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991.
Krystyna Kamieńska‐Trela Elena Dvornikova Zenobia Biedrzycka Michał Witanowski 《Journal of Physical Organic Chemistry》2012,25(12):1127-1138
An excellent linear correlation is found between a large set of experimental spin–spin carbon–carbon coupling constants, J(CC), in thiophene, pyrrole, and furan systems and the corresponding B3PW91/6‐311++G(2d,p)//B3PW91/6‐311++G(2d,p) calculated estimates. The correlation does not differ significantly from the simplest relationship possible, J(CC)exp. = J(CC)calcd., within a small and random spread of about 1 Hz. There are 285 experimental values considered, and 202 out of these are new and come from the present work. The character of the correlation indicates that rovibronic effects on aromatic J(CC)'s, and those of nuclear motions on aromatic J(CC)'s are practically negligible. All of this is in a perfect agreement with our recent extensive studies on aromatic J(CC)'s in pyridine and benzene ring systems. As has been shown by computations, not only large one‐bond couplings but also almost all long‐range ones occurring between the carbons of the heteroaromatic rings are, with a few exceptions, positive. Significant substituent effects experimentally observed in the one‐bond as well as long‐range couplings are very accurately reproduced by the computation. The experimental coupling magnitudes vary from ca. 1 to 98 Hz. The J(CC)'s computed for the model variously substituted trimethylsilyl and fluoro derivatives, which are not easily accessible experimentally, span a range of about 130 Hz, from ca. ?2 in up to ca. +125 Hz . Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
992.
Zuzanna Kabacińska Ryszard Krzyminiewski Bernadeta Dobosz Danuta Nawrocka 《Radiation measurements》2012,47(9):825-829
This study presents the preliminary results of investigation of the types and dynamics of paramagnetic centres in lime mortars from Sveta Petka church in Budinjak, Croatia, using Electron Spin Resonance (ESR) spectroscopy. The excavation in Budinjak discovered a very unique four lobed plan object Sveta Petka, with no additional finds or reliable historical records about the time of its construction. The lime mortars from the church were chosen for analysis in order to characterize the building material and to verify the site chronology by dating them. Lime mortar is valuable but problematic material for luminescence and radiocarbon dating. This type of material has not been dated before using ESR; therefore, careful studies are required to identify the useful paramagnetic centres. The ESR approach suggested in this work concentrates on a calcium carbonate signal. All samples were γ-irradiated in 60C bomb with the doses of 1, 10, 20, 50, 80 and 100 kGy. In all spectra signals from Fe3+ and Mn2+ ions have been observed. Paramagnetic centres which give the ESR signals may be interpreted as CO2?, CO3?, CO33?, HCO32?, SO2?, SO3?, PO2? and PO32? species. However, all spectra are complex and signals are interfering; therefore, computer resolution enhancement method will be needed in further research. The changes in ESR signals amplitude measured at magnetic field range about 3440–3450 G were analysed versus the dose of irradiation, using Mn2+ signals as a reference. Exponential growth of the curve and saturation for doses above 20 kGy were observed; therefore, irradiation with smaller doses is required. These preliminary studies will be helpful in future attempts of dating lime mortars by ESR method. 相似文献
993.
Nino R. Pereira B.V. Weber D.G. Phipps J.W. Schumer J.F. Seely J.J. Carroll J.R. Vanhoy K. Słabkowska M. Polasik E. Szymańska J. Rzadkiewicz 《High Energy Density Physics》2013,9(3):500-504
A recent measurement [1] demonstrates that iridium's Kα2-line, centered at ?63286.96 eV for a cold atom, increases ?+10 eV in energy when it is emitted by a modestly (~17×) ionized plasma. This measurement, enabled by a near-coincident lutetium K-edge filter, agrees well with atomic physics computations. Not understood at the time was a similar measurement with a thulium filter at the ?59370 eV energy of ytterbium's Kβ1 line, which indicated that its photon energy decreases with ionization. The computation reported here shows that the ionization energy shift for Yb's Kβ lines is indeed negative and agrees qualitatively with the measurements. For the K-lines the ionization energy shift may be most interesting in atomic physics, while for the L-lines the ionization energy shift is a promising plasma diagnostic [2]. 相似文献
994.
Jolanta Kowalska Agata Marzec Ewa Domian Sabina Galus Agnieszka Ciurzyska Rita Brzeziska Hanna Kowalska 《Molecules (Basel, Switzerland)》2021,26(16)
The polyphenol content of tea depends on the growing region, harvest date, the production process used, and the brewing parameters. In this study, research was undertaken that included an analysis of the influence of the brewing process parameters on the content of total polyphenols (Folin-Ciocalteu), epigallocatechin gallate (HPLC), and antioxidant activity (against DPPH radicals) of fresh tea shrub leaves grown from Taiwan and of teas obtained from them (oolong, green in bags, and green loose from the spring and autumn harvest). The antioxidant potential was determined in the methanol and aqueous extracts, as well as in infusions that were obtained by using water at 65 or 100 °C and infusing the tea for 5 or 10 min. The highest content of total polyphenols and epigallocatechin gallate was found in green tea extracts from the spring harvest. However, in the case of infusions, the highest content of these compounds was found in green tea in bags. Steaming at 100 °C for 10 min, turned out to be the most favourable condition for the extraction. Oolong tea, brewed at 100 °C for 5 min was characterised by the highest antioxidant activity against stable DPPH radicals. 相似文献
995.
The portable XRF spectrometer has been applied in situ for the non-destructive elemental mapping of the pigment components of the XV c. mural painting and frescos of the Little Christopher chamber in the Main Town Hall of Gdańsk, Poland. For a sufficiently large data collection the principal component analysis (PCA) was applied in order to associate the most intense lines of the elements Ca, Cu, Fe, Pb, and Hg in the XRF spectra with the palette of colors: white, brown, green, blue, red, yellow, and black observed in the painting. This allowed to limit the number of extractions of the micro-samples for the complementary Raman measurements thus assuring the practically non-destructive character of the entire analysis. The reliable identification of the pigment compositions was based on coincidence of the XRF, PCA and the Raman results which confirmed the presence of the chalk, malachite, azurite, red lead, mars red, mars yellow and candle black in the historical paints, except of the carbon-based black pigment being out of the XRF detection range. Different hues of the green paint were specified and the variety of the red and brown ones was ascribed to compositions of the Pb- and Fe-based red pigments (Fe2O3 and Pb3O4) with addition of the vermilion (HgS) and carbon black, in agreement with literature. The traces of elements: Ba and Sr, Sb and Mo, and also Cd, were ascribed to the impurities of Ca, those of some ochre pigments, and to the soluble Cd salts, respectively. 相似文献
996.
Dutkiewicz J Lityńska L Maziarz W Kocisko R Molnarová M Kovácová A 《Micron (Oxford, England : 1993)》2009,40(1):1-5
Amorphous structure of Ti(25)Zr(17)Ni(29)Cu(29) composition was studied. Alloys were prepared either by rapid solidification using melt spinning or by high-energy ball milling. The composition of multi-component eutectic in slowly cooled samples of ZrNiTiCu alloy was determined using EDS measurements in scanning microscope of slowly cooled cast samples. The alloys of eutectic composition were melt-spun or ball-milled. Transmission electron microscopy (TEM) studies of melt-spun ribbons from alloys near eutectic composition did not show presence of nanocrystals within the amorphous structure. TEM studies of ball-milled powders showed presence of nanocrystallites of size 2-5 nm. The electron diffraction pattern showed intense diffused ring due to the presence of the amorphous phase and a weak spot due to crystalline phases which were difficult to identify. The high temperature high-pressure compaction in vacuum of amorphous ball-milled powders resulted in a similar structure like in the powders showing nanocrystals embedded in the amorphous matrix. The crystallites were imaged using HREM. Interplanar distances were measured in pictures obtained by inverse fast Fourier transform (IFFT) of atomic planes to obtain better contrast. Analysis of the IFFT from high-resolution micrographs allowed to identify Cu(10)Zr(7) phase. Point analysis and elemental mapping performed using nondispersive X-ray energy spectroscopy showed uniform elements distribution indicating that chemical segregation to nanocrystals is within measurement error. 相似文献
997.
998.
A 1,3-alternate 25,27-bis-(pentafluorobenzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene-bonded silica gel stationary phase (CalixBzF10) was synthesized, structurally characterized, and used as a selector in liquid chromatography. The selectivity study of this phase was done by using fluorine-containing compounds (fluorobenzenes, fluoro-pyrimidine bases), as well as non-fluorinated analytes (non-steroidal anti-inflammatory drugs, sulfonamides, xanthines and polynuclear aromatic hydrocarbons). The effects of organic modifiers on the retention of various compounds possessing basic, acidic and neutral characteristics were studied. It was shown that only basic analytes exhibit a “U-shaped” retention profile and that retention depends on the mobile phase pH. Selectivity comparisons of the novel phase vs. the 1,3-alternate 25,27-bis-(benzyloxy)-26,28-bis-(3-propyloxy)-calix[4]arene phase (CalixBz) were performed. The retention mechanism is also discussed. The results indicate that the fluorinated calixarene stationary phase behaves like reversed-phase packing material; however, fluorine–fluorine interactions seem to be involved in the separation process of fluorine-containing analytes. 相似文献
999.
1000.
Urszula Domańska Marek Królikowski Katarzyna Ślesińska 《The Journal of chemical thermodynamics》2009,41(11):1303-1311
(Solid + liquid) equilibria (SLE) and (liquid + liquid) equilibria (LLE) for the binary systems: {ionic liquid (IL) N-butyl-4-methylpyridinium tosylate (p-toluenesulfonate) [BM4Py][TOS], or N-butyl-3-methylpyridinium tosylate [BM3Py][TOS], or N-hexyl-3-methylpyridinium tosylate [HM3Py][TOS], or N-butyl-4-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide [BM4Py][NTf2], or 1,4-dimethylpyridinium tosylate [M1,4Py][TOS], or 2,4,6-collidine tosylate [M2,4,6Py][TOS], or 1-ethyl-3-methylimidazolium thiocyanate [EMIM][SCN], or 1-butyl-3-methylimidazolium thiocyanate [BMIM][SCN], or 1-hexyl-3-methylimidazolium thiocyanate [HMIM][SCN], or triethylsulphonium bis(trifluoromethylsulfonyl)imide [Et3S][NTf2] + thiophene} have been determined at ambient pressure. A dynamic method was used over a broad range of mole fractions and temperatures from (270 to 390) K. In the case of systems (pyridinium IL, or sulphonium IL + thiophene) the mutual immiscibility with an upper critical solution temperature (UCST) was detected at the very narrow and low mole fraction of the IL. For the binary systems containing (imidazolium thiocyanate IL + thiophene), the mutual immiscibility with the lower critical solution temperature (LCST) was detected at the higher mole fraction range of the IL. The basic thermal properties of the pure ILs, i.e. melting and glass-transition temperatures as well as the enthalpy of fusion have been measured using a differential scanning microcalorimetry technique (DSC). The well-known NRTL equation has been used to correlate experimental SLE/LLE data sets. 相似文献