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21.
[reaction: see text] The stereoselective aldol reaction of 3-silyloxyfurans with aldehydes in the presence of a Lewis acid is described. N-Bromosuccinimide (NBS)-mediated cyclization of the aldol product leads to the formation of the 2,7-dioxa-bicyclo[2.2.1]heptan-3-one ring system, which represents the formal product of hetero Diels-Alder reaction of the furan with the aldehyde. 相似文献
22.
Sylvie BertinJean-Jacques Robin 《European Polymer Journal》2002,38(11):2255-2264
Recycling of mixed plastic wastes composed of low-density polyethylene (LDPE) matrix and polypropylene (PP) was carried out by compounding using single-screw or twin-screw extruders. Blends of virgin polymers have been prepared to compare mechanical properties of both virgin and regenerated materials. First, a model composition of virgin LDPE/PP blend was prepared to study the effect of process parameters and that of different types of compatibilizers. Second, the results were applied to plastic wastes coming from industrial post-consumer plastic wastes. By adding compatibilizing agents such as ethylene-propylene-diene monomer, ethylene-propylene monomer, or PE-g-(2-methyl-1,3-butadiene) graft copolymer, elongation at break and impact strength were improved for all blends. The effect of these various copolymers is quite different and is in relation with their chemical structure. The recycled blends exhibit suitable properties leading to applications that require good mechanical properties. 相似文献
23.
Hartl F Mahabiersing T Chardon-Noblat S Da Costa P Deronzier A 《Inorganic chemistry》2004,43(22):7250-7258
IR, UV-vis, and EPR spectroelectrochemistry at variable temperatures and in different solvents were applied to investigate in situ the formation of electroactive molecular chains with a nonbridged Os-Os backbone, in particular, the polymer [Os(0)(bpy)(CO)(2)](n) (bpy = 2,2'-bipyridine), from a mononuclear Os(II) carbonyl precursor, [Os(II)(bpy)(CO)(2)Cl(2)]. The one-electron-reduced form, [Os(II)(bpy(.)(-))(CO)(2)Cl(2)](-), has been characterized spectroscopically at low temperatures. This radical anion is the key intermediate in the electrochemical propagation process responsible for the metal-metal bond formation. Unambiguous spectroscopic evidence has been gained also for the formation of [[Os(0)(bpy(*)(-))(CO)(2)](-)](n), the electron-rich electrocatalyst of CO(2) reduction. The polymer species are fairly well soluble in butyronitrile, which is important for their potential utilization in nanoscience, for example, as conducting molecular wires. We have also shown that complete solubility is accomplished for the monocarbonyl-acetonitrile derivative of the polymer, [Os(0)(bpy)(CO)(MeCN)(2)Cl](n). 相似文献
24.
Chardon-Noblat S Horner O Chabut B Avenier F Debaecker N Jones P Pécaut J Dubois L Jeandey C Oddou JL Deronzier A Latour JM 《Inorganic chemistry》2004,43(5):1638-1648
Reaction of the unsymmetrical phenol ligand 2-((bis(2-pyridylmethyl)amino)methyl)-6-(((2-pyridylmethyl)benzylamino)methyl)-4-methylphenol (HL-Bn) or its 2,6-dichlorobenzyl analogue (HL-BnCl(2)) with Fe(H(2)O)(6)(ClO(4))(2) in the presence of disodium m-phenylenedipropionate (Na(2)(mpdp)) followed by exposure to atmosphere affords the diiron(II,III) complexes [Fe(2)(L-Bn)(mpdp)(H(2)O)](ClO(4))(2) and [Fe(2)(L-BnCl(2))(mpdp)(CH(3)OH)](ClO(4))(2), respectively. The latter complex has been characterized by X-ray crystallography. It crystallizes in the monoclinic system, space group P2(1)/n, with a = 13.3095(14) A, b = 20.1073(19) A, c = 19.4997(19) A, alpha = 90 degrees, beta = 94.471(2) degrees, gamma = 90 degrees, V = 5202.6(9) A(3), and Z = 4. The structure of the compound is very similar to that of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) determined earlier, except for the replacement of a water by a methanol on the ferrous site. Magnetic measurements of [Fe(2)(L-Bn)(mpdp)(H(2)O)](BPh(4))(2) reveal that the two high-spin Fe ions are moderately antiferromagnetically coupled (J = -3.2(2) cm(-)(1)). Upon dissolution in acetonitrile the terminal ligand on the ferrous site is replaced by a solvent molecule. The acetonitrile-water exchange has been investigated by various spectroscopic techniques (UV-visible, NMR, M?ssbauer) and electrochemistry. The substitution of acetonitrile by water is clearly evidenced by M?ssbauer spectroscopy by a reduction of the quadrupole splitting value from 3.14 to 2.41 mm/s. In addition, it causes a 210 mV downshift of the oxidation potential of the ferrous site and a similar reduction of the stability domain of the mixed-valence state. Exhaustive electrolysis of a solution of [Fe(2)(L-Bn)(mpdp)(H(2)O)](2+) shows that the aqua diferric species is not stable and undergoes a chemical reaction which can be partly reversed by reduction to the mixed-valent state. This and other electrochemical observations suggest that upon oxidation of the diiron center to the diferric state the aqua ligand is deprotonated to a hydroxo. This hypothesis is supported by M?ssbauer spectroscopy. Indeed, this species possesses a large quadrupole splitting value (DeltaE(Q) >or= 1.0 mm.s(-)(1)) similar to that of analogous complexes with a terminal phenolate ligand. This study illustrates the drastic effects of aqua ligand exchange and deprotonation on the electronic structure and redox potentials of diiron centers. 相似文献
25.
Rijssenbeek JT Malo S Caignaert V Poeppelmeier KR 《Journal of the American Chemical Society》2002,124(10):2090-2091
Sr(3)CaRu(2)O(9), a new 2:1 B-site ordered perovskite ruthenate, was synthesized and its structure determined based on powder X-ray, neutron and electron diffraction data. It is composed of one layer of CaO(6) alternating with two layers of RuO(6) perpendicular to the [111] axis of the cubic perovskite structure. The ordering leads to a [-Ru-Ru-Ca-] repeat unit along each of the pseudocubic directions. Sr(3)CaRu(2)O(9) is the first example of this structure-type to include a majority metal with d electrons (Ru(V), d(3)). Three-dimensional Sr(3)CaRu(2)O(9) can be transformed to the layered Ruddlesden-Popper phase Sr(1.5)Ca(0.5)RuO(4) (i.e., Sr(3)CaRu(2)O(8)) by reduction at 1200 degrees C in flowing argon. The original structure can be restored by oxidation of Sr(1.5)Ca(0.5)RuO(4) at 1000 degrees C in flowing oxygen. This remarkable transformation highlights the structural versatility afforded by the combination of ruthenium and calcium. 相似文献
26.
Walsh CT Garneau-Tsodikova S Gatto GJ 《Angewandte Chemie (International ed. in English)》2005,44(45):7342-7372
The diversity of distinct covalent forms of proteins (the proteome) greatly exceeds the number of proteins predicted by DNA coding capacities owing to directed posttranslational modifications. Enzymes dedicated to such protein modifications include 500 human protein kinases, 150 protein phosphatases, and 500 proteases. The major types of protein covalent modifications, such as phosphorylation, acetylation, glycosylation, methylation, and ubiquitylation, can be classified according to the type of amino acid side chain modified, the category of the modifying enzyme, and the extent of reversibility. Chemical events such as protein splicing, green fluorescent protein maturation, and proteasome autoactivations also represent posttranslational modifications. An understanding of the scope and pattern of the many posttranslational modifications in eukaryotic cells provides insight into the function and dynamics of proteome compositions. 相似文献
27.
E.Peter Kündig MundruppadyS. Laxmisha Rita Cannas Sylvie Tchertchian Liu Ronggang 《Helvetica chimica acta》2005,88(5):1063-1080
An efficient dearomatization process of [Cr(arene)(CO)3] complexes initiated by a nucleophilic acetaldehyde equivalent is detailed. It generates in a one‐pot reaction three C? C bonds and two stereogenic centers. This process allowed a rapid assembly of a cis‐decalin ring system incorporating a homoannular diene unit in just two steps starting from aromatic precursors (Scheme 2). The method was applied to the total synthesis of the eudesmane‐type marine furanosesquiterpene (±)‐15‐acetoxytubipofuran ( 2 ). Two routes were successfully used to synthesize the γ‐lactone precursor of the furan ring. The key step in the first approach was a Pd‐catalyzed allylic substitution (Scheme 3), while in the second approach, an Eschenmoser–Claisen rearrangement was highly successful (Scheme 4). The Pd‐catalyzed allylic substitution could be directed to give either the (normal) product with overall retention as major diastereoisomer or the unusual product with inversion of configuration (see Table). For the synthesis of the (?)‐enantiomer (R,R)‐ 2 of 15‐acetoxytubipofuran, an enantioselective dearomatization in the presence of a chiral diether ligand was implemented (Scheme 7), while the (+)‐enantiomer (S,S)‐ 2 was obtained via a diastereoselective dearomatization of an arene‐bound chiral imine auxiliary (Scheme 8). Chiroptical data suggest that a revision of the previously assigned absolute configuration of the natural product is required. 相似文献
28.
29.
Veronika Pilařová Tomáš Gottvald Pavel Svoboda Ondřej Novák Karolína Benešová Sylvie Běláková Lucie Nováková 《Analytica chimica acta》2016
The goal of this study was to develop an effective supercritical fluid chromatography method using single quadrupole MS for analysis of all isomeric forms of vitamin E. Finally, two fast and effective methods, the high resolution one and the high speed one, for the determination of 8 vitamin E isomers in human serum were developed. 相似文献
30.
Hussein Awada Hussein Medlej Sylvie Blanc Marie‐Hélène Delville Roger C. Hiorns Antoine Bousquet Christine Dagron‐Lartigau Laurent Billon 《Journal of polymer science. Part A, Polymer chemistry》2014,52(1):30-38
We demonstrate an efficient strategy to anchor poly(3‐hexylthiophene) (P3HT) onto zinc oxide (ZnO) surfaces. Synthesis of a novel triethoxysilane‐terminated regioregular P3HT is herein reported and supported by thorough characterization. Three triethoxysilane‐terminated P3HTs of different molar masses were prepared via a hydrosilylation reaction from allyl‐terminated P3HT. MALDI‐TOF and 1H NMR were performed to characterize the polymer and show that around 80% of the chains are end‐functionalized. These polymers were then grafted onto the ZnO nanorods to create a macromolecular self‐assembled monolayer. This versatile technique could be subsequently applied to different metal oxide surfaces, such as silicon, titanium, or indium‐tin oxide, and represents a new one‐pot strategy based on triethoxysilane coupling reaction. Importantly, the influence of the molar mass on the grafting density and the polymer shell thickness was studied via thermo gravimetric analysis and transmission electron microscopy. The optical properties of the hybrid materials were determined by UV–visible absorption and photoluminescence to show a quenching effect of P3HT fluorescence by ZnO when grafted. This electronic transfer associated with an improved miscibility of the ZnO@P3HT, makes these hybrid materials suitable candidates for photovoltaic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014 , 52, 30–38 相似文献