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61.
Nucleophilic displacement of halide from 2-halo 1,4-quinones occurs at the carbon or at the carbon vicinal to it depending on the nature of the nucleophile and the solvent. 相似文献
62.
Alberto Girlando Cristina Sissa Francesca Terenziani Anna Painelli Anna Chwialkowska Geoffrey J Ashwell 《Chemphyschem》2007,8(15):2195-2201
We report visible, Raman, and infrared spectra of self-assembled monolayers (SAMs) formed by the donor-(pi-bridge)-acceptor chromophore, Z-beta-[N-(omega-acetylthioalkyl)-4-quinolinium]-alpha-cyano-4-styryldicyanomethanide (CH3CO-S-CnH2n-Q3CNQ where n=8, 10), on gold-coated substrates. The data are compared with the spectra collected for the same compound in solution and in the solid state, and with those obtained for a Langmuir-Blodgett (LB) monolayer of C16H33-Q3CNQ deposited on gold. Spectral analysis confirms that in solution, in the solid state and in the LB film the chromophore has a zwitterionic (D+-pi-A-) ground state. At variance with this well-known result, our data show that in SAMs deposited on gold the chromophore has a more neutral, quinoid ground state. We relate this difference to the different packing of the molecules in the two different films: in SAMs in fact the chromophores stand almost vertical with respect to the substrate, whereas in LB films they make an angle of about 45 degrees. The Q3CNQ molecule is a well-known molecular rectifier, and for SAMs we were able to check the direction of electron flow at forward bias on the same samples that have been characterized spectroscopically, shedding light on the rectification mechanism. 相似文献
63.
Rieth LR Moore DR Lobkovsky EB Coates GW 《Journal of the American Chemical Society》2002,124(51):15239-15248
Polymerization of beta-butyrolactone (BBL) and beta-valerolactone (BVL) using the zinc alkoxide initiator (BDI-1)ZnO(i)()Pr [(BDI-1) = 2-((2,6-diisopropylphenyl)amido)-4-((2,6-diisopropylphenyl)imino)-2-pentene] proceeds very rapidly under mild conditions to produce poly(3-hydroxybutyrate) (PHB) and poly(3-hydroxyvalerate) (PHV), respectively. For the monomer-to-initiator ratio 200:1, PHB number-average molecular weights (M(n)) are proportional to conversion throughout the reaction and polydispersity indices (PDIs) are narrow, consistent with a living polymerization. Higher monomer-to-initiator ratios can be used to achieve high molecular weight PHB (M(n) > 100 000). End-group analysis verifies that the polymerization of BBL follows a coordination-insertion mechanism, where complexes of the form (BDI-1)ZnOCH(Me)CH(2)CO(2)R are the active species. Variable temperature NMR experiments show that (BDI-1)ZnO(i)()Pr is monomeric in benzene-d(6) solution. In contrast, (BDI-2)ZnO(i)()Pr [(BDI-2) = 2-((2,6-diethylphenyl)amido)-4-((2,6-diethylphenyl)imino)-2-pentene] is a poor initiator at room temperature because it prefers to form a bis-mu-isopropoxide dimer in solution. According to kinetic studies, propagation by (BDI-1)ZnO(i)()Pr is first order in both monomer as well as (BDI-1)ZnO(i)()Pr concentration. These results lead us to propose a monometallic active species. Several results suggest that elimination side reactions are slowly catalyzed by zinc alkoxides, leading to degradation of the polymer. 相似文献
64.
Halfyard J Galloro J Ginzburg M Wang Z Coombs N Manners I Ozin GA 《Chemical communications (Cambridge, England)》2002,(16):1746-1747
Direct visualization of organometallic-organic and novel all-organometallic multilayer superlattices prepared by layer-by-layer assembly of cationic/anionic polyferrocenylsilane and anionic polystyrene sulfonate polyelectrolytes using a gold coating/transmission electron microscopy (TEM) technique is reported. 相似文献
65.
66.
Kulbaba K Cheng A Bartole A Greenberg S Resendes R Coombs N Safa-Sefat A Greedan JE Stöver HD Ozin GA Manners I 《Journal of the American Chemical Society》2002,124(42):12522-12534
Pt(0)-catalyzed ring-opening precipitation copolymerization of [1]silaferrocenophanes fcSiMe(2) (3) and the spirocyclic cross-linker fcSi(CH(2))(3) (4) (fc = Fe(eta(5)-C(5)H(4))(2)) was used to prepare polyferrocenylsilane microspheres (PFSMSs) under mild conditions. By varying the reaction conditions, a wide variety of other morphologies was obtained. The effects of temperature, monomer ratio, solvent composition, catalyst concentration, and time on the observed morphology were investigated and interpreted in terms of a mechanism for microsphere formation. The most well-defined particles were formed using equimolar amounts of 3 and 4, in a 50:50 mixture of xylenes and decane at 60 degrees C with gentle agitation. Chemical oxidation of the polymeric microspheres led to positively charged particles (OPFSMSs) which underwent electrostatically driven self-assembly with negatively charged silica microspheres to form core-corona composite particles. Redox titration with controlled amounts of the one-electron oxidant [N(C(6)H(4)Br-p)(3)][PF(6)] in acetonitrile led to the oxidation of the outer 0.15 microm (ca. 32%) of the PFSMSs. The resulting OPFSMSs were reduced back to their neutral form by reaction with hydrazine in methanol. Pyrolysis of the PFSMSs led to spherical magnetic ceramic replicas with tunable magnetic properties that organize into ordered 2-D arrays at the air-water interface under the influence of a magnetic field. 相似文献
67.
Geoffrey Laforte 《Mathematical Logic Quarterly》1996,42(1):83-103
In the present paper we prove that the isolated differences of r. e. degrees are dense in the r. e. degrees. Mathematics Subject Classification: 03D25. 相似文献
68.
The main reaction products resulting from the addition of atomic hydrogen to acetylene are shown to be ethylene, 1,3-butadiene, and benzene. The mechanism involves chain reactions of the vinyl and butadienyl radicals, which regenerate atomic hydrogen. Some of the rate parameters are estimated. 相似文献
69.
Kwok W. Chiu David Lyons Geoffrey Wilkinson Mark Thornton-Pett Michael B. Hursthouse 《Polyhedron》1983,2(8):803-810
The reduction of WCl4(PMe3)3 by sodium amalgam in presence of phenylacetylene gives W(PMe3)(PhCCH)3 (A). Reduction in presence of methylisocyanide gives W(PMe3)2(MeNC)4 (B), while in presence of excess PMe3 in tetrahydrofuran under hydrogen, WH2Cl2(PMe3)4 (C) is formed. The reaction of WCl2(PMe3)4 with methanol in tetrahydrofuran gives mixtures of WH2Cl2(PMe3)4 and WOC12(PMe3)3 (D).The structures of A, B, and D have been determined by X-ray diffraction. 相似文献
70.
On the dynamics of plastic circular plates 总被引:5,自引:0,他引:5
H. Geoffrey Hopkins William Prager 《Zeitschrift für Angewandte Mathematik und Physik (ZAMP)》1954,5(4):317-330
The paper is concerned with the dynamics of a thin circular plate made of a plastic-rigid material that obeys the yield condition ofTresca and the associated flow rule. The basic equations are established in the case of rotational symmetry, and their complete solution is given for a simply supported plate subjected to a uniformly distributed load which is brought on suddenly and, after a certain time interval, removed suddenly.
Résumé Cet article étudie la dynamique d'une plaque circulaire infiniment mince fabriquée avec un matériau plastique qui obéit à la condition de plasticité deTresca et à la loi d'écoulement associée. Les équations fondamentales sont établies dans le cas où existe une symétrie de révolution. Leur solution complète est donnée pour une plaque reposant sur des appuis simples, soumise à une charge uniformément répartie qui est appliquée rapidement et demeure constante pendant un certain temps, après lequel elle est rapidement retirée.相似文献