Synthesis of Aminopyridazines from Aminocyclopropenylium Salts and Diazomethyl Compounds [1]

Amino-substituted cyclopropenylium salts ( 11a,b ) react with diazomethyl compounds ( 12a-i ) in dichloromethane or acetonitrile in the presence of a base (ethyldiisopropylamine, 1,5-diazabicyclo[4.3.0] non-5-ene) to form 4-aminopyridazines ( 13a-i ) specifically. The reaction is interpreted in terms of an initial electrophilic diazoalkane substitution to give diazomethylcyclopropenes ( 11 + 12 → 14 ) which undergo a [1.5]-cyclisation to form the betaines 16 which, in turn, isomerise with opening of the bridging bond to give the aminopyridazines 13 . In a similar manner, the tris[amino] cyclopropenylium salts 8a,b and 10a-c are converted to the 3,4,5-tris[amino]-pyridazines ( 21a-k ) by treatment with diazomethyl compounds ( 12a, c-f ).     

Beyond low-level activity: on a "non-radioactive" gas mantle

Gas mantles for camping gas lanterns sometimes contain thorium compounds. During the last years, the use of thorium-free gas mantles has become more and more popular due to the avoidance of a radioactive heavy metal. We investigated a gas mantle type that is declared to be "non-radioactive" and that can be bought in Austria at the moment. Methods used were Instrumental Neutron Activation Analysis (INAA), gamma-spectroscopy, and Liquid Scintillation Counting (LSC). We found massive thorium contents of up to 259 mg per gas mantle. Leaching experiments showed that only 0.4% of the Th but approximately 90% of the decay products of (232)Th can be leached under conditions simulating sucking and chewing with human saliva. In this paper, the investigation of these gas mantles including the consideration of the environmental hazard caused by disposed mantles and the health hazard for unsuspecting consumers is presented and legal consequences are discussed for this fraud.     

Penicillium expansum Volatiles Reduce Pine Weevil Attraction to Host Plants

The pine weevil Hylobius abietis (L.) is a severe pest of conifer seedlings in reforested areas of Europe and Asia. To identify minimally toxic and ecologically sustainable compounds for protecting newly planted seedlings, we evaluated the volatile metabolites produced by microbes isolated from H. abietis feces and frass. Female weevils deposit feces and chew bark at oviposition sites, presumably thus protecting eggs from feeding conspecifics. We hypothesize that microbes present in feces/frass are responsible for producing compounds that deter weevils. Here, we describe the isolation of a fungus from feces and frass of H. abietis and the biological activity of its volatile metabolites. The fungus was identified by morphological and molecular methods as Penicillium expansum Link ex. Thom. It was cultured on sterilized H. abietis frass medium in glass flasks, and volatiles were collected by SPME and analyzed by GC-MS. The major volatiles of the fungus were styrene and 3-methylanisole. The nutrient conditions for maximum production of styrene and 3-methylanisole were examined. Large quantities of styrene were produced when the fungus was cultured on grated pine bark with yeast extract. In a multi-choice arena test, styrene significantly reduced male and female pine weevils’ attraction to cut pieces of Scots pine twigs, whereas 3-methylanisole only reduced male weevil attraction to pine twigs. These studies suggest that metabolites produced by microbes may be useful as compounds for controlling insects, and could serve as sustainable alternatives to synthetic insecticides.     

Isolation and Spectroscopic Characterization of Eu@C72

A new Eu-endohedral fullerene cage, namely, Eu@C₇₂, was synthesized, separated, and a single isomer, Eu@C₇₂-I, has been isolated by multi-step HPLC for the first time and characterized by LDI-TOF mass spectrometry, UV-Vis and EPR spectroscopy. Additionally, a second isomer, Eu@C₇₂-II, has been separated by HPLC and identified by LDI-TOF mass spectrometry.     

Effect of viscosities of dispersed and continuous phases in microchannel oil-in-water emulsification

Although many aspects of microchannel emulsification have been covered in literature, one major uncharted area is the effect of viscosity of both phases on droplet size in the stable droplet generation regime. It is expected that for droplet formation to take place, the inflow of the continuous phase should be sufficiently fast compared to the outflow of the liquid that is forming the droplet. The ratio of the viscosities was therefore varied by using a range of continuous and dispersed phases, both experimentally and computationally. At high viscosity ratio (η _d/η _c), the droplet size is constant; the inflow of the continuous phase is fast compared to the outflow of the dispersed phase. At lower ratios, the droplet diameter increases, until a viscosity ratio is reached at which droplet formation is no longer possible (the minimal ratio). This was confirmed and elucidated through CFD simulations. The limiting value is shown to be a function of the microchannel design, and this should be adapted to the viscosity of the two fluids that need to be emulsified.     

Mathematical model of security of the information circulating in the open optical data link channel

The analysis of probability of erroneous reception of one binary code are lead for transfer of the information to the open optical data links, including IR-keyboards. Theoretical estimations for maximum permissible values of the attitude a signal/noise are received.     

Spatially resolved positron annihilation spectroscopy on friction stir weld induced defects

A friction stir welded (FSW) Al alloy sample was investigated by Doppler broadening spectroscopy (DBS) of the positron annihilation line. The spatially resolved defect distribution showed that the material in the joint zone becomes completely annealed during the welding process at the shoulder of the FSW tool, whereas at the tip, annealing is prevailed by the deterioration of the material due to the tool movement. This might be responsible for the increased probability of cracking in the heat affected zone of friction stir welds. Examination of a material pairing of steel S235 and the Al alloy Silafont36 by coincident Doppler broadening spectroscopy (CDBS) indicates the formation of annealed steel clusters in the Al alloy component of the sample. The clear visibility of Fe in the CDB spectra is explained by the very efficient trapping at the interface between steel cluster and bulk.     

Bone regeneration with glass ceramic implants and calcium phosphate cements in a rabbit cranial defect model

Hydroxyapatite cement (BoneSource®) and brushite calcium phosphate cement (chronOS? Inject) were tested for fixation of glass ceramic implants (Bioverit®) in experimentally created cranial defects in 24 adult New Zealand White rabbits. Aim of the in vivo study was to assess and compare the biocompatibility and osseointegration of the implanted materials. Macroscopic and histological evaluations were performed 1 month, 3 months, and 6 months postoperatively. All implanted materials were well tolerated by the surrounding tissue. Both bone cements exhibited osteoconductive properties. Differences could be detected regarding to the rates of cement resorption and new bone formation. The brushite cement was resorbed faster than the hydroxyapatite cement. The chronOS? Inject samples exhibited a higher rate of connective tissue formation and an insufficient osseointegration. BoneSource® was replaced by bone with minimal invasion of connective tissue. New bone formation occurred faster compared to the chronOS? Inject group. Bioverit® implants fixed with BoneSource® were successfully osseointegrated.