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31.
de Meijere A Kozhushkov SI Rauch K Schill H Verevkin SP Kümmerlin M Beckhaus HD Rüchardt C Yufit DS 《Journal of the American Chemical Society》2003,125(49):15110-15113
The enthalpies of formation [Delta(g)] of tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),10(14),11-heptaene (2, 1,2-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1-ene) and tricyclo[8.2.2.2(4,7)]hexadeca-1(13),2,4(16),5,7(15),8,10(14),11-octaene (3, 1,2,9,10-dehydro[2.2]paracyclophane or [2.2]paracyclophane-1,9-diene) have been determined by measuring their heats of combustion in a microcalorimeter and their heats of sublimation by the transpiration method. Values of the strain energies (SE) [SE(2) = 34.7 kcal mol(-)(1), SE(3) = 42.0 kcal mol(-)(1)] have been derived from the gas-phase heats of formation and are compared with those from MM3 and PM3 calculations and with the corresponding value SE(1) = 30.1 kcal mol(-)(1) for the parent tricyclo[8.2.2.2(4,7)]hexadeca-1(13),4(16),5,7(15),10(14),11-hexaene (1, [2.2]paracyclophane). The higher strain energies of 2 and 3 (by 4.6 and 11.9 kcal mol(-)(1)) are in accord with the well-known increased reactivities of their aromatic rings as a consequence of their increased bending. As revealed by an X-ray crystal structure analysis, the bending in the monoene 2 corresponds to that of 1 and 3 at one of two bridging corners. 相似文献
32.
Rock porosity determination by combination of X-ray computerized tomography with mercury porosimetry
P. Klobes H. Riesemeier K. Meyer J. Goebbels K.-H. Hellmuth 《Fresenius' Journal of Analytical Chemistry》1997,357(5):543-547
First results are described of coupling of mercury porosimetry with X-ray computerized tomography (CT) as a new combination
technique for rock porosity studies. This technique is suitable for rock samples with a pronounced mercury intrusion-extrusion
hysteresis and includes CT measurements before and after mercury intrusion. The entrapped portion of mercury, when the pressure
after the intrusion into the rock sample is reduced to 0.1 MPa, serves as a contrast agent in the porous network to localize
spatial distribution of rock porosity by CT. The results obtained show that the mercury intrusion and therefore the porosity
were quite different for the separate mineral phases. Therefore the combination of mercury porosimetry and computer tomography
can give 3-D data on mineral-specific porosity distributions with additional pore size information. In contrast to mercury
porosimetry as a single method, results of the combination technique with CT represent a direct visualization of porosity
variation and do not depend on any special pore network model.
Received: 2 July 1996 / Revised: 20 November 1996 / Accepted: 22 November 1996 相似文献
33.
The novel versatile cobalt(I) tris-carbene complex [(TIMEN(xyl))Co]Cl (1) (where TIMEN = (tris[2-(3-arylimidazol-2-ylidene)ethyl]amine) reacts with CO, one-electron oxidizers such as CH(2)Cl(2), and O(2) to yield the cobalt complexes [(TIMEN(xyl))Co(CO)]Cl (2), [(TIMEN(xyl))Co(Cl)]Cl (3), and peroxo species [(TIMEN(xyl))Co(O(2))](BPh(4)) (5). All new complexes were fully characterized by (1)H NMR, UV/vis, and IR spectroscopy as well as superconducting quantum interference device (SQUID) magnetization measurements and single-crystal X-ray crystallography. The nucleophilic character of the eta(2)-bound dioxygen ligand in 5 was confirmed by density functional theory (DFT) studies and allows for oxygen-transfer reactions with electron-deficient organic substrates, such as benzoyl chloride. 相似文献
34.
Heinz Berner Gerhard Schulz Gernot Fischer Hellmuth Reinshagen 《Monatshefte für Chemie / Chemical Monthly》1978,109(3):557-566
In order to obtain a better partition of a prodigiosin derivative in biological media, two hydroxy groups were introduced into theansa-part of the molecule. The synthesis of the title compound is described in detail. 相似文献
35.
Hellmuth Stachel 《Journal of Geometry》1979,13(2):144-153
It is shown that in the quasielliptic space there exist two different sets of respectively quasielliptic congruent curves with the same natural equations =(s), =(s). On the curves of one set the sense of increasing arc length s corresponds with the positive orientation, to say with the sense of increasing x1/x0; on curves of the other set the orientation of s is negativ. Further we prove that the fundamental quantities of surface theory as defined in [3] cannot always characterize an unique parametrized surface apart from quasielliptic motions. In the exceptional case one Christoffel symbol must be given too. 相似文献
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Abstract Solids like layer silicates (kaolinite and montmorillonite) as well as ZnO are in use in pharmacy. They are pressure treated and subsequently analyzed by means of ESR spectroscopy. The structural changes indicated by Fe3+ ions and paramagnetic defects are reponsible for the enhanced chemical activity of the pressurized systems. Especially active Fe-O-species are formed which can react with intercacalated organic molecules. The most probable first step of such reactions will be a solid state single electron transfer. Spin probes and spin traps were used to prove this statements. The activation of the drug delivery systems by mechanical treatments is of importance for the stability of the drugs incorporated. 相似文献
39.
Dr. James Biggs Dr. Karsten Danielmeier Dr. Julia Hitzbleck Dr. Jens Krause Tom Kridl Dr. Stephan Nowak Dr. Enrico Orselli Dr. Xina Quan Dirk Schapeler Will Sutherland Dr. Joachim Wagner 《Angewandte Chemie (International ed. in English)》2013,52(36):9409-9421
We present the development and applications of dielectric elastomers. For the last 10 years the significance of this class of polymers has risen as more applications seem possible and first products have been commercialized. 相似文献
40.