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1.
Vladimir A. Khripach Vladimir N. Zhabinskii Vladimir V. Gromak Jaap van der Louw 《Tetrahedron letters》2006,47(38):6715-6718
Treatment of 3β,17β-diacetoxy-5,10-secoandrost-1(10)-en-5-one with BF3·Et2O was shown to proceed with cleavage of the macrocycle and formation of a new compound containing a cyclopentenone ring. Based on DFT calculations, an intramolecular Lewis acid promoted [2+2]cycloaddition, followed by a cycloreversion of the intermediate oxetane, is proposed as a possible reaction mechanism. 相似文献
2.
Claire Gervais Jaap J. Boon Federica Marone Ester S. B. Ferreira 《Applied Physics A: Materials Science & Processing》2013,111(1):31-38
The study of the early oeuvre of the Swiss painter Cuno Amiet (1868–1961) has revealed that, up to 1907, many of his grounds were hand applied and are mainly composed of chalk, bound in protein. These grounds are not only lean and absorbent, but also, as Synchrotron radiation X-ray microtomography has shown, porous. Our approach to the characterization of pore structure and quantity, their connectivity, and homogeneity is based on image segmentation and application of a clustering algorithm to high-resolution X-ray tomographic data. The issues associated with the segmentation of the different components of a ground sample based on X-ray imaging data are discussed. The approach applied to a sample taken from “Portrait of Max Leu” (1899) by Amiet revealed the presence of three sublayers within the ground with distinct porosity features, which had not been observed optically in cross-section. The upper and lower layers are highly porous with important connectivity and thus prone to water uptake/storage. The middle layer however shows low and nonconnected porosity at the resolution level of the X-ray tomography images, so that few direct water absorption paths through the entire sample exist. The potential of the method to characterize porosity and to understand moisture-related issues in paint layer degradation are discussed. 相似文献
3.
Murat Belivermis Önder Kılıç Yavuz Çotuk Sayhan Topçuoğlu Mahmut Coşkun Akın Çayır 《辐射效应与固体损伤》2013,168(11):903-913
The activity concentrations of gamma emitting radionuclides were measured in surface soil samples from the Thrace region. 232Th, 238U, 226Ra, 40K and 137Cs activities and physico-chemical parameters of the soil samples were determined in samples collected from 73 sampling stations. Radionuclide concentrations measured were compared with those found in the samples from other locations of Turkey and from different countries. The average activity concentrations of 232Th, 238U, 226Ra, 40K and 137Cs were found to be 24.71 ± 8.79, 22.30 ± 7.93, 32.09±12.44, 509.00±160.05, 32.74±29.24 Bq kg?1, respectively. The mean value of the annual effective dose equivalent from the outdoor terrestrial gamma radiation was calculated as 57.2 μ Sv. 相似文献
4.
van Werven JR Marsman HA Nederveen AJ ten Kate FJ van Gulik TM Stoker J 《Magnetic resonance imaging》2012,30(1):112-121
Purpose
To investigate the feasibility of in vivo assessment of hepatic lipid composition using 3.0-T proton magnetic resonance spectroscopy (1H-MRS) in a steatotic rat model and compare it to histopathological and biochemical assessment.Materials and Methods
Hepatic steatosis was induced by feeding rats with a methionine/choline-deficient (MCD) diet for 1, 2, 3, 5 or 7 weeks (n=5 per group). At the end of the diet period, 1H-MRS of the liver was performed, and rats were sacrificed for histopathological and biochemical assessment of the liver. Spectra were acquired in a single voxel (1.2 cc) using a point-resolved spectroscopic sequence with TE/TR=35/2000 ms and 64 signal acquisitions. From the MR spectra, peak area ratios were calculated to estimate hepatic lipid composition.Results
During MCD diet periods, hepatic steatosis significantly increased on histopathology (P<.001). The 1H-MRS measurements of total hepatic fat content [1.3/(1.3+4.65) ppm] correlated strongly with histological macrovesicular hepatic steatosis (r=0.93, P<.001) and with the biochemical total hepatic fatty acids (r=0.94, P<.001). Total unsaturated fatty acids [TUFA, 5.4/(1.3+4.65) ppm] estimated with 1H-MRS strongly correlated with the biochemical unsaturated fatty acids (r=0.90, P<.001). Polyunsaturated fatty acids [PUFA, 2.8/(1.3+4.65) ppm] estimated with 1H-MRS strongly correlated with biochemical PUFA (r=0.91, P<.001). The proportion of total unsaturated fatty acids relative to the amount of total fatty acids (rTUFA, 5.4/1.3ppm) measured with 1H-MRS strongly correlated with the biochemical amount of unsaturated relative to total hepatic fatty acids (r=0.81, P<.001). The proportion of PUFA relative to the amount of total fatty acids (rPUFA, 2.8/1.3 ppm) measured with 1H-MRS correlated with the biochemical amount of PUFA relative to total fatty acids (r=0.59, P=0.005,) and with the biochemical amount of omega-6 PUFA relative to total fatty acids (r=0.73, P<.001).PUFA at 1H-MRS correlated with the histopathologically assessed degree of lobular inflammation in the liver (r=0.57, P=.001).Conclusion
3.0T 1H-MRS is able to measure poly- and unsaturated hepatic fatty acids and this strongly correlates with biochemical assessment. This study provides evidence that 3.0-T 1H-MRS is a noninvasive technique to assess hepatic lipid composition. 相似文献5.
Jaap F. Vente Steven McIntosh Wim G. Haije Henny J. M. Bouwmeester 《Journal of Solid State Electrochemistry》2006,10(8):581-588
The present paper discusses the oxygen transport properties, oxygen stoichiometry, phase stability, and chemical and mechanical
stability of the perovskites (BSCF) and (SCF) for air separation applications. The low oxygen conductive brownmillerite phase in SCF is characterized using in-situ
neutron diffraction, thermographic analysis and temperature programmed desorption but this phase is not present for BSCF under
the conditions studied. Although both materials show oxygen fluxes well above 10 ml/cm2·min at T=1,273 K and pO2=1 bar for self-supporting, 200 μm-thick membranes, BSCF is preferred as a membrane material due to its phase stability. However,
BSCF’s long-term stable performance remains to be confirmed. The deviation from ideal oxygen stoichiometry for both materials
is high: δ>0.6. The thermal expansion coefficients of BSCF and SCF are 24×10−6 and 30×10−6 K−1, respectively, as determined from neutron diffraction data. The phenomenon of kinetic demixing has been observed at pO2<10−5 bar, resulting in roughening of the surface and enrichment with alkaline earth metals. Stress–strain curves were determined
and indicated creep behavior that induces undesired ductility at T=1,073 K for SCF. Remedies for mechanical and chemical instabilities are discussed. 相似文献
6.
Possibilities and practical aspects of implementation of splitless injection of larger volumes for fast GC purposes utilizing narrow-bore column, hydrogen as carrier gas, fast temperature programming under programmed flow conditions and commercial instrumentation were searched. As a model sample semivolatile compounds of a broad range of volatility and polarity (7 n-alkanes and 19 pesticides) were chosen. Peak shapes, peak broadening and peak areas and its repeatability were evaluated under various experimental set-ups (liner/injection technique combinations). Various factors, such as liner design, injection technique, retention gap length, compound volatility and polarity, the solvent used, initial oven temperature influenced compound focusation and/or maximal injection volume. Combination of analytical column (CP-Sil 13 CB 25 m long, 0.15 mm i.d., film thickness 0.4 microm) with normal-bore retention gap (1 m long, 0.32 mm i.d.) allowed maximal injection volume 8 microl for 4 mm i.d. liner used without any peak distortion when solvent recondensation in the retention gap was employed. 相似文献
7.
The static polarizabilities and the second-order hyperpolarizabilities of a series of tri-nuclear metal cluster models MS4(M′PPh3)2(M′PPh3)(M=Mo,W;M′=Cu,Ag,Au)have been calculated within the first-principle theoretical framework. The model clusters have two fragments of rhombic units and it is the charge ransfer from one of these moieties to the other that is responsible for nonlinear optical property. This kind of electronic delocaization, differentiated from that of planar π-system, is very interesting and is worthy for further investigation. 相似文献
8.
Ivan panik Jan Krupcik Ivan Skacani Jaap De Zeeuw Mario Galli Pat Sandra 《Journal of separation science》1997,20(12):688-692
The separation of isomers and enantiomers of branched C10-C12 phenylalkanes by gas chromatography on fused silica capillary columns coated with some modified β- and γ-cyclodextrins was studied. It was shown that the separation of positional isomers of C10-C12 phynylalkanes on modified cyclodextrin capillary columns is not better than that on a column coated with modified polyethylene glycol. Differences were found in the enantioselectivity of modified β- and γ-cyclodextrins for the separation of C10-C12 secondary phenylalkane enantiomers. While alkylderivatives of β-CDs resolve enantiomers of 3-phenylalkanes, alkyl derivatives of γ-CD resolve enantiomers of 2-phenylalkanes. Since shape selectivity factors of modified cyclodextrins have indicated no inclusion of the considered solutes in cyclodextrin cavities, enantioselective interactions most probably occur on the outer sphere of cyclodextrins. 相似文献
9.
A mixed ladderane/n-alkyl glycerol diether membrane lipid in an anaerobic ammonium-oxidizing bacterium 总被引:1,自引:0,他引:1
Sinninghe Damsté JS Rijpstra WI Strous M Jetten MS David OR Geenevasen JA van Maarseveen JH 《Chemical communications (Cambridge, England)》2004,(22):2590-2591
A novel glycerol diether containing ladderane and tetradecyl moieties has been identified in an anaerobic ammonium-oxidizing bacterium by GC/MS and high-field NMR spectroscopy. 相似文献
10.
Benaskar F Engels V Rebrov EV Patil NG Meuldijk J Thüne PC Magusin PC Mezari B Hessel V Hulshof LA Hensen EJ Wheatley AE Schouten JC 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(6):1800-1810
New routes for the preparation of highly active TiO(2)-supported Cu and CuZn catalysts have been developed for C-O coupling reactions. Slurries of a titania precursor were dip-coated onto glass beads to obtain either structured mesoporous or non-porous titania thin films. The Cu and CuZn nanoparticles, synthesized using a reduction by solvent method, were deposited onto calcined films to obtain a Cu loading of 2 wt%. The catalysts were characterized by inductively coupled plasma (ICP) spectroscopy, temperature-programmed oxidation/reduction (TPO/TPR) techniques, (63)Cu nuclear magnetic resonance (NMR) spectroscopy, X-ray diffraction (XRD), scanning and transmission electron microscopy (S/TEM-EDX) and X-ray photo-electron spectroscopy (XPS). The activity and stability of the catalysts obtained have been studied in the C-O Ullmann coupling of 4-chloropyridine and potassium phenolate. The titania-supported nanoparticles retained catalyst activity for up to 12 h. However, catalyst deactivation was observed for longer operation times due to oxidation of the Cu nanoparticles. The oxidation rate could be significantly reduced over the CuZn/TiO(2) catalytic films due to the presence of Zn. The 4-phenoxypyridine yield was 64% on the Cu/nonporous TiO(2) at 120 °C. The highest product yield of 84% was obtained on the Cu/mesoporous TiO(2) at 140 °C, corresponding to an initial reaction rate of 104 mmol g(cat) (-1) s(-1). The activation energy on the Cu/mesoporous TiO(2) catalyst was found to be (144±5) kJ mol(-1), which is close to the value obtained for the reaction over unsupported CuZn nanoparticles (123±3 kJ mol(-1)) and almost twice the value observed over the catalysts deposited onto the non-porous TiO(2) support (75±2 kJ mol(-1)). 相似文献