Binukleare Nickel(0)-Alkin-Koordinationsverbindungen – Zusammenhang zwischen Ligandperipherie und supramolekularer Struktur

Binuclear Nickel(0) Alkyne Coordination Compounds – Correlation between Ligand Periphery and Supramolecular Structure Reaction of Ni(cdt: 1,5,9-cyclododecatriene) with functionalized alkynes and subsequent reaction with ethylenediamines gives binuclear compounds of the type (diamine)Ni(μ-alkyne)Ni(alkyne). Compounds with alkyne-diols (N?N)Ni₂(HOR¹R²C? C?C? CR¹R²OH)₂ show supramolecular structures in which two identical intramolecular and one intermolecular hydrogen bonds are realized. 1 and 2 (chelate ligand in each case N,N,N′,N′-tetramethylethylenediamine, TMEDA, in 1 R¹ = R² = Me, in 2 R¹ = R² = Et) polymer-like chains are built up by connecting the binuclear units. Via two intermolecular hydrogen bonds per organometallic unit in 1 and via one intermoleculare hydrogen bond in 2 the chains are connected to give double chains. By substitution of one methyl group of TMEDA by hydrogen ( 3 : R¹ = R² = Me) a polymerlike network is produced by connecting the polymer-like chains. In compound 4 in which one of the methyl groups of TMEDA is substituted by CH₂CH₂NMe₂ the polymer-like chains remain unconnected. In 5 (diamine = TMEDA, alkyne = (CH₃)₃C? C?C? CMe₂OH) one intermolecular hydrogen bond per organometallic unit is observed forming again polymer-like chains that are independent of each other.     

The elimination of carbon monoxide from molecular ions of phenol and other [C6H6O]+˙ isomers

Phenol and five acyclic isomeric compounds have been investigated using electron impact and field ionization techniques, mass analysed ion kinetic energy spectrometry and collision induced dissociation mass analysed ion kinetic energy spectrometry. The kinetic energy release data corresponding to the elimination of carbon monoxide from the molecular ions show that at least two structures of the reactant ion are involved. The electron impact and field ionization collision induced dissociation mass analysed ion kinetic energy spectra indicate that under electron impact conditions, the phenol ion partially isomerizes to another ion structure. An isomerization of about 40% to the structure of cis-2-hexen-4-yn-1-al is in good accordance with the spectral data.     

31P- und 195Pt-NMR-Untersuchungen an Diplatin(I)-Komplexen des Typs [Pt2(μ-SPR2)2L2] (L = PR3, PhP(OPh)2, P(OPh)3, CNR)

³¹P and ¹⁹⁵Pt N.M.R. Investigations on Diplatinum (I) Complexes of the Type [Pt₂(μ-SPR₂)₂L₂] (L = PR₃, PhP(OPh)₂, P(OPh)₃, CNR) ³¹P-, ¹⁹⁵Pt-chemical shifts and ¹⁹⁵Pt–³¹P- resp. ³¹P–³¹P-coupling constants of a series of doubly bridged diplatinum(I) complexes are reported. ³¹P-coordination chemical shifts of the terminal ligands of complexes of type [Pt₂(μ-SPR₂)₂(P′R₃′)₂] and some of the various coupling constants are strongly influenced by the π-acceptor strength of these ligands. J(¹⁹⁵Pt–¹⁹⁵Pt) is found to change the sign among the series of complexes investigated. Thermal singlett triplet exitation giving rise to the paramagnetism of these complexes observed by preliminary EPR-measurements and confirmed by EHT-calculations is deduced from the large values of ²J(P–P′) and ³J(P′P′) as well as the unusually high temperature dependence of some coupling constants and other NMR features. The chemical stability of the doubly bridged core, the coordination shifts of the bridging phosphorus atoms and EHT-calculations suggest a view of aromaticity of the [Pt₂(μ-SPR₂)₂](M–M) unit of these complexes.     

Ultra performance liquid chromatography – mass spectrometry studies of formalin‐induced alterations of human brain lipidome

The development of ‘omics’ sciences offers new opportunities for the study of neurodegenerative diseases but increases at the same time the sample demand on brain banks that collect and store valuable human post‐mortem tissue. Our study aims to evaluate in lipidomics the potential of formalin‐fixed tissue compared with the cryopreservation method, considered as the gold standard for biochemical research. Two complementary liquid chromatography/mass spectrometry analytical platforms were used on the basis of hybrid quadrupole time‐of‐flight and triple quadrupole mass spectrometers. Untargeted fingerprinting, semitargeted profiling of specific lipid classes and targeted monitoring of lipid species were performed in formalin‐fixed and cryopreserved samples to provide detailed information at the molecular level on the formalin‐induced alterations of the brain tissue. In vitro incubations of lipid standards were also performed to further describe the degradation processes induced by formaldehyde. Phospholipid compounds were found to be extensively hydrolysed, whilst the sphingolipid ones were preserved. N‐methylation and N‐formylation of amine‐containing phospholipids have also been evidenced. These findings show that the potential detrimental effect of formalin on the analytes of interest must be taken into account when analysing formalin‐fixed samples. Copyright © 2014 John Wiley & Sons, Ltd.     

Studies on drug metabolism by fungi colonizing decomposing human cadavers. Part I: DNA sequence-based identification of fungi isolated from postmortem material

Cadavers can be colonized by a wide variety of bacteria and fungi. Some of these microbes could change the concentration or the metabolic pattern of drugs present in postmortem samples. The purpose of this study was to identify fungi from human postmortem material and to further assess their potential role in the metabolism of drugs. Aliquots of 252 postmortem samples (heart blood, liver, kidney, and lung) taken from 105 moderately to severely decomposed bodies were streaked on Sabouraud agar for isolation of fungal species. One part of the samples was worked up immediately after autopsy (group I). The second part had previously been stored at ?20 °C for at least 1 year (group II). Identification of the isolates was achieved morphologically by microscopy and molecularly by polymerase chain reaction amplification and sequencing of markers allowing species identification of the respective genera. Depending on the genus, different gene fragments were used: calmodulin for Aspergillus, β-tubulin for Penicillium, translation elongation factor 1α for Fusarium, and the internal transcribed spacer region of the ribosomal DNA for all remaining genera. A total of 156 fungal strains were isolated from 62 % of the postmortem materials. By using these primers, 98 % of the isolates could be identified to the species level. The most common genera were Candida (60.0 %—six species), Penicillium (10.3 %—two species), Rhodotorula (7.1 %—one species), Mucor (6.4 %—four species), Aspergillus (3.2 %—four species), Trichosporon (3.2 %—one species), and Geotrichum (3.2 %—one species). Group I samples contained 53 % more fungal species than stored samples suggesting some fungi did not survive the freezing process. The isolated fungi might be characteristic for decomposed bodies. The proposed methodology proved to be appropriate for the identification of fungi in this type of material.