Synthese und Konformationsanalyse von Pyranophanonen und Pyrylophanium-Verbindungen mit intraannularen Substituenten

Synthesis and Conformational Analysis of Pyranophanones and Pyrylophanium Compounds with Intraannular Substituents The synthesis of [3.3]dithiapyranophanone 6 and 11 is accomplished by use of the two-components-dilution-principle. Pyrolysis of their bis(sulfones) 7 and 12 gives the [2.2]pyranophanones 8 , 9 and 13 . Under preservation of conformation the intraannular carbonyl-function is used for the synthesis of methylpyranophanoles 14 , 16 and 17 . The synthesis of pyrylophanium compounds 15 and 18 is possible by elimination in trifluoroacetic acid. 6 exhibits anti-conformation within its crystal-structure and like 7 reveals temperature-dependent behavior in solution. Using 6 as an example, a combination of ¹³C-NMR-spectroscopy, forcefield-calculation and computer-simulation is applied for the first time to give evidence for molecular-dynamic processes of cyclophanes. 8 and 9 are the syn- and anti-conformers of the desired product, as shown by X-ray structural analysis. 13 reveals anti-conformation within its crystal structure as well as in solution. The conformational analysis of other new phanes described here is based on the ¹H-NMR-spectra of these pyrolysis products. As expected the intraannular substituents of Pyrylophanium-lons 15 and 18 show the characteristic upfield-shift within their ¹H-NMR-spectra.     

Photochlorierung und metallorganische Folgereaktionen eines verzweigten Poly(carbosilans)

Photochlorination and Metalorganic Following Reactions of a Cross-linked Poly(carbosilane) The synthesis of a perchlorinated cross-linked poly(carbosilane) of the general composition [(Cl₂Si)_1,5(SiCl) (CCl₂)₃]_x ( II ) was achieved through the photochlorination of [(Cl₂Si)_1,5(SiCl)(CH₂)₃]_x ( I ). The perchlorinated product was investigated by elemental analysis and spectroscopic methods. Furthermore the permethylated and perphenylated compounds [(Me₂Si)_1,5(SiMe)(CMe₂)₃]_x ( III ) and [(Ph₂Si)_1,5(SiPh)(CPh₂)₃]_x ( IV ) were synthesized by reactions with methyl- and phenyllithium. The products obtained were characterized by elemental analysis and ¹H, ¹³C, ²⁹Si NMR and IR spectroscopy. The number and weight averages M_n and M_w were determined by gel permeation chromatography.     

Photochemie von Acylaziden. VIII [1]. Reagieren Acylnitrene wie 1,3-Dipole??

Photochemistry of Acylazides. VIII. Do Acylnitrenes React like 1,3-Dipoles? The formation of three- ore five-membered heterocyclic rings by the reaction of acylnitrenes with olefins depends on the electron density at the double bond. The generally expected formation of aziridines by a cheletropic reaction was observed by photolysis of aroylazides 1 in the presence of 2,5-dihydrofuran 2 . But with enolethers 3 and 4 oxazolines were directly formed. This [3 + 2] cycloaddition is regiospecific. The cycloaddition is modestly stereoselective by steric hindrance within the cyclic enolether 3b . Very small de-values were found with chiral substituents in the acylazide 13 . The azide decomposition was also achieved by photoinduced electron transfer. The same cycloaddition products as obtained by direct photolysis of the azides were obtained via radical anions of the acylazide. Using Michler's ketone as electron donor in the triplet state the formation of isocyanate which diminishes the yield of cycloadducts can be avoided.     

Zur Existenzfähigkeit von 2-Imino-2H-1,3-thiazinen

On the Existence of 2-Imino-2H-1,3-thiazines The title compounds 2 are readily liberated from the 2-amino-1,3-thiazinium salts 1 by treatment with bases. Their stability depends sensitively on the substituents at the imino-N. The imino-N substituted 2a – i are isolable as well-defined coloured substances. Reaction of the 2 as well 1 with nucleophilic agents affords pyrimidine-2-thiones ( 4 , 9 – 11 , 16 – 18 ). In these ring transformations a nucleophilic addition at ring position 6 as primary reaction step is preferred. The imino-N unsubstituted representatives display a more complicated behaviour; the highly enhanced reactivity prevents or handicaps, respectively, any isolation. As exemplified in the base-induced ring-transformation of 1 m to the pyrimidine derivative 19 , these 2 are able to react as nucleophiles too, and versatile intermolecular self-reactions are increasingly favoured.     

Comparison of Automated Ribotyping,spa Typing,and MLST in 108 Clinical Isolates of Staphylococcus aureus from Orthopedic Infections

108 isolates of Staphylococcus aureus, belonging to six large ribogroups according to the automated Ribo-Printer^® system, were studied with two highly used molecular methods for epidemiological studies, namely multi-locus sequence typing (MLST) and spa typing, followed by BURP and eBURST v3 analysis for clustering spa types and sequence (ST) types. The aim was to evaluate whether automated ribotyping could be considered a useful screening tool for identifying S. aureus genetic lineages with respect to spa typing and MLST. Clarifying the relationship of riboprinting with these typing methods and establishing whether ribogroups fit single clonal complexes were two main objectives. Further information on the genetic profile of the isolates was obtained from agr typing and the search for the mecA, tst genes, and the IS256 insertion sequence. Automated ribotyping has been shown to predict spa clonal complexes and MLST clonal complexes. The high cost and lower discriminatory power of automated ribotyping compared to spa and MSLT typing could be an obstacle to fine genotyping analyzes, especially when high discriminatory power is required. On the other hand, numerous advantages such as automation, ease and speed of execution, stability, typeability and reproducibility make ribotyping a reliable method to be juxtaposed to gold standard methods.     

COVID-19 and Lung Mast Cells: The Kallikrein–Kinin Activation Pathway

Mast cells (MCs) have relevant participation in inflammatory and vascular hyperpermeability events, responsible for the action of the kallikrein–kinin system (KKS), that affect patients inflicted by the severe form of COVID-19. Given a higher number of activated MCs present in COVID-19 patients and their association with vascular hyperpermeability events, we investigated the factors that lead to the activation and degranulation of these cells and their harmful effects on the alveolar septum environment provided by the action of its mediators. Therefore, the pyroptotic processes throughout caspase-1 (CASP-1) and alarmin interleukin-33 (IL-33) secretion were investigated, along with the immunoexpression of angiotensin-converting enzyme 2 (ACE2), bradykinin receptor B1 (B1R) and bradykinin receptor B2 (B2R) on post-mortem lung samples from 24 patients affected by COVID-19. The results were compared to 10 patients affected by H1N1pdm09 and 11 control patients. As a result of the inflammatory processes induced by SARS-CoV-2, the activation by immunoglobulin E (IgE) and degranulation of tryptase, as well as Toluidine Blue metachromatic (TB)-stained MCs of the interstitial and perivascular regions of the same groups were also counted. An increased immunoexpression of the tissue biomarkers CASP-1, IL-33, ACE2, B1R and B2R was observed in the alveolar septum of the COVID-19 patients, associated with a higher density of IgE⁺ MCs, tryptase⁺ MCs and TB-stained MCs, in addition to the presence of intra-alveolar edema. These findings suggest the direct correlation of MCs with vascular hyperpermeability, edema and diffuse alveolar damage (DAD) events that affect patients with a severe form of this disease. The role of KKS activation in events involving the exacerbated increase in vascular permeability and its direct link with the conditions that precede intra-alveolar edema, and the consequent DAD, is evidenced. Therapy with drugs that inhibit the activation/degranulation of MCs can prevent the worsening of the prognosis and provide a better outcome for the patient.     

Profiling of the Bacterial Microbiota along the Murine Alimentary Tract

Here, the spatial distribution of the bacterial flora along the murine alimentary tract was evaluated using high throughput sequencing in wild-type and Tff3-deficient (Tff3^KO) animals. Loss of Tff3 was linked to increased dextran sodium sulfate-induced colitis. This systematic study shows the results of 13 different regions from the esophagus to the rectum. The number of bacterial species (richness) increased from the esophagus to the rectum, from 50 to 200, respectively. Additionally, the bacterial community structure changed continuously; the highest changes were between the upper/middle and lower gastrointestinal compartments when comparing adjacent regions. Lactobacillus was the major colonizer in the upper/middle gastrointestinal tract, especially in the esophagus and stomach. From the caecum, a drastic diminution of Lactobacillus occurred, while members of Lachnospiraceae significantly increased. A significant change occurred in the bacterial community between the ascending and the transverse colon with Bacteroidetes being the major colonizers with relative constant abundance until the rectum. Interestingly, wild-type and Tff3^KO animals did not show significant differences in their bacterial communities, suggesting that Tff3 is not involved in alterations of intraluminal or adhesive microbiota but is obviously important for mucosal protection, e.g., of the sensitive stem cells in the colonic crypts probably by a mucus plume.     

Stereochemische Untersuchungen mit der 13C-NMR-Spektroskopie. V. Methyl- und tert.-butylsubstituierte Cyclohexane

Stereochemical Investigations by Means of ¹³C-N.M.R.-Spectroscopy. V. Methyl- and tert.-Butyl-substituted Cyclohexanes The ¹³-chemical shifts of some cyclohexanes with methyl and tert. butyl as substituents in configurational different positions are discussed. The substituent effects of the methyl and t-butyl groups, respectively, on the C-atoms of the ring are different and can be explained with the aid of long range (γ and δ) steric interactions. It is shown, that in all investigated compounds a twisted conformation of the ring is prefered instead of an axial arrangement of a t-butyl group.