Nachweis von Maillard-Produkten in Malzen, Bieren und Braucouleuren

Zusammenfassung Bei der Maillard-Reaktion reagieren primär reduzierende Zucker mit den freien Aminogruppen der Aminosäuren. Dabei entstehen aus Aldosen als erste stabile Zwischenprodukte die 1-Aminosäure-1-desoxy-ketosen (Amadori-Verbindungen). In Malzen konnten zehn Amadori-Verbindungen quantitativ bestimmt werden. Sie entstehen während des Darrens des Malzes. Aufgrund unterschiedlicher Darrbedingungen unterscheiden sich die Malztypen im Gehalt und im Muster dieser Substanzen. Während der Erhitzungsvorgänge beim Brauprozeß (Maischen, Würzekochung) werden die Amadori-Verbindungen etwa zur Hälfte abgebaut, dagegen sind bei der an schließenden Gärung keine Veränderungen zu beobachten. Aus dem Gehalt und dem Muster der Amadori-Verbindungen im Bier können somit Rückschlüsse auf das verwendete Malz gezogen werden. Bei der Herstellung von Braucouleuren werden Ammoniak bzw. Ammoniumverbindungen als Aminokomponenten eingesetzt. Die Couleure enthalten deshalb keine 1-Aminosäure-l-desoxy-ketosen, dafür aber Desoxyfructosazine, die bei der Reaktion von Zuckern mit Ammoniak entstehen. Diese Pyrazinderivate wurden in Braucouleuren in hohen Mengen (2–6 g/100 g) gefunden. Es wird eine Methode vorgestellt, mit der ein Zusatz von Braucouleuren zum Bier über die Bestimmung der Desoxyfructosazine eindeutig nachgewiesen werden kann.

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Detection of Maillard products in malts, beers, and brewing couleurs

During the Maillard reaction, the reducing sugars first react with the free amino groups of the amino acids. With aldoses, 1-amino-l-deoxyketoses (ketose-amino acids, Amadori compounds) are the first stable intermediates to be formed. In malts ten different Amadori compounds could be determined that formed during the kiln-drying of malt. Dependent on the kiln-drying conditions, the different types of malt contain different amounts and proportions of these compounds. During the brewing process (mashing, mash wort cooking) about half of the Amadori compounds are decomposed, whereas during fermentation no changes can be observed. Therefore the amount and composition of Amadori compounds detected in beer may indicate the type of malt used. During the production of brewing couleurs, ammonia or ammonium compounds react with sugars and deoxyfructosazines are formed. In brewing coleurs, relatively high amount of these pyrazine derivatives (2–6 g/100 g) could be found. An analytical method is described for the quantitative determination of deoxyfructosazines, indicating an addition of brewing couleur to beer.

     

Assessing forest fire as a potential PCDD/F source in Queensland, Australia

Forest fires are suggested as a potential and significant source of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs), even though no studies to date provide sufficient evidence to confirm forest fires as a source of PCDD/Fs. Recent investigations in Queensland, Australia have identified a widespread contamination of PCDDs (in particular OCDD) in soils and sediments in the coastal region from an unknown source of PCDD/Fs. Queensland is predominately rural; it has few known anthropogenic sources of PCDD/Fs, whereas forest fires are a frequent occurrence. This study was conducted to assess forest fires as a potential source of the unknown PCDD/F contamination in Queensland. A combustion experiment was designed to assess the overall mass of PCDD/Fs before and after a simulated forest fire. The results from this study did not identify an increase in sigmaPCDD/Fs or OCDD after the combustion process. However, specific non-2,3,7,8 substituted lower chlorinated PCDD/Fs were elevated after the combustion process, suggesting formation from a precursor. The results from this study indicate that forest fires are unlikely to be the source of the unknown PCDD contamination in Queensland, rather they are a key mechanism for the redistribution of PCDD/Fs from existing sources and precursors.     

Microbial incorporation of 13C-labeled acetate at the field scale: detection of microbes responsible for reduction of U(VI)

A field-scale acetate amendment experiment was performed in a contaminated aquifer at Old Rifle, CO to stimulate in situ microbial reduction of U(VI) in groundwater. To evaluate the microorganisms responsible for microbial uranium reduction during the experiment, 13C-labeled acetate was introduced into well bores via bio-traps containing porous activated carbon beads (Bio-Sep). Incorporation of the 13C from labeled acetate into cellular DNA and phospholipid fatty acid (PLFA) biomarkers was analyzed in parallel with geochemical parameters. An enrichment of active sigma-proteobacteria was demonstrated in downgradient monitoring wells: Geobacter dominated in wells closer to the acetate injection gallery, while various sulfate reducers were prominent in different downgradient wells. These results were consistent with the geochemical evidence of Fe(III), U(VI), and SO(4)2- reduction. PLFA profiling of bio-traps suspended in the monitoring wells also showed the incorporation of 13C into bacterial cellular lipids. Community composition of downgradient monitoring wells based on quinone and PLFA profiling was in general agreement with the 13C-DNA result. The direct application of 13C label to biosystems, coupled with DNA and PLFA analysis,     

Chlorophyll Fluorescence Imaging for Monitoring the Effects of Minimal Processing and Warm Water Treatments on Physiological Properties and Quality Attributes of Fresh-Cut Salads

In this study, chlorophyll fluorescence imaging (CFI) was used to monitor plant stress induced by cutting of mini romaine lettuce (Lactuca sativa L. var. longifolia) and by cutting and washing of endive (Cichorium endivia L.) during storage. Regarding the more detailed study of endive fresh-cut salads, we additionally monitored respiratory activity, phenylalanine ammonia lyase (PAL) activity, contents of plant pigments, and cut edge browning. Determination of maximum quantum efficiency F _v/F _m was feasible through sealed consumer-sized film bags, thus, enabling the non-invasive monitoring of both fresh-cut salad types in the corresponding modified atmosphere during storage. Cutting of romaine lettuce provoked a partially reversible drop of F _v/F _m during the first 24 h. Subsequently, F _v/F _m of cut romaine strongly decreased with elapsing shelf life, whereas intact leaves exhibited only a slight decline. Regarding minimally processed endive, warm water washing progressively reduced F _v/F _m with increasing heat exposure, while respiratory activities and the content of accessory pigments remained unaffected. The heat-dependent decrease of F _v/F _m was correlated to the inhibition of the PAL activity. Mildly warm washing (40 °C, 120 s; 45 °C, 60 s) reduced PAL activities, while F_v/F_m remained widely unaffected and visual quality was only partially improved. However, warm water washing at elevated temperatures (45 °C, 120 s; 50 °C, 30–60 s) enabled maximum visual quality retention, accompanied by a significant decrease of F _v/F _m. CFI may represent a useful tool to monitor the stress conditions due to cutting and warm water treatments, hence, allowing the systematic improvement of fresh-cut produce.     

Hexabromocyclododecane enantiomers: microsomal degradation and patterns of hydroxylated metabolites

The degradation of the enantiomers of α-, β-, and γ-hexabromocyclododecane (HBCD) by phase I metabolism was investigated using induced rat liver microsomes. HBCD isomers were quantified using HPLC-MS/MS (ESI(-)) after separation on a combination of a reversed phase and a chiral analytical column. The degradation of all six isomers followed first-order kinetics and the estimated half-lives ranged from 6.3 min for both β-HBCD enantiomers to 32.3 min in case of (+)-γ-HBCD. (+)-α- and (-)-γ-HBCD displayed significantly shorter half-lives than their corresponding antipodes. It could be shown that this degradation led to a significant enrichment of the first eluting enantiomers (-)-α- and (+)-γ-HBCD. Individual patterns of mono- and dihydroxylated derivatives obtained from each α- and γ-HBCD enantiomer were seen to be distinctly characteristic. The patterns of monohydroxylated HBCD derivatives detected in liver and muscle tissues of pollack, mackerel and in herring gull eggs were largely similar to those observed in the in vitro experiments with rat liver microsomes. This enabled individual hydroxy-HBCDs to be assigned to their respective parent HBCD enantiomers.     

Mixtures of potassium sulphate and iron sulphate as catalysts for water vapour gasification of carbon: 3. Chemsitry of the in situ activation of the catalyst

Previously it was shown that certain mixtures of K₂SO₄ and FeSO₄ were excellent raw materials for catalytic water vapour gasification of carbon. It was suggested from the results that the iron salt catalyses the reduction of K₂SO₄ to K as the main catalyticly active species of gasification. This paper is concentrated on this activation process. Using TGA, DTA, ESCA, EPMA and visual observations of the melting behaviour after or during treatment of varying $\text{K}{}_2\text{SO}{}_4\text{FeSO}{}_4$ mixtures in H₂ and $\text{H}{}_2\text{H}{}_2\text{O}$ atmospheres it is found that elemental iron is formed in an early stage during heating up. This then catalyses the reduction of K₂SO₄ to K₂S, which is readily hydrolysed by water vapour to liquid KOH. K₂SO₄ and K₂S form an intermediate eutectic (m.p. = 610 °C), which favours wettability of the carbon surface and hydrolysis of K₂S. As well as FeSO₄ any iron salts can be used that are easily reduced to elemental iron in the gasification atmosphere. A general reaction scheme, including activation and catalytic gasification, is proposed. The activation of K₂SO₄ to catalytically active KOH can be described as follows: Fe-saltγFe3K₂SO₄ + 8Feγ3K₂S + 4Fe₂O₃Fe₂O₃ + 3H₂γ 2Fe + 3H₂OK₂S + H₂OγKHS+KOHKHS + H₂OγKOH + H₂S