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11.
Tetramethyl- and hexamethyl-substituted [2.2]metacyclophane monoenes (10 and 11) are transformed into their corresponding trans-dimethyldihydroethanophenanthrenium dications (14(2+) and 15(2+)) in FSO(3)H x SbF(5) (4:1) and FSO(3)H x SbF(5) (1:1) with SO(2)ClF or SO(2) as the solvent; these 10 pi-dications are equivalent to the C-4/C-5 diprotonated dications of the 2,7-dimethyl derivative of trans-DMDHP, 3a. The trans-12c,12d-dimethyl-12c,12d-dihydrobenzo[e]pyrene (6) reacts with FSO(3)H/SO(2)ClF under surprisingly mild conditions to give initially a persistent diprotonated dication (6H(2)(2+)) and, subsequently, the oxidation dication (6(2+)); the 6(2+):6H(2)(2+) ratio reaches 4:1 after 1 week at low temperature. Protonation of the anti-metacyclophane (13) was also examined. Charge delocalization mode and tropicity in the resulting dications are gauged via detailed NMR studies at 500 MHz. 相似文献
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16.
J. A. Moore T. D. Mitchell 《Journal of polymer science. Part A, Polymer chemistry》1983,21(5):1305-1314
Polyenaminoesters were prepared by condensation of succinyl succinic ester (SSE) and p-bis-carbomethoxy diacetyl benzene (CDB) with 1,3-bis(3-aminopropyl)-1,1,3,3-tetramethyldisiloxane. Conditions of solvent and temperature were discovered which yielded soluble polymer from SSE after heat treatment. CDB yields only tough, rubbery, insoluble products. 相似文献
17.
We investigate the static and dynamic behaviors of a Br adlayer electrochemically deposited onto single-crystal Ag(100) using an off-lattice model of the adlayer. Unlike previous studies using a lattice-gas model, the off-lattice model allows adparticles to be located at any position within a two-dimensional approximation to the substrate. Interactions with the substrate are approximated by a corrugation potential. Using density functional theory (DFT) to calculate surface binding energies, a sinusoidal approximation to the corrugation potential is constructed. A variety of techniques, including Monte Carlo and Langevin simulations, are used to study the behavior of the adlayer. The lateral root-mean-square (rms) deviation of the adparticles from the binding sites is presented along with equilibrium coverage isotherms, and the thermally activated Arrhenius barrier-hopping model used in previous dynamic Monte Carlo simulations is tested. 相似文献
18.
Molecular mechanics and dynamics calculations have been used in conjunction with experimental data to study the effects of amine ligand bulk on the formation of both guanine and methionine complexes with platinum diamine compounds. The AMBER force field has been supplemented with previous modifications [Yao; et al. Inorg. Chem. 1994, 33, 6061-6077. Cerasino; et al. Inorg. Chem. 1997, 36, 6070-6079] and has been further modified to include parameters for platinum bound to the sulfur atom of methionine. Molecular mechanics calculations with this modified AMBER force field have suggested that a platinum complex with two sulfur-bound methionine ligands and a bulky diamine ligand (N,N,N',N'-tetramethylethylenediamine, Me(4)en) would have severe interligand clashes; such interligand clashes are less pronounced in bis(9-ethylguanine) complexes. Consistent with these observations, NMR studies with [Pt(Me(4)en)(D(2)O)(2)](2+) have indicated that guanine 5'-monophosphate reacts in a 2:1 guanine:platinum ratio while both methionine and N-acetylmethionine react with only a 1:1 stoichiometry. Methionine forms a chelate via the sulfur and nitrogen atoms whereas N-acetylmethionine forms a chelate via the sulfur and oxygen atoms. The oxygen of the latter chelate can be displaced by the addition of guanosine 5'-monophosphate, although complete displacement of the N-acetylmethionine was not observed. 相似文献
19.
R.?Mitchell C.?M.?CarrEmail author M.?Parfitt J.?C.?Vickerman C.?Jones 《Cellulose (London, England)》2005,12(6):629-639
The surface chemical composition of raw unscoured cotton was successfully investigated by the surface analytical techniques
X-ray Photoelectron Spectroscopy (XPS) and Time of Flight Secondary Ion Mass Spectrometry (ToF-SIMS). The presence of non-cellulosic
material at the fibre surface was established and determined to be a complex mixture of fatty acids, alcohols, alkanes, esters
and glycerides. The effect of scouring and bleaching was to reduce the surface concentration of these materials but even after
aqueous processing some non-cellulosic material residue was still detected at the fibre surface. 相似文献
20.
J.K. Furdyna W. Giriat D.F. Mitchell G.I. Sproule 《Journal of solid state chemistry》1983,46(3):349-352
The lattice parameter of the diluted magnetic semiconductor Zn1?xMnxTe has been determined as a function of composition. This material crystallizes in the zinc-blende structure for values of x below about 0.75. The results show that for this range of composition the lattice parameter satisfies Vegard's law and is given by a(x) = (6.103 + 0.237x) Å. This result corrects earlier published values of a(x) for this material (Juza et al., Z. anorg. allg. Chem.285, 61 (1956)), which are in considerable error. Because of its rather pronounced dependence on x, the lattice parameter provides an excellent method for determining sample composition. By extrapolating the expression of a(x) to x = 1, the results also provide a value of 6.340 ± 0.005 Å for the lattice parameter of the hypothetical zinc-blende phase of pure MnTe. The strong dependence of the lattice parameter of Zn1?xMnxTe on x is responsible for most of the variation of its density with composition. 相似文献