Zur Analytik von Zuckercouleuren I. Mitteilung: Differenzierung der Couleurklassen mittels Curiepunkt-Pyrolyse-Capillargaschromatographie-Massenspektrometrie

Summary After an introduction on the production, classification, legislative regulations, toxicology, and analysis of caramel colours, a report is given on the examination of these colourings by Curie-point pyrolysis-capillary gas chromatography-mass spectrometry. This method enables the differentiation between the four classes of caramel colours on the basis of the most concentrated of more than 100 identified pyrolysis products, which requires small quantities of substance (100 g) and short periods of time (1 h).

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Zur Analytik von Zuckercouleuren I. Mitteilung: Differenzierung der Couleurklassen mittels Curiepunkt-Pyrolyse-Capillargaschromatographie-Massenspektrometrie

Zusammenfassung Nach einer Einführung zur Herstellung, Klassifizierung, rechtlichen Stellung, Toxikologie und Analytik der Zuckercouleure wird über die Untersuchung dieser Farbstoffe mittels Curiepunkt-Pyrolyse-Capillargaschromatographie-Massenspektrometrie berichtet. Anhand der konzentrationsstärksten der über 100 identifizierten Pyrolyseprodukte ist es möglich, die vier Couleurklassen bei geringem Substanz- (100 g) and Zeitbedarf (1 h) sicher zu differenzieren.

     

Biosynthesis and identification of volatiles released by the myxobacterium Stigmatella aurantiaca

The volatiles released by agar plate cultures of two strains of the myxobacterium Stigmatella aurantiaca (strains Sg a15 and DW4/3-1) were collected in a closed-loop stripping apparatus (CLSA) and analyzed by GC-MS. Large numbers of substances from different compound classes (ketones, esters, lactones, terpenes, and sulfur and nitrogen compounds) were identified; several of them are reported from natural sources for the first time. The volatiles 2-methyltridecan-4-one (17), its isomer 3-methyltridecan-4-one (20), and the higher homologue 2-methyltetradecan-4-one (18) were identified in the extracts of both strains and were synthesized. In addition, strain Sg a15 produced 2,12-dimethyltridecan-4-one (19), 2-methyltridec-2-en-4-one (23), and a series of phenyl ketones, among them 1-phenyldecan-1-one (14) and 9-methyl-1-phenyldecan-1-one (16), whereas strain DW4/3-1 emitted traces of 10-methylundecan-2-one (21). The biosynthesis of 14 and 16 was examined in feeding experiments with deuterated precursors carried out on agar plate cultures. The leucine-derived starter unit isovalerate was shown to be incorporated into 16, as was phenylalanine-derived benzoic acid into both 14 and 16. The results point to formation both of the phenyl ketones and of the structurally related aliphatic ketones through an unusual head-to-head coupling between a starter unit such as benzoyl-CoA and a fatty acyl-CoA, followed by decarboxylation.     

An ionene with spirane structure (spiroionene)

The secondary diamine 1,3,5,7-tetrahydro[1,2c:4,5c'] benzodipyrrole (3) and 1,2,4,5-tetrabromomethylbenzene (1) form a polymeric ionene with spirane structure through a repetitive alkylation reaction. The structure of the product could be proven by¹³C-NMR spectroscopy by comparison with suitable reference compounds. Solutions in aqueous methanol exhibit a typical polyelectrolyte effect. Variation of the counterions produces sufficient solubility in organic solvents. From the crystal structure of a similar model compound one can conclude that the synthesized polymer has a rod-like shape.     

Input design for guaranteed fault diagnosis using zonotopes

An input design method is presented for guaranteeing the diagnosability of faults from the outputs of a system. Faults are modeled by discrete switches between linear models with bounded disturbances and measurement errors. Zonotopes are used to efficiently characterize the set of inputs that are guaranteed to lead to outputs that are consistent with at most one fault scenario. Provided that this set is nonempty, an element is then chosen that is minimally harmful with respect to other control objectives. This approach leads to a nonconvex optimization problem, but is shown to be equivalent to a mixed-integer quadratic program that can be solved efficiently. Methods are given for reducing the complexity of this program, including an observer-based method that drastically reduces the number of binary variables when many sampling times are required for diagnosis.     

Multiple inhibitory effects of garlic extracts on cholesterol biosynthesis in hepatocytes

Exposure of primary rat hepatocytes and human HepG2 cells to water-soluble garlic extracts resulted in the concentration-dependent inhibition of cholesterol biosynthesis at several different enzymatic steps. At low concentrations, sterol biosynthesis from [¹⁴C]acetate was decreased in rat hepatocytes by 23% with an IC₅₀ (half-maximal inhibition) value of 90μg/mL and in HepG2 cells by 28% with an IC₅₀ value of 35 μg/mL. This inhibition was exerted at the level of hydroxymethylglutaryl-COA reductase (MHG-CoA reductase) as indicated by direct enzymatic measurements and the absence of inhibition if [¹⁴C]mevalonate was used as a precursor. At high concentrations (above 0.5 mg/mL), inhibition of cholesterol biosynthesis was not only seen at an early step where it increased considerably with dose, but also at later steps resulting in the accumulation of the precursors lanosterol and 7-dehydrocholesterol. No desmosterol was formed which, however, was a major precursor accumulating in the presence of triparanol. Thus, the accumulation of sterol precursors seem to be of less therapeutic significance during consumption of garlic, because it requires concentrations one or two orders of magnitude above those affecting HMG-CoA reductase. Alliin, the main sulfur-containing compound of garlic, was without effect itself. If converted to allicin, it resulted in similar changes of the sterol pattern. This suggested that the latter compound might contribute to the inhibition at the late steps. In contrast, nicotinic acid and particularly adenosine caused moderate inhibition of HMG-CoA reductase activity and of cholesterol biosynthesis suggesting that these compounds participate, at least in part, in the early inhibition of sterol synthesis by garlic extracts. Dedication: This article is dedicated to Prof. Dr. D. Mecke on the occasion of his 60th birthday.     

Nachweis und Identifizierung von archäologischen Fetten

Indication and Identification of Archaeologic Fats In comparison to the food chemistry, the special tasks of fat indication in archaeologic discoveries consist in regarding possible changes of the fatty acid chains by soil storage. But changes of the composition expressed as percentages need not inevitably occur. There are many examples especially from zoologically determined subrecent bones that the total fat amount is indeed highly reduced, but the remaining residue seems unsignificantly altered. In case of alteration on an empiric basis a solution possibility can be achieved from two sides: pure fatty acid methylates are left to the effects of the natural environment. After some time the occurred changes are analysed. Since because of the relatively short period only introducing changes can be determined, you start from the other end: For archaeological findings enough time for changes has been available. Fats are extracted from objects which were identified by an archaeobotanist as seeds of certain plants or by an archaeozoologist as bones of certain animals and compared with recent fats. Ways of conversion get visible especially by a graduation of the findings according to the age.     

Five-year experience with setup and implementation of an integrated database system for clinical documentation and research

In radiation oncology, where treatment concepts are elaborated in interdisciplinary collaborations, handling distributed, large heterogeneous amounts of data efficiently is very important, yet challenging, for an optimal treatment of the patient as well as for research itself. This becomes a strong focus, as we step into the era of modern personalized medicine, relying on various quantitative data information, thus involving the active contribution of multiple medical specialties. Hence, combining patient data from all involved information systems is inevitable for analyses. Therefore, we introduced a documentation and data management system integrated in the clinical environment for electronic data capture. We discuss our concept and five-year experience of a precise electronic documentation system, with special focus on the challenges we encountered. We specify how such a system can be designed and implemented to plan, tailor and conduct (multicenter) clinical trials, ultimately reaching the best clinical performance, and enhancing interdisciplinary and clinical research.     

Rückgewinnung von Metallen aus niedrigkonzentrierten Lösungen

Recycling of metals from low concentrated solutions. A review is given of processes used for the separation of metals from aqueous solutions, especially low concentration waste waters. Purification processes for waste water used only to reach values set by law are compared with processes that allow recovery of metals. Precipitation with and without additives, adsorption, processes with ion exchange resins, solvent extraction and membrane processes, especially liquid membrane permeation, are described. As a result of these considerations, a qualitative comparison of all the described processes becomes possible. For the separation of zinc from a waste water stream, a special economic comparison is also shown between precipitation processes and the liquid membrane permeation process. Finally, the latest developments in the fields of solvent extraction and liquid membrane permeation are discussed.     

Hydrierende Vergasung von Kohle – Neuere Betriebsergebnisse

Hydrogasification of coal – recent operational results . The Rheinische Braunkohlenwerke AG has built and has been operating a semi-technical pilot plant for hydrogasification of coal in a fluidized bed. The objective is to develop a coal gasification process with hydrogen for producing directly substitute natural gas. Between 1976 and 1981, the semitechnical pilot plant having a capacity of 100 kg C/h was operated for about 22,900 h under test conditions, more than 9,500 h of which were under gasification conditions. During this time, approximately 1,400 metric tons of dry coal were gasified. The longest coherent operational phase under gasification conditions was 748 h in which 86.4 metric tons of dry lignite were gasified. Carbon gasification rates up to 82% and methane contents in the dry raw gas (free of N₂) up to 48 vol.-% were obtained. A detailed evaluation of the test results provided information on the influence of additional parameters on the efficiency dates of the gasifier and a considerable refining of the results obtained previously. Moreover, several components were tested for which no operational experience had previously been gained; these were newly developed devices, e. g. the inclined tube for feeding coal into the fluidized bed. Within the framework of scale-up work to large-scale coal gasification plants, a pilot plant having a capacity of approximately 6 t C/h will be commissioned in late 1982.     

Nutrient balance of shifting cultivation by burning or mulching in the Eastern Amazon – evidence for subsoil nutrient accumulation

For over a hundred years shifting cultivation with slash-and-burn land preparation has been the predominant type of land use by smallholders in the Bragantina region of the Brazilian Eastern Amazon. This study contrasts the nutrient balance of slash-and-burn agriculture with a fire-free cultivation. Therefore, one half of a 3.5-year-old (28.7 t DM ha^–1) and a 7-year-old woody fallow vegetation (46.5 t DM ha^–1) was burnt and the other half mulched, leaving the biomass as a surface residue. Subsequently, a sequence of maize, beans and cassava was cropped for 1.5 year. Burning the 3.5- and 7-year-old fallow removed 97 and 94% of the C, 98 and 96% of the N, 90 and 63% of the P-stocks, and between 45 and 70% of the cations K, Mg and Ca of the aboveground biomass by volatilization or ash-particle transfer. These losses were avoided with the slash-and-mulch land preparation. Mulching did not increase the losses of nutrients by leaching, despite the high amount of rapidly decomposing surface mulch. Also the length of preceding fallow had no significant influence on leaching losses. At a depth of 3 m, leached nutrients were quantitatively negligible in both treatments. Comparing the nutrient fluxes at soil depths of 0.9 m, 1.8 m and 3 m, the amounts of all mobile nutrients, and also of chloride and sodium were markedly reduced during percolation and must have been retained. It is likely that nutrient retention in the subsoil layer is only temporary, emphasizing the need for a rapid re-establishment of the naturally deep-rooting secondary vegetation after abandonment of sites to enable uptake of these nutrients. The overall nutrient balance was highly negative for slash-and-burn. 291 and 403 kg N ha^–1, 21 and 18 kg P ha^–1, and 70 and 132 kg K ha^–1 were removed from the burnt plots with a preceding fallow of 3.5 and 7 years, respectively. A reduced fallow period (3.5 years), which is a common trend in the region, resulted in a higher mean annual rate of nutrient loss averaged over the duration of the cycle than a fallow period of 7 years. Eliminating the burning losses by mulching brought the agricultural system back to an equilibrated or even slightly positive nutrient balance, even after a reduced fallow period. Thus, slash-and-mulch is a viable alternative to maintain agricultural productivity and ecosystem functioning.