Beiträge zur Chemie der Pyrrolpigmente, 31. Mitt.: Die Spin-Gitter-Relaxation in den1H-NMR-Spektren von Bilatrienen-abc

The¹H-NMR spin lattice relaxation times of aetiobiliverdin-IV- and biliverdindimethylester were determined using the inversion recovery technique. The relaxation times of protons attached to the terminal rings A and D are longer than those situated at the rings B and C which points to a higher mobility of rings A and D. Moreover these measurements allowed an independent assignment of the¹H-NMR-signals of the methyl groups of biliverdindimethylester.

30. Mitt.:H. Falk undT. Schlederer, Ann. Chem., im Druck.     

The reactivity of dimethylaluminum hydride with the aminoarsines Me2AsNMe2, MeAs(NMe2)2, and As(NMe2)3

The reactions of (Me₂AlH)₃ with Me₂AsNMe₂, MeAs(NMe₂)₂, and As(NMe₂)₃ were investigated as a function of time at room temperature and over the temperature range −90 to 24°C by use of ¹H and ¹³C NMR spectroscopy. (Me₂AlH)₃ was found to be very reactive toward the aminoarsines, even at −90°C, and no stable Me₂AlH-aminoarsine adducts were observed. Instead, the initial stages of the reactions involved AS---N bond cleavage with the generation of highly reactive AlN- and AsH-bonded species. The subsequent course of each reaction and the final arsenic-containing product distribution depended upon the original AL:N stoichiometric ratio and the respective aminoarsine. When the Al:N ratio was 1:1, the reactions were straightforward for each aminoarsine. However, in every case, [Me₂AlNMe₂]₂ was the final AlN-containing product. Independent reactions were carried out to verify many of the proposed decomposition pathways that lead to thermodynamically stable products. The results of this study are compared with those of the analogous, previously reported (Me₃Al)₂-aminoarsine systems. Additionally, a new synthetic route to [Me₂AlAsMe₂]₃ has been established from the reaction of (Me₂AlH)₃ with Me₂AsH.     

The effect of sampling conditions on the thermal decomposition of electrolytic manganese dioxide

The effect of sampling conditions on the decomposition of electrolytic manganese dioxide using thermal methods is reported. Significant differences were observed in the mechanism of the decomposition by simply changing the reaction environment from a closed pan to an open pan configuration. The purge gas atmosphere was also observed to influence the decomposition mechanism. As a product of the decomposition is oxygen, the change in the mechanism observed between the experimental conditions may be explained in terms of the ease of removal of oxygen from the reaction site. This revised version was published online in August 2006 with corrections to the Cover Date.     

Liquid chromatographic determination of 4,4'-dinitrocarbanilide, the active component of the infertility agent nicarbazin, in chicken, duck, goose, and snake eggs

4,4'-Dinitrocarbanilide (DNC) was extracted from chicken, duck, goose, and snake eggs and isolated by reversed-phase liquid chromatography. DNC was detected by ultraviolet absorbance at 347 nm and quantitated by comparison with a calibration standard. Recoveries of DNC from fortified control chicken, duck, goose, and snake egg samples were determined for DNC levels of 0.16, 10, and 16 microg/g. The mean recoveries from chicken, duck, goose, and snake eggs were 92 +/- 4, 88 +/- 9, 87 +/- 7, and 95 +/- 6%, respectively. The method limits of detection for DNC in chicken, duck, goose, and snake eggs ranged from 0.015 to 0.035 microg/g. The reported method is much simpler than and equally efficient as previous methods developed for the determination of DNC residues in egg contents.     

Correlation between Site ll-Specific Human Serum Albumin (HSA) Binding Affinity and Murine in vivo Photosensitizing Efficacy of Some Photofrin Components

Human serum albumin (HSA) is one of the key components in human blood that may influence drug distribution. As such, it is important to know the affinity of any drug for albumin. Previously, Photofrina mixture of monomeric, dimeric and oligomeric porphyrins, has been subjected to HSA binding studies. However, due to its complex nature, binding studies on Photofrin or other hematoporphyrin derivatives with HSA are inconclusive. In this report, the binding properties of some components (dimers and trimers) of Photofrin® and the relationship between murine photosensitizing efficacy and those binding properties were investigated. The interaction of these porphyrins with HSA was investigated by direct ultrafiltration and fluorescent titration techniques with fluorescent probes such as dansyl-L-proline (DP), which is known to interact selectively with site II on HSA. Porphyrins also were tested for antitumor activity in a mouse model following intravenous administration and exposure to laser light. Together, the results suggest that the photosensitizers that were preferentially bound to site II of HSA were most effective at controlling murine tumor regrowth     

Odd/even effect in the chain length on the enthalpy of micellization of gemini surfactants in aqueous solution

The micellization properties of cationic symmetric gemini surfactants, [CmH(2m+1)(CH3)2N(CH2)6N(CH3)2CmH(2m+1)]Br2 (designated as CmC6CmBr2, with m = 7, 8, 9, 10, 11, 12, and 16), has been investigated by isothermal titration microcalorimetry. The critical micelle concentration (CMC) and enthalpy of micellization (DeltaHmic) were determined from calorimetric titration curves. The linear decreasing of log CMC with increasing the length of the hydrophobic chain is consistent with an increase in the hydrophobicity of the alkyl chain. Interestingly, with increasing the length of the alkyl chain, the DeltaHmic values of the surfactants with even numbered alkyl chains vary from endothermic to exothermic, whereas the DeltaHmic values of the surfactants with odd numbered alkyl chains are all endothermic and tend to become more endothermic. The pronounced even/odd effect in DeltaHmic is discussed with respect to the "donor-acceptor" interaction.