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31.
In the present work, the validity of the helicity rule relating the absolute configuration of the bridgehead carbon atom in bicyclic β-lactams to the sign of the 220 nm band observed in their electronic circular dichroism (ECD) spectra is examined for ring-expanded cephalosporin analogues. To this end, a series of model compounds with a seven-membered ring condensed with the β-lactam unit was synthesized. A key step of their synthesis was either the ring-closing metathesis (RCM) or the free radical cyclization leading to the seven-membered ring with an S, O, or C atom at the 6 position in the bicyclic skeleton. To investigate the scope and limitations of the simple, empirically established helicity rule, a combination of ECD spectroscopy, variable-temperature ECD measurements, X-ray analysis, and time-dependent density functional theory (TD-DFT) calculations was used. A comparison of the experimental ECD spectra with the spectra simulated by TD-DFT calculations gives a reasonable interpretation of the Cotton effects observed in the 240-215 nm spectral range. The results suggest that the helicity rule does not apply to the investigated compounds because of the planarity of their amide chromophore. Thus, these compounds do not constitute an exception to the rule that was established for bi- and polycyclic β-lactams with the nonplanar amide chromophore only.  相似文献   
32.
Summary The possibility of comparing various chromatographic sorbents in respect of their activity is discussed utilizing a simple thermodynamic approach presented earlier.  相似文献   
33.
Summary Three different sorbents, one with high activity (silica gel), the second with medium activity (cellulose powder) and the third having low activity (chromatographic paper) were compared in respect of their usefulness for the evaluation of the self association of selected higher fatty alcohols and acids. The obtained results are correlated with IR spectroscopic data and theoretical considerations.  相似文献   
34.
The autoxidation process of oleyl alcohol, oleic acid, and methyl oleate at 40, 50, and 60 °C was considered with the special stress laid upon the mechanism of cumulating and destruction of peroxidic products. Interpretation of the observed differences was based on the hydrogen-bond association patterns.  相似文献   
35.
In our paper the influence of association in the methyl oleate-propionic acid system on the course of autoxidation of this system was discussed. The course of autoxidation of the a/m system was characterized with the help of peroxide number and dielectric constant measurements.  相似文献   
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Since 2006 the ISOLTRAP mass spectrometer has provided high-precision masses of many short-lived nuclides located all across the nuclear chart with half-lives down to a few 10 ms. These nuclides range from the two-proton halo candidate 17Ne, via the neutron-rich magic 80Zn and 132Sn, up to 229Rn which was identified for the first time. The results show that ISOLTRAP is a versatile tool well suited to address physics topics such as nuclear structure, stellar nucleosynthesis, or the weak interaction.  相似文献   
38.
Accreditation and Quality Assurance - Enabling the possibility of “tracing” the route of a food product is a legal requirement for all participants of the food chain. It allows...  相似文献   
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Laser-induced breakdown spectroscopy (LIBS) was applied to the preliminary examination of Polish documents – passports and identity cards – for forensic purposes. Several security features of potentially high discrimination capability were selected at both the passports (Alphagram, serial number, the contour map of Europe, and emblem) and identity cards (kinegram, the date of birth, and emblem). Different elemental compositions were identified after comparing the spectra recorded from various measurement locations. It was possible to identify characteristic atomic emission from several elements (such as Ti, Ca, K, Fe, Cr, Mg, Na, La, Cd, Li, V, Al, Mn, Ni, and Cu) based on the type of document, issue date, and evaluated area. In the case of passports, the potentially good discriminators with unique elemental composition were identified, e.g., the serial number and the contour map of Europe printed with the use of intaglio printing technique. Identity cards with the cover of polycarbonate foil constitute a very difficult sample to analyze because of the foil’s influence on the laser ablation phenomenon. This study presents the potential of LIBS as an effective and useful technique to analyze Polish passports for forensic purposes. Its many advantages provide a good alternative to the analytical methods routinely used for the examination of these objects.  相似文献   
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