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1.
The absorption of pulsed CO2-laser radiation by ethylene has been measured at total pressures from 25 to 3000 Torr, using the P(12) and P(14) lines in the 10.6 m band, with incident fluences from 0.1 to 0.7 J/cm2. Marked deviations from the Beer-Lambert absorption law were observed, with the effective absorption coefficient varying with pressure, fluence, absorption path-length and the addition of non-absorbing gas. Pressure broadening of the rotational lines of the ethylene absorption spectrum was shown to be the major cause of these deviations, together with lesser effects which can be attributed to the rise in temperature of the absorbing gas during the laser pulse. 相似文献
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Publications on the binding characteristics of metals with humic acid (HA) are sparse. Here we investigated the release of nickel from Ni(II)-HA complexes using model solutions of three different [Ni(II)]/[HA] mole ratios at three different pH values; we also compared the results with those of [Ni(II)]/[FA] complexes from previous work in this laboratory. Ligand exchange kinetics using the competing ligand exchange method (CLEM) were studied using two different techniques: graphite furnace atomic absorption spectrometry (GFAAS) with Chelex 100 resin as the competing ligand, and adsorptive cathodic stripping voltammetry (AdCSV) with dimethylglyoxime as the competing ligand to measure the rate of dissociation of Ni(II)-HA complexes. The results of the kinetic studies showed that as the [Ni(II)]/[HA] mole ratio was decreased, the rate of dissociation of Ni(II)-HA complexes decreased, and the proportion of free Ni2+ ions plus very labile nickel complexes decreased while the proportion of the less labile kinetically distinguishable components increased. Generally, the rate of dissociation of Ni(II)-HA complexes was slower than that of Ni(II)-FA complexes. Studies on the validity of the kinetic model showed that the concentrations of chemical species varied in a reasonable way with pH and the [Ni(II)]/[HA] mole ratios, indicating that the kinetically distinguishable components have chemical significance and the kinetic model is valid. 相似文献
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The synthesis of some novel bakkenolides and their epi-spiro analogues was achieved by a new approach. Photolysis of allyl 1-(phenylseleno)-2-oxocyclopentanecarboxylates 7-9 afforded the corresponding spiro lactones 10-12 by radical cyclization via group transfer of the phenylseleno group. Selenoxide elimination of 11 and 12 produced the corresponding beta-methylene lactones 14 and 15. Diels-Alder cycloaddition of lactone11 with piperylene failed at ambient pressure, but proceeded in generally good yield in the presence of various Lewis acids at pressures of ca. 16 kbar, to give mixtures of beta-exo, alpha-endo, and beta-endo cycloadducts 19, 21, and 23, respectively. The preponderance of endo products 21 and 23, formed via highly hindered, but more compact, transition states was attributed to the high pressure and resulted in trans-dimethyl configurations of the products. The facial selectivity was dependent upon the Lewis acids, and the greatest alpha:beta ratio was observed with catalysts of the type TiCl(2)(OR)(2). Epimerization of the C-4 methyl group in 21 and 23 to furnish the corresponding cis-dimethyl analogues was achieved via exo-epoxidation, regioselective reduction, oxidation to the corresponding 3-keto derivatives, and base-catalyzed equilibration, thereby affording (+/-)-3,6-dioxobakkenolide-A (39) and its epi-spiro derivative 28, respectively. When the radical cyclization step was performed subsequent to the Diels-Alder cycloaddition by photolysis of perhydrindane 43, only the epi-spiro product 44 was obtained. 相似文献
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Oliver Back Dr. Christoph Förster Prof. Dr. Thomas Basché Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2019,25(26):6542-6552
2-Iminopyrroles [HtBuL, 4-tert-butyl phenyl(pyrrol-2-ylmethylene)amine] are non-fluorescent π systems. However, they display blue fluorescence after deprotonation with alkali metal bases in the solid state and in solution at room temperature. In the solid state, the alkali metal 2-imino pyrrolates, M(tBuL), aggregate to dimers, [M(tBuL)(NCR)]2 (M=Li, R=CH3, CH(CH3)CNH2), or polymers, [M(tBuL)]n (M=Na, K). In solution (solv=CH3CN, DMSO, THF, and toluene), solvated, uncharged monomeric species M(tBuL)(solv)m with N,N′-chelated alkali metal ions are present. Due to the electron-rich pyrrolate and the electron-poor arylimino moiety, the M(tBuL) chromophore possesses a low-energy intraligand charge-transfer (ILCT) excited state. The chelated alkali cations rigidify the chromophore, restricting intramolecular motions (RIM) by the chelation-enhanced fluorescence (CHEF) effect in solution and, consequently, switch-on a blue fluorescence emission. 相似文献
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Franziska Back Matthias Bockmeyer Eveline Rudigier-Voigt Peer Löbmann 《Journal of Sol-Gel Science and Technology》2013,66(1):73-83
Hybrid polymer solutions suitable for UV-nanoimprint were synthesized by combination of an alkoxysilane binder mixture with silica nanoparticles. Hydrolysis and condensation reactions were monitored by NMR and viscosity measurements. Thereby long-term stable systems were produced as a prerequisite for industrial application. Dip-coating of glass substrates and subsequent UV-curing yielded thin films. Their thermal densification and microstructural evolution resulted in pure glassy porous coatings, which were in detail characterized by N2-sorption measurements and ellipsometric porosimetry. Results emphasize the importance of the binder-particle interaction within these materials that are destined for the fabrication of microstructured surfaces by cost efficient and industrially feasible UV-based soft lithography. Structured glassy layers with high inorganic content show thermal stability up to >500 °C and have a high structure accuracy >85 %. 相似文献