buzin N. M. Surin A. M. Muzafarov 《Russian Chemical Bulletin》2011,60(12):2544-2549
Novel hyperbranched functional and non-functional carbosilane polymers bearing the thioether groups were synthesized. Thioether derivatives were prepared by the UV initiated hydrothiolation of the hyperbranched poly(allyl)carbosilane polymer with 1-decanethiol and 3-mercaptopropyl(methyl)dimethoxysilane. 相似文献
15.
The metalation of allyl benzyl thioether involves the benzylic or the allylic hydrogens. The benzylic carbanion undergoes a rapid[2,3] sigmatropic shift whereas the allylic carbanion gives rise to various rearrangements, among them migration of the allylic unit to the para position with allylic inversion. The temperature dependence of the ratio of products arising from the benzylic carbanion vs those from the allylic carbanion shows that the allylic-to-benzylic carbanion transformation occurs only under special conditions: (a) with slow addition of the base; (b) with thioether in excess relative to the base, and (c) on raising the temperature of the reaction medium from ?78° to ?15°. In the last instance, the proton transfer is intramolecular as shown with labeled thioethers. The extent of the different rearrangements depends on the temperature and solvent. A choice of mechanism cannot be made at this time for the para migration 5→9a. A leaving group effect on the reaction regioselectivity of the carbanion from allyl methyl thioether with benzyl halides has been noticed. The presence of dibenzyl indicates that, in addition to SN2 reactions, some electron transfer process is occurring. 相似文献
16.
Charles G. Riordan 《Coordination chemistry reviews》2010,254(15-16):1815-1825
This review traces the development and application of the tris(thioether)borate ligands, tripodal ligands with highly polarizable thioether donors. Areas of emphasis include the basic coordination chemistry of the mid-to-late first row transition metals (Fe, Ni, Co, Cu), and the role of the thioether substituent in directing complex formation, the modeling of zinc thiolate protein active sites, high-spin organo-iron and organo-cobalt chemistry, the preparation of monovalent complexes of Fe, Co and Ni, and dioxygen and sulfur activation by monovalent nickel complexes. 相似文献
17.
Functionalized 1-nitrohydrazones 5 react with sodium hydride in boiling benzene to afford different types of ring-closed products. The formation of the latter can be ascribed to competitive modes of evolution of first-formed nitrile imines. 相似文献
18.
Self-assembly of cationic surfactants that contain thioether groups in the hydrophobic tails 总被引:1,自引:0,他引:1
Lundberg D Shi L Menger FM 《Langmuir : the ACS journal of surfaces and colloids》2008,24(9):4530-4536
Self-assembly in aqueous solutions of cationic surfactants that carry thioether groups in their hydrophobic tails has been investigated. Of particular interest was the identification of possible changes in the aggregate structure due to the presence of sulfur atoms. Solutions of four different compounds [CH(3)CH(2)S(CH(2))(10)N(CH(3))(3)(+)Br(-) (2-10), CH(3)(CH(2))(5)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (6-6), CH(3)(CH(2))(7)S(CH(2))(6)N(CH(3))(3)(+)Br(-) (8-6), and CH(3)(CH(2))(7)S(CH(2))(8)N(CH(3))(3)(+)Br(-) (8-8)] were characterized by (1)H NMR, (13)C NMR, NMR diffusometry, and conductivity measurements. In addition to investigating aqueous solutions containing each of the thioethers present as the sole solute, mixtures of 2-10 or 6-6 with dodecyltrimethylammonium bromide (DTAB) were studied. The addition of a sulfide group to the hydrophobic tail causes an increase in the critical micelle concentration but has a limited effect on the aggregate structure. Micelles are formed at a well-defined concentration for all of the investigated surfactants and surfactant mixtures. However, a comparison of the behavior of concentrated solutions of 8-8 to that of solutions of hexadecyltrimethylammonium bromide (CTAB) of similar concentrations suggests that the presence of a sulfur atom decreases the tendency for micellar growth. This may be a consequence of a slightly higher preference for the micellar surface of a sulfur atom as compared to that of a methylene group in a similar position, an idea that is also supported by results for the surfactant mixtures. 相似文献
19.
改性Y型分子筛对硫醇硫醚的吸附脱除研究 《燃料化学学报》2017,45(12):1467-1472
通过液相离子交换法制备了Cu(I)Y、Ni Y、Ce Y分子筛,以XRD、低温N2吸附-脱附、NH3-TPD、吡啶红外Py-FTIR等方法对其进行物性表征。利用固定床技术、WK-2D微库伦仪及硫化学发光检测GC-SCD色谱评价了改性分子筛对于硫含量300μg/g模拟油(含硫化合物二丙硫醚、环己硫醇和1-庚硫醇与壬烷配制)及HDS汽油的吸附脱硫性能。结果表明,吸附剂对模拟油和HDS燃料油品中硫醇硫醚具有吸附效果,且改性后的分子筛在吸附脱硫过程中,强的B酸对于吸附脱硫有负作用,会使油品中硫醇硫醚发生催化反应,聚合的大分子硫化物遮盖及阻塞吸附活性位点,从而使吸附剂不能够完全地吸附硫化物,造成吸附硫容较小,而弱L酸无催化活性对吸附脱硫有正面影响。 相似文献
20.
Copper(I) complexes of the tridentate thioether ligands [PhB(CH(2)SCH(3))(3)] (abbreviated PhTt), [PhB(CH(2)SPh)(3)] (PhTt(Ph)), [PhB(CH(2)S(t)()Bu)(3)] (PhTt(t)()(Bu)), and [PhB(CH(2)S(p)()Tol)(3)] (PhTt(p)()(Tol)) and bidentate thioether ligands [Ph(2)B(CH(2)SCH(3))(2)] (Ph(2)Bt), [Et(2)B(CH(2)SCH(3))(2)] (Et(2)Bt), and [Ph(2)B(CH(2)SPh)(2)] (Ph(2)Bt(Ph)) have been prepared and characterized. The solution and solid state structures are highly sensitive to the identity of the borato ligand employed. Ligands possessing the smaller (methylthio)methyl donors, [PhTt] and [Ph(2)Bt], yielded tetrameric species, [(PhTt)Cu](4) and [(Ph(2)Bt)Cu](4), containing both terminal and bridging thioether ligation. The ligands containing the larger (arylthio)methyl groups, [PhTt(Ph)] and [PhTt(p)()(Tol)], form monomeric [PhTt(Ar)]Cu(NCCH(3)) in solution and one-dimensional extended structures in the solid state. Each complex type reacted cleanly with acetonitrile, pyridine, or triphenylphosphine generating the corresponding four-coordinate monomer, of which [PhTt(Ph)]Cu(PPh(3)), [PhTt(p)()(Tol)]Cu(PPh(3)), and [Et(2)Bt]Cu(PPh(3))(2) have been structurally characterized. 相似文献