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.     

Small Prokaryotic DNA-Binding Proteins Protect Genome Integrity throughout the Life Cycle

Genomes of all organisms are persistently threatened by endogenous and exogenous assaults. Bacterial mechanisms of genome maintenance must provide protection throughout the physiologically distinct phases of the life cycle. Spore-forming bacteria must also maintain genome integrity within the dormant endospore. The nucleoid-associated proteins (NAPs) influence nucleoid organization and may alter DNA topology to protect DNA or to alter gene expression patterns. NAPs are characteristically multifunctional; nevertheless, Dps, HU and CbpA are most strongly associated with DNA protection. Archaea display great variety in genome organization and many inhabit extreme environments. As of yet, only MC1, an archaeal NAP, has been shown to protect DNA against thermal denaturation and radiolysis. ssDNA are intermediates in vital cellular processes, such as DNA replication and recombination. Single-stranded binding proteins (SSBs) prevent the formation of secondary structures but also protect the hypersensitive ssDNA against chemical and nuclease degradation. Ionizing radiation upregulates SSBs in the extremophile Deinococcus radiodurans.     

Zur Darstellung und Charakterisierung von Vinylsenfölen

Synthesis and Characterisation of Vinylisothiocyanates The preparation of vinylisothiocyanates by treatment of γ-chloroallylchlorides with KSCN followed by rearrangement of the γ-chloroallylthiocyanates is described. The structure is proved by the reaction of the vinylisothiocyanates with mercaptides and by spectroscopic methods.     

Reaktionen mit N-Acylimino-dithiokohlensäurediestern

Reactions with N-Acylimino-dithiocarbonic-acid-diesters . Reactions of N-acylimino-dithiocarbonic-acid-S,S-diesters 1 with nucleophilic com-pounds present new possibilities to synthesize heterocycles. With amines 1a reacts by mono- and disubstitution, respectively, of methylthio-groups to isothioureas 2 and guanidines 3 , with 1,2-bi-nucleophilic arenes to benzoheterocycles 4 , with aliphatic diamines to imidazolidines 5 , pyrimidines 6 , diazepines 7 and the hexamethylene-diamine-derivatives 8. 1a reacts also with hydrazines to 1,2,4-triazoles 9 and with hydrazides to the thiosemicarbazones 10 or 1,3,4-oxadiazoles 11 . Heterocyclisations of 1 with guanidines, thiourea, salts of thiourea and amidines give the 1,3,5-triazines 12, 14, 15 and 16 . N-benzoyl-dithiocarbonic-acid-methylester -amid reacts with CH-acidic compounds to thiazoles 17 . The structures of the final products are determined by i.r.-, ¹H-n.m.r.-, u.v.- and mass-spectras.     

Effects of organic and conventional growth systems on the content of carotenoids in carrot roots, and on intake and plasma status of carotenoids in humans

BACKGROUND: The demand for organic food products has increased during the last decades due to their probable health effects, among others. A higher content of secondary metabolites such as carotenoids in organic food products has been claimed, though not documented, to contribute to increased health effects of organic foods. The aim was to study the impact of organic and conventional agricultural systems on the content of carotenoids in carrots and human diets. In addition, a human cross‐over study was performed, measuring the plasma status of carotenoids in humans consuming diets made from crops from these agricultural systems. RESULTS: The content of carotenoids in carrot roots and human diets was not significantly affected by the agricultural production system or year, despite differences in fertilisation strategy and levels. The plasma status of carotenoids increased significantly after consumption of the organic and conventional diets, but no systematic differences between the agricultural production systems were observed. CONCLUSION: The expected higher content of presumed health‐promoting carotenoids in organic food products was not documented in this study. Copyright © 2011 Society of Chemical Industry     

3β-Chlorsteroide – Ernährungsphysiologische und toxikologische Eigenschaften in Mäusen

3β-Chlorosteroids - Nutritional and Toxicological Effects in Mice 3-Chlorosteroids, e.g. 3-chlorocholest-5-ene and 3-chlorostigmast-5-ene, are formed from the corresponding sterols during the industrial hydrolysis of proteins for the production of flavor enhancers. In future, these compounds may also attract attention as environmental contaminants. A simple method for the fractionation and quantitative determination of 3β-chlorosteroids by C₁₈ reversed-phase HPLC has been developed and used for the analysis of these chlorinated steroids in protein hydrolysates. In addition, the biological effects of orally administrated 3β-chloro-steroids were tested in mice that were fed 3β-chlorocholest-5-ene and 3β-chlorostigmast-5-ene in doses of 1 and 10 mg/animal/day. The results of our study showed that body and organ weights as well as feed intake of the various experimental groups were not significantly different from those of the control group. The quantitative determination of 3β-chlorosteroids in organs and tissues revealed that intestinal absorption of 3β-chlorocholest-5-ene was higher than that of 3β-chlorostigmast-5-ene. Highest concentration of 3β-chlorocholest-5-ene was detected in liver and adipose tissue. Absorption and distribution in tissues as well as metabolism of both radioactive 3β-chloro-[4-¹⁴C]cholest-5-ene and 3β-chloro-[4-¹⁴C]stigmast-5-ene have also been studied in mice. At 2 hours after stomach incubation of the two substrates, large proportions of radioactivity had passed through the small intestine and were concentrated in the contents of caecum and colon. Only small proportions of radioactivity were detected outside the alimentary canal, predominantly in the liver. Histopathological examination of sections of organs and tissues such as stomach, duodenum, liver, kidneys, and spleen showed no indications of irreversible cell damages caused by 3β-chlorosteroids.     

Three‐dimensional modeling of porosity development during the gasification of a char particle

This work is devoted to the three‐dimensional, direct modeling of porosity and specific surface development during the gasification of a char particle. The model was developed for heterogeneous reactions occurring inside a char particle in a kinetically controlled regime. The main goal of this work is to analyze the impact of different pore size distributions on the particle carbon conversion rate. In particular, it is shown that under certain conditions the outer particle surface can influence the specific surface area. In this context the possible adaptation of the parameter ψ from the random pore model (RPM) developed by Bhatia and Perlmutter is explained. The results of simulations are compared against the RPM and discussed. Additionally, based on the results of simulations, the physics behind several input parameters used by the RPM are explored. Finally, the possible fragmentation of a chemically reacting char particle during its gasification in dependence of instantaneous porosity was investigated numerically. It was shown that the earliest fragmentation occurs at a carbon conversion of about 0.5–0.6 due to the disaggregation of the pore walls. The results are discussed and compared implicitly with data published in the literature. © 2016 American Institute of Chemical Engineers AIChE J, 63: 1638–1647, 2017     

The effect of fertilizer placement on nitrogen uptake and yield of wheat and maize in Chinese loess soils

Field trials were carried out to study the fate of¹⁵N-labelled urea applied to summer maize and winter wheat in loess soils in Shaanxi Province, north-west China. In the maize experiment, nitrogen was applied at rates of 0 or 210 kg N ha^–1, either as a surface application, mixed uniformly with the top 0.15 m of soil, or placed in holes 0.1 m deep adjacent to each plant and then covered with soil. In the wheat experiment, nitrogen was applied at rates of 0, 75 or 150 kg N ha^–1, either to the surface, or incorporated by mixing with the top 0.15 m, or placed in a band at 0.15 m depth. Measurements were made of crop N uptake, residual fertilizer N and soil mineral N. The total above-ground dry matter yield of maize varied between 7.6 and 11.9 t ha^–1. The crop recovery of fertilizer N following point placement was 25% of that applied, which was higher than that from the surface application (18%) or incorporation by mixing (18%). The total grain yield of wheat varied between 4.3 and 4.7 t ha^–1. In the surface applications, the recovery of fertilizer-derived nitrogen (25%) was considerably lower than that from the mixing treatments and banded placements (33 and 36%). The fertilizer N application rate had a significant effect on grain and total dry matter yield, as well as on total N uptake and grain N contents. The main mechanism for loss of N appeared to be by ammonia volatilization, rather than leaching. High mineral N concentrations remained in the soil at harvest, following both crops, demonstrating a potential for significant reductions in N application rates without associated loss in yield.     

Influence of Molybdenum Silicide Additions on High-Temperature Oxidation Resistance of Silicon Nitride Materials

The influence of additions of molybdenum disilicide (MoSi₂) on the microstructure and the mechanical properties of a silicon nitride (Si₃N₄) material, with neodymium oxide (Nd₂O₃) and aluminum nitride (AIN) as sintering aids, was studied. The composites, containing 5, 10, and 17.6 wt% MoSi₂, were fabricated by hot pressing. All materials exhibited a similar phase composition, detected by X-ray diffractometry. Up to MoSi₂ additions of 10 wt%, mechanical properties such as strength, fracture toughness, or creep at 1400°C were not affected significantly, in comparison to that of monolithic Si₃N₄. The oxidation resistance of the composites, in terms of weight gain, degraded. After 1000 h of oxidation at 1400° and 1450°C in air, a greater weight gain (by a factor of approximately three) was obtained, in comparison to that of the material without MoSi₂. Nevertheless, after 1000 h of oxidation, the degradation in strength of the composites was considerably less severe than that of the material without MoSi₂. An additional layer was formed, caused by processes at the surface of the Si₃N₄ material, preventing the formation of pores, cracks, or glassy-phase-rich areas, which are common features of oxidation damage in Si₃N₄ materials. This surface layer, containing Mo₅Si₃ and silicon oxynitride (Si₂ON₂), was the result of reactions between MoSi₂, Si₃N₄, and the oxygen penetrating by diffusion into the material during the hightemperature treatment.     

Formulation effects on the distribution of pigment particles in paints

Modern water-borne paints are widely used in different areas of applications ranging from high-gloss lacquers to flat, scrub-resistant interior paints. From this point of view, the pigment volume concentration (PVC) is one key-parameter adjusting the desired application properties. In high-gloss paints, for example, a low PVC is required to accommodate the proper surface roughness to achieve a high gloss. Consequently, a high concentration of TiO₂ is needed to obtain a good hiding power at the same time. Flat paints nonetheless are highly filled due to cost reasons preferentially by CaCO₃ and the pigment binding capacity of the binder is crucial. In this work, paint formulations differing in PVC, and the type of binder or dispersing agent were investigated by various techniques concerning the distribution and aggregation of pigment particles, e.g. TiO₂. To get a detailed insight into the structure of the liquid paints and the corresponding dried paint films, suitable analytical tools were applied for characterization. The structure of the liquid paints was analyzed by remission light spectroscopy (RLS), disc centrifugation, cryogenic-replication transmission electron microscopy (Cryo-replica TEM) and cryogenic-scanning electron microscopy (Cryo-SEM). The pigment distribution in the corresponding dried paint films was examined by means of atomic force microscopy (AFM), TEM and RLS. The tendency of the TiO₂-pigments to form aggregates was found to depend on both: first on the type of binder used in the formulation and second on the employed dispersing agent. It is shown that only by adjusting the properties of the binder in combination with common dispersants, it is possible to get well-distributed TiO₂ particles within the paint. Correlation of application properties, e.g. gloss and blocking to the microscopic structure is presented.