N-Aminierung von Isochinolinbasen

N-Amination of Isoquinoline Bases 3, 3-Pentamethylene oxaziridine 1 forms an N N-bond with secondary isoquinoline bases 2a – f to give the cyclohexylidene hydrazines 3a – f . In some cases nitrogen elimination yielding indane derivatives 13b, 13e competes with hydrazone formation. The cyclic Schiff'base 14 and the β-carboline derivative 16 can also be aminated.     

Finite element analyses of slope stability problems using non-associated plasticity

In recent years, finite element analyses have increasingly been utilized for slope stability problems. In comparison to limit equilibrium methods, numerical analyses do not require any definition of the failure mechanism a priori and enable the determination of the safety level more accurately. The paper compares the performances of strength reduction finite element analysis (SRFEA) with finite element limit analysis (FELA), whereby the focus is related to non-associated plasticity. Displacement-based finite element analyses using a strength reduction technique suffer from numerical instabilities when using non-associated plasticity, especially when dealing with high friction angles but moderate dilatancy angles. The FELA on the other hand provides rigorous upper and lower bounds of the factor of safety (FoS) but is restricted to associated flow rules. Suggestions to overcome this problem, proposed by Davis (1968), lead to conservative FoSs; therefore, an enhanced procedure has been investigated. When using the modified approach, both the SRFEA and the FELA provide very similar results. Further studies highlight the advantages of using an adaptive mesh refinement to determine FoSs. Additionally, it is shown that the initial stress field does not affect the FoS when using a Mohr-Coulomb failure criterion.     

Untersuchungen an Caramel Curiepunkt-Pyrolyse von Caramelzuckersirupen und andere strukturspezifische Untersuchungen

Zusammenfassung Es wird über die Curiepunkt-Pyrolyse handelsüblicher Caramelzuckersirup-Proben und die Identifizerung von über 80 Pyrolysefragmenten durch kombinierte Capillargaschromatographie/ Massenspektrometrie berichtet. Mit dieser Methode sind die Proben untereinander and gegenüber Couleuren differenzierbar. Mittels Ultrafiltration wurden die Komponenten einer intensiv braunen Probe in Fraktionen unterschiedlicher Molekülmasse getrennt and nach Pyrolyse miteinander verglichen. In einer niedermolekularen Fraktion wurden nach Permethylierung Laevoglucosan, 1,6-Anhydro--d-glucofuranose, Trehalose, Cellobiose, Maltose, Isomaltose und Gentiobiose Bowie einige Difructosedianhydride nachgewiesen.

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Investigations of caramel. Curiepoint pyrolysis of caramel syrups and other investigations of structure

Summary A report is given on the investigation of commercial caramel syrups by Curiepoint pyrolysis and the identification of more than 80 pyrolysis products by capillary gas chromatography mass spectrometry. This method enables the differentiation between different caramel syrups and, additionally, between caramel syrups and caramel colours. Compounds of different molecular masses have been examined in the same manner after they have been isolated from an intense brown caramel sample by ultrafiltration. In a fraction consisting of compounds with low molecular masses laevoglucosan, 1,6-anhydro--d-glucofuranose, trehalose, cellobiose, maltose, isomaltose, gentiobiose and some difructosedianhydrides were identified by GC/MS after permethylation.

     

Processing and analytical characterisation of pulp-enriched cloudy apple juices

Pulp-enriched cloudy apple juices were manufactured from two apple varieties by blending of apple puree with natural cloudy apple juice in order to enrich bioactive secondary plant substances. Finishing of the puree with a 0.6-mm mesh screen and final product homogenisation revealed as the optimum processing technology for the novel 100% fruit beverage. The presence of large particles originating from the puree prevented long-term cloud stability, but due to the proportion of cloud-stable juice a complete phase separation did not occur. Optimal drinkability was achieved at a viscosity of 11.5 mPa s. Polyphenol compositions and concentrations were determined by means of RP-HPLC/PDA. The results ranged from 109 to 610 mg/l. All samples showed the typical polyphenol pattern of apples with dominating hydroxycinnamic acids followed by flavanols and flavonols. The puree addition to the cloudy apple juices increased the polyphenol concentrations by average 100%. Relatively, the highest increase could be observed for dimeric procyanidins. Different technological variants did not affect significantly the polyphenol concentrations. The dietary fibre contents of the pulp-enriched cloudy apple juices ranged from 5.8 to 9.4 g/l.     

Oxidation resistant ceramic foam from a silicone preceramic polymer/polyurethane blend

Silicon oxycarbide (SiOC) ceramic foams, produced by the pyrolysis of a foamed blend of a methylsilicone preceramic polymer and polyurethane (PU) in a 1/1 wt.% ratio, exhibit excellent physical and mechanical properties. The proposed process allows to easily modify the density and morphology of the foams, making them suitable for several engineering applications. However, it has been shown that, due to residual carbon present in the oxycarbide phase after pyrolysis, the foams are subjected to an oxidation process that reduces their strength after high temperature exposure to air (12 h 1200°C). A modified process, employing the same silicone resin preceramic polymer but a much lower PU content (silicone resin/PU=5.25/1 wt.% ratio), has been developed and is reported in this paper. Microstructural investigations showed that carbon rich regions deriving from the decomposition of the polyurethane template are still present in the SiOC foam, but have a much smaller dimension than those found in foams with a higher PU content. Thermal gravimetric studies performed in air or oxygen showed that the low-PU containing ceramic foams display an excellent oxidation resistance, because the carbon-rich areas are embedded inside the struts or cell walls and are thus protected by the dense silicon oxycarbide matrix surrounding them. SiOC foams obtained with the novel process are capable to maintain their mechanical strength after oxidation treatments at 800 and 1200°C (12 h), while SiOC foams obtained with a higher amount of PU show about a 30% strength decrease after oxidation at 1200°C (12 h).     

Method of Calculating the Charge Acceptance of Organic Photoconductors

The charge acceptance of organic photoconductors (OPC) consisting of thin layers must attain the correct value in order to produce constant copy quality. In practice, however, it can be kept constant only by taking elaborate precautions, since a number of parameters have an adverse effect on charge acceptance. The limits are described within which the photoconductors and corona properties fluctuate in actual running machines. The properties of the photo-conductor can scarcely be influenced by the user, but proper choice of the electric parameters of the charging scorotron can largely suppress the influence of the fluctuations on the final charge of the photo-conductor. If the charging device exhibits the behavior of an ideal constant voltage supply characteristic, charge acceptance would depend solely on the tolerances of this device. If the charging device supplies constant current, charge acceptance depends primarily on the properties of the photoconductor. A careful estimate must be made to determine, under conditions as practical as possible, reasons for variations in charge acceptance. There are those caused by fluctuations in the charging device and those caused by fluctuations in the photoconductor. A mathematical method is described which makes it relatively simple to determine the actual OPC charge acceptance depending on application and variation of the electrical parameters.     

Single amino acid substitutions can further increase the stability of a thermophilic L-lactate dehydrogenase

Lactate dehydrogenases are of considerable interest as stereospecificcatalysts in the chemical preparation of enantiomerically pure-hydroxyacid synthons. For such applications in synthetic organicchemistry it would be desirable to have enzymes which tolerateelevated temperatures for prolonged reaction times, to increaseproductivity and to extend then applicability to poor substrates.Here, two examples are reported of significant thermostabilizations,induced by sitedirected mutagenesis, of an already thermostableprotein, the L-lactate dehydrogenase (EC 1.1.1.27 [EC] , 35 kDa permonomer subunit) from Bacillus stearothermophilus. Thermal inactivationof this enzyme is accompanied by irreversible unfolding of thenative protein structure. The replacement of Argl71 by Tyr stabilizesthe enzyme against thermal inactivation and unfolding. Thisstabilizing effect appears to be based on improved interactionsbetween the subunits in the core of the active dimeric or tetramericforms of the enzyme. The thermal stability of L-lactate dehydrogenasevariants with an active site Arg residue, either in the 171(wild-type) or in the 102 position, is further increased bysulfate ions. The two stabilizing effects are additive, as foundfor the Argl71Tyr/ Gln1O2Arg double mutant, for which the stabilityof the protein in 100 mM sulfate solution reaches that of L-lactatedehydrogenases from extreme thermophiles. All mutant proteinsretain significant catalytic activity, both in the presenceand absence of stnhilfoing salts, and are viable catalysts inpreparative scale reactions.     

The influence of various reaction parameters on the performance of (α‐diimine)nickel(II) catalysts in ethylene oligomerization reactions

Modified (α‐diimine)nickel(II) catalysts are suitable for ethylene oligomerization reactions. Due to the mechanism (“chain running”), the formation of double‐bond isomers and branched olefins can be observed. The obtained oligomer mixtures show a Schulz–Flory distribution. Increasing ethylene pressure favors the selectivity of α‐olefin formation. The same effect can be observed when Lewis bases like thiophene or furane are added to the oligomerization reaction mixture. These results can be related to an interaction of the additives with the catalytic active species during the oligomerization process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1356–1361, 2003