Cyanide und Halogene

Ohne Zusammenfassung     

Advanced TMAH and TMAAc thermochemolysis–pyrolysis techniques for molecular characterization of size-separated fractions from aquatic dissolved organic matter

The structural similarities and differences between the original DOM and the eight size fractions separated were studied in detail with the pyrolysis technique in combination with gas chromatography and mass spectrometry (Py-GC-MS) using two alkylating reagents: TMAH (tetramethylammonium hydroxide), to find both esterified and free carboxylic acids; and TMAAc (tetramethylammonium acetate), to specify only free carboxylic acids. A statistical analysis of the original multidimensional TMAH and TMAAc pyrograms disclosed that the overall structural compositions of the five most important size fractions, accounting for 84% of the original DOM, greatly resembled each other. The remaining three minor size fractions were not classified as homogeneous associations, but they also contained the same total, covalently bound and free carboxylic acid species as the other size fractions and the original DOM mixture, thus representing some kind of intermediate forms. This fundamental outcome strongly supports the opinion that the native dissolved humic-like macromolecules resemble supramolecular associations of smaller molecular size moieties with similar structural functionalities. The concentrations of free aliphatic and aromatic dicarboxylic acids in the DOM solution were so low that their effects on the potential formation of multiply charged ions in electrospray ionization-MS (ESI-MS) studies are likely insignificant.     

MR imaging of fatigue stress injuries to bones: intra- and interobserver agreement

The aim of this study was to determine the validity of MR imaging (MRI) in the assessment of stress-related injuries to bone.MR images of 50 military recruits (8 females and 42 males; 18-27 (mean 20) years of age) were retrospectively evaluated twice for stress injuries to bone by 4 radiologists (2 musculoskeletal radiologists, 2 radiology residents). Coronal T1-weighed (T1W) and STIR images, as well as axial and coronal T2-weighted (T2W) fat-suppressed images were taken using a 1.0T scanner. Rates for sensitivity, specificity, and accuracy of MRI of the stress-related injuries were calculated. Intraobserver and interobserver agreement was determined with kappa statistics.Rates for MRI sensitivity were 27-96%, for specificity 65-100%, and for diagnostic accuracy 58-97%. Lowest rates were seen when reading T1W images and highest when reading STIR images. Readers showed moderate to excellent intraobserver agreement (kappa 0.75-0.95). Interobserver agreement was fair to excellent (kappa 0.41-0.91), and the lowest values were seen in the interpretation of T1W images. Normal findings could be differentiated from various grades of stress injury to bone.MRI is a valid means of revealing the presence of stress injuries to bone and their staging. Observer agreement is good to excellent when using T2W images and STIR images, while T1W images are of lesser value.     

IR-induced processes for allyl alcohol dimers involving an intermolecular OH...π Bond in low-temperature matrices

Sharp peaks were observed in the IR spectra of allyl alcohol dimers in the νOH and τOH regions in low-temperature Ar and N₂ matrices. In Ar a peak at 3587 cm^?1 was found to increase in intensity upon annealing and decrease upon IR irradiation; it is concluded that this peak is due to an OH...π interaction (of a cyclic structure) present in part of the dimers. This is the first time such an interaction and photoprocess have been found for an alcohol in matrices. Also a faster photo-process was found. Confomer changes in the monomers accompany the photoprocess in allyl alcohol dimers.     

A special method of deformational correction in N.M.R. of molecules dissolved in liquid crystals

A simple method of deformational correction for the N.M.R. spectral parameters of molecules dissolved in liquid crystals is described. The method is applicable to the different isotopically substituted derivatives of the molecules belonging to the cubic point groups. Its validity is verified for the dipolar and quadrupolar couplings observed in the molecules CH₄, CD₄ and CH₃D dissolved in the liquid crystals Merck Phase IV, Merck ZLI 1167 and their mixtures.