S?uren

Ohne Zusammenfassung     

Den Einfluss der Schwefels?ure auf die Empfindlichkeit der Strychninreaction mit saurem chromsaurem Kali

Ohne Zusammenfassung     

Unexpected reactions associated with the xanthate‐mediated polymerization of N‐vinylpyrrolidone

The monomer N‐vinylpyrrolidone (NVP) undergoes side reactions in the presence of R group functional xanthates and impurities. The fate of the monomer NVP and a selection of six O‐ethyl xanthates during xanthate‐mediated polymerization were studied via NMR spectroscopy. A high number of by‐products were identified. Significant side reactions affecting NVP include the formation of an unsaturated dimer and hydration products in bulk or in solution in C₆D₆. In addition, the xanthate adjacent to a NVP unit was found to undergo elimination at moderate temperature (60–70 °C), resulting in unsaturated species and the formation of new xanthate species. The presence of the chlorinated compound α‐chlorophenyl acetic acid, ethyl ester, a precursor in the synthesis of the xanthate S‐(2‐ethyl phenylacetate) O‐ethyl xanthate, resulted in a dramatic increase in the rate of side reactions such as unsaturated dimer formation and a high ratio of unsaturated chain ends. The conditions for the occurrence of such side reactions are discussed in this article, with relevance to increasing the control over the polymerization kinetics, endgroup functionality, and control over the molar mass distribution. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 6575–6593, 2008     

Antioxidant inhibition of porphyrin-induced cellular phototoxicity.

Porphyrins such as protoporphyrin IX (PP IX) and uroporphyrin I (UP I) can be phototoxic to human cells. To study the protective ability of antioxidants (beta-carotene, lycopene, ascorbic acid and alpha-tocopherol), against such porphyrin phototoxicity, membrane destruction experiments (Jurkat cells) and human cell cultures (fibroblasts) were performed. Both beta-carotene and lycopene and also the combination of beta-carotene, ascorbic acid and alpha-tocopherol offered cell protection against PP IX phototoxicity. Investigations of both cell membrane protection and of cell growth showed differences in terms of the protection afforded by the anti-oxidants. Thus, for PP IX, carotenoids alone, and in combination with ascorbic acid and alpha-tocopherol, showed higher protection factors in general than UP I. However, for membrane protection there was significant protection against UP I by the combination of beta-carotene, ascorbic acid and alpha-tocopherol but not by any of these anti-oxidants alone. The membrane protection against PP IX by beta-carotene, and especially lycopene, is significant presumably because of the high lipophilicity of all these molecules. However, the hydrophilic UP I will cause phototoxicity mainly via H(2)O(2), radical or singlet oxygen production in the aqueous phase, and these reactive species may be generated some distance from the cell membrane. This may lead to the little or no protection observed for UP I by the individual antioxidants. Nevertheless, a combination of beta-carotene, ascorbic acid and alpha-tocopherol offers membrane protection against the phototoxicity of both porphyrins. This is believed to occur as a result of synergistic processes. Our results suggest that the treatment of porphyria cutanea tarda and erythropoietic protoporphyria may be improved by the use of a combination of the antioxidants studied.     

On the complexity of the absorption spectrum of molecular nitrogen

The spectral properties of molecular nitrogen are crucial to a better understanding of radiative-transfer phenomena and activated N/N₂ chemistry in the Earth's upper atmosphere. Excited states of N₂ are difficult to access experimentally, and analysis of its electric dipole-allowed spectrum is notoriously complex. In this paper, we give an overview of these complexities and of the power of extreme ultraviolet ionization spectroscopy in unraveling many of the observed features. Some illustrative examples from our own research will be discussed.     

Degradation kinetics of telithromycin determined by HPLC method

The degradation kinetics of the antibiotic telithromycin using a stability-indicating high-performance liquid chromatography (HPLC) method is demonstrated. The photodegradation is performed by UVC lamp-254 nm (15W), installed in a chamber internally coated with mirrors, where telithromycin solutions prepared from coated tablets are placed in quartz cells. To promote oxidation, the reaction between the telithromycin solution and 3% hydrogen peroxide solution is carried out. The kinetics parameters of order of reaction and the rate constants of the degradation are determined for both conditions. The degradation process of telithromycin can be described by first-order kinetics under both experimental conditions used in this study. The results reveal the photo and oxidation lability of the drug and confirm the reliability of HPLC method for telithromycin in the presence of its degradation products.     

Prediction of the influence of reverberation on binaural speech intelligibility in noise and in quiet

Reverberation usually degrades speech intelligibility for spatially separated speech and noise sources since spatial unmasking is reduced and late reflections decrease the fidelity of the received speech signal. The latter effect could not satisfactorily be predicted by a recently presented binaural speech intelligibility model [Beutelmann et al. (2010). J. Acoust. Soc. Am. 127, 2479-2497]. This study therefore evaluated three extensions of the model to improve its predictions: (1) an extension of the speech intelligibility index based on modulation transfer functions, (2) a correction factor based on the room acoustical quantity "definition," and (3) a separation of the speech signal into useful and detrimental parts. The predictions were compared to results of two experiments in which speech reception thresholds were measured in a reverberant room in quiet and in the presence of a noise source for listeners with normal hearing. All extensions yielded better predictions than the original model when the influence of reverberation was strong, while predictions were similar for conditions with less reverberation. Although model (3) differed substantially in the assumed interaction of binaural processing and early reflections, its predictions were very similar to model (2) that achieved the best fit to the data.