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171.
The complete assignment of 19F, 1H and 13C NMR spectra for a monosubstituted octafluoro[2.2]paracyclophane derivative is described for the first time. The unambiguous assignments were achieved through the combination of 19F--1H HOESY, 1H COSY and 19F COSY techniques and then further confirmed employing a complementary approach using a Karplus-dependent 3JCF interaction. Interesting aspects of the coupling patterns for various JHH, JHF, JCF and JFF interactions are also discussed. 相似文献
172.
T. Graule A. von Bohlen J. A. C. Broekaert E. Grallath R. Klockenk?mper P. Tsch?pel G. T?lg 《Fresenius' Journal of Analytical Chemistry》1989,335(7):637-642
Summary Direct analysis methods and multistage combined analytical procedures for the determination of impurities at the g/g level and the upper ng/g level in high-purity powders of Al2O3, AlN, Si3N4 and SiC are described. Results obtained with a novel direct slurry-atomization technique using a Babington nebulizer and inductively coupled plasma optical emission spectrometry (ICP-OES) are presented. A comparison of analysis results of combined analytical procedures including wet chemical decomposition and determinations with graphite furnace atomic absorption spectrometry (ETAAS) or ICP-OES with those of slurry-atomization ICP-OES show the capabilities of this technique for routine analysis in production control. Detection limits for Al, B, Ca, Co, Cu, Fe, Mg, Mn, Si, Ti, W, V, and Zn in the matrices mentioned are between 0.03 and 2.5 g/g. For elemental concentrations 10 g/g relative standard deviations of the measurements are generally below 10%. The technique is shown to be a powerful tool for trace determinations in powder samples. This is shown by its use for analysis of a series of the ceramic powders mentioned and comparative results of other direct techniques such as total reflection X-ray fluorescence spectrometry and instrumental neutron activation analysis.
Herrn Prof. Dr. G. Tölg zum 60. Geburtstag von seinen Mitarbeitern gewidmet 相似文献
OES und AAS von hochreinen Pulvern für die Keramikherstellung
Herrn Prof. Dr. G. Tölg zum 60. Geburtstag von seinen Mitarbeitern gewidmet 相似文献
173.
Gonzales JM Barden CJ Brown ST Schleyer Pv Schaefer HF Li QS 《Journal of the American Chemical Society》2003,125(4):1064-1071
The adiabatic electron affinities of cyclopentadiene and 10 associated benzannelated derivatives have been predicted with both density functional and Hartree-Fock theory. These systems can also be regarded as benzenoid polycyclic aromatic hydrocarbons (PAHs) augmented with five-membered rings. Like the PAHs, the electron affinities of the present systems generally increase with the number of rings. To unequivocally bind an electron, cyclopentadiene must have at least two conventionally fused benzene rings. 1H-Benz[f]indene, a naphthalene-annulated cyclopentadiene, is predicted to have a zero-point energy corrected adiabatic electron affinity of 0.13 eV. Since the experimental E(A) of naphthalene is negative (-0.19 eV), the five-membered ring appendage contributes to the stability of the naphthalene-derived 1H-benz[f]indene radical anion significantly. The key to binding the electron is a contiguous sequence of fused benzenes, since fluorene, the isomer of 1H-benz[f]indene, with separated six-membered rings, has an electron affinity of -0.07 eV. Each additional benzene ring in the sequence fused to cyclopentadiene increases the electron affinity by 0.15-0.65 eV: the most reliable predictions are cyclopentadiene (-0.63 eV), indene (-0.49 eV), fluorene (-0.07 eV), 1H-benz[f]indene (0.13 eV), 1,2-benzofluorene (0.25 eV), 2,3-benzofluorene (0.26 eV), 12H-dibenzo[b,h]fluorene (0.65 eV), 13H-indeno[1,2-b]anthracene (0.82 eV), and 1H-cyclopenta[b]naphthacene (1.10 eV). In contrast, if the six-membered ring-fusion is across the C(2)-C(3) cyclopentadiene single bond, only a single benzene is needed to bind an electron. The theoretical electron affinity of the resulting molecule, isoindene, is 0.49 eV, and this increases to 1.22 eV for 2H-benz[f]indene. The degree of aromaticity is responsible for this behavior. While the radical anions are stabilized by conjugation, which increases with the size of the system, the regular indenes, like PAHs in general, suffer from the loss of aromatic stabilization in forming their radical anions. While indene is 21 kcal mol(-1) more stable than isoindene, the corresponding radical anion isomers have almost the same energy. Nucleus-independent chemical shift calculations show that the highly aromatic molecules lose almost all aromaticity when an extra electron is present. The radical anions of cyclopentadiene and all of its annulated derivatives have remarkably low C-H bond dissociation energies (only 18-34 kcal mol(-1) for the mono-, bi-, and tricyclics considered). Hydrogen atom loss leads to the restoration of aromaticity in the highly stabilized cyclopentadienyl anion congeners. 相似文献
174.
175.
Threshold energies Et are determined for photoelectron emission by 20 inorganic anions in aqueous solution (7.1 < Et < 9.1 eV). Calculated values of Et for Cl?, Br?, I? agree with experiment. The Et are correlated with charge-transf absorption spectra. 相似文献
176.
Alex Berlin Neil Gilkes Douglas Kilburn Vera Maximenko Renata Bura Alexander Markov Anton Skomarovsky Alexander Gusakov Arkady Sinitsyn Oleg Okunev Irina Solovieva John N. Saddler 《Applied biochemistry and biotechnology》2006,130(1-3):528-545
Seven cellulase preparations from Penicillium and Trichoderma spp. were evaluated for their ability to hydrolyze the cellulose fraction of hardwoods (yellow poplar and red maple) pretreated by organosolv extraction, as well as model cellulosic substrates such as filter paper. There was no significant correlation among hydrolytic performance on pretreated hardwood, based on glucose release, and filter paper activity. However, performance on pretreated hardwood showed significant correlations to the levels of endogenous β-glucosidase and xylanase activities in the cellulase preparation. Accordingly, differences in performance were reduced or eliminated following supplementation with a crude β-glucosidase preparation containing both activities. These results complement a previous investigation using softwoods pretreated by either organosolv extraction or steam explosion. Cellulase preparations that performed best on hardwood also showed superior performance on the softwood substrates. 相似文献
177.
178.
Ottmar Steinhauser Paul von Fragstein und Claus Harzdorf 《Fresenius' Journal of Analytical Chemistry》1967,232(4):241-251
Zusammenfassung Die Analyse hochprozentigen Flußspats wird in ihrer derzeitigen Ausführungsform beschrieben. Nach Beseitigung carbonatischer Begleiter durch eine Behandlung mit verd. Essigsäure wird die Kieselsäure entweder mit Flußsäure verflüchtigt und aus dem Gewichtsverlust bestimmt oder in einer gesonderten, mit Soda aufgeschlossenen Probe als Tetrapyridiniumdodecamolybdatosilicat gefällt und als SiO2 + 12 MoO3 ausgewogen. Der Bariumsulfatgehalt wird nach Verflüchtigung der Kieselsäure durch Abrauchen des verbleibenden Rückstandes mit Schwefelsäure und anschließendes Kochen mit verd. Salzsäure/Schwefelsäure in der üblichen Art ermittelt. Im Filtrat der Bariumsulfatfällung wird Calcium nach Abtrennung oder Maskierung der dreiwertigen Begleiter als Oxalat gefällt und zum Oxid verglüht oder direkt durch eine photometrische Titration mit ÄDTA bestimmt. Der kleine Sulfidschwefelgehalt in Flußspat wird durch Säure als Schwefelwasserstoff ausgetrieben, als Cadmiumsulfid gebunden und anschließend jodometrisch bestimmt.Für Kieselsäure, Bariumsulfat und Calciumfluorid ergibt die Fehlerrechnung Standardabweichungen von
s
SiO2=0.04%; sBaSO4=±0,04%; sCaF2=±0,09%.
Summary The present form of the analysis of high-percentage fluorspar is described. After removal of accompanying carbonates by treatment with dilute acetic acid, the silica is either volatilized with hydrofluoric acid and determined from the loss of weight or precipitated in a separate sample, decomposed with sodium carbonate, as tetrapyridinium dodecamolybdatosilicate and weighed as SiO2 + 12 MoO3. After volatilization of silica the remaining residue is fumed with sulphuric acid, boiled with a dilute hydrochloric/sulphuric acid mixture and the barium sulphate determined gravimetrically. In the filtrate of the barium sulphate precipitation the trivalent elements are either separated or masked. Then calcium is precipitated as oxalate and weighed after conversion to the oxide or directly determined by photometric titration with EDTA. After conversion to hydrogensulphide, the small sulphide-sulphur content in fluorspar is bound as cadmium sulphide and determined iodometrically.The error calculation results in the following standard deviations for silica, barium sulphate, and calcium fluoride: s SiO2=0.04%; sBaSO4=±0,04%; sCaF2=±0,09%.相似文献
179.
Structure of Tetraphenyldisiloxane Tetraphenyldisiloxane 1 crystallizes at 298 K monoclinically (P21/n; a = 1407.6; b = 610.7; c = 1262.7 pm; β = 95.87° Z = 2) and undergoes a second order phase transition at 200 K, in an almost unchanged structure of triclinic symmetry. At 298 K the molecules are already bent (Si? O? Si = 160°) with static or dynamical disorder of the bridging atom. Both Si? O distances are different (156 or 169 pm), because the shift of the bridging O atom is not perpendicular to the Si? to? Si vector. The reason for this remarkable behavior is not yet clear. According to the vibrational spectra, the Si? O? Si bridge is bent in the crystal but, in CCl4 solution a dynamical oscillation through the linear configuration may occur. 相似文献
180.
UV.-irradiation (λ ≥ 327 nm) of the α,β-unsaturated γ,δ-epoxy ketone 2 in pentane gives the isomers oxidoketone 3 and diketone 4, in high yield. On treatment with BF3O(C2H5)2, 2 undergoes rearrangement to the diketone 4 and the isomeric lactone 8 and yields also the dimer 9. 相似文献