Über Belichtungsprodukte von Mutterkornalkaloiden. 39. Mitteilung über Mutterkornalkaloide
TL;DR: In this paper, the photochemisch hervorgerufene neuartige Reaktion von Ergotamin and andern lyserg- and isolysergsaurehaltigen Verbindungen in saurer, wasseriger Losung studiert and dabei festgestellt, dass sich unter dem Einfluss des Lichts an die Doppelbindung Δ9,10 des Rings D im Lyserg- bzw. IsolysergSAurerest 1 Mol Wasser anlagert.
Abstract: Es wurde die photochemisch hervorgerufene neuartige Reaktion von Ergotamin und andern lyserg- und isolysergsaurehaltigen Verbindungen in saurer, wasseriger Losung studiert und dabei festgestellt, dass sich unter dem Einfluss des Lichts an die Doppelbindung Δ9,10 des Rings D im Lyserg- bzw. Isolysergsaurerest 1 Mol Wasser anlagert. Die mit der Vorsilbe „Lumi” (Lumi-ergotamin, Lumi-ergotaminin, Lumi-lysergsaure etc.) bezeichneten Belichtungsprodukte sind in manchen ihrer Eigenschaften (z. B. Fehlen der Fluoreszenz im ultravioletten Licht, UV.-Absorptionsspektren) den entsprechenden Dihydroverbindungen, bei denen durch Anlagerung von Wasserstoff die Doppelbindung Δ9,10 ebenfalls abgesattigt ist, sehr ahnlich. Auch durch die Anlagerung von Wasser an die Doppelbindung Δ9,10 entsteht an C 10 ein neues Asymmetriezentrum, so dass je zwei stereoisomere Belichtungsprodukte, die wir in Beispielen fassen, analysieren und beschreiben konnten, entstehen. Durch die reduktive Spaltung von Lumi-ergotamin(I) zu Dihydro-lysergol(I) und Dihydro-isolysergol(I) ist wahrscheinlich gemacht, dass die Hydroxylgruppe bei den Lumi-Verbindungen an C 10 sitzt.
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TL;DR: Estimates of exposure for livestock based on example diets and levels of EAs in cereal grains reported suggest that under normal conditions the risk of toxicosis is low and the Panel concluded that whilst the available data do not indicate a concern for any population subgroup, the dietary exposure estimates relate to a limited number of food groups and a possible unknown contribution from other foods cannot be discounted.
Abstract: The European Food Safety Authority (EFSA) was asked by the European Commission to deliver a scientific opinion on ergot alkaloids (EAs) in food and feed. EAs are produced by several members within the fungal orders of Hypocreales and Eurotiales. In Europe, Claviceps purpurea is the most widespread Claviceps species within the Hypocreales. A total of 20 558 analytical results for EAs in 1 716 food, 496 feed and 67 unprocessed grain samples were considered in this opinion. Based on the EAs identified in sclerotia of C. purpurea, and recent literature data, the EFSA Panel on Contaminants in the Food Chain (CONTAM Panel) based its risk assessment on the main C. purpurea EAs, namely ergometrine, ergotamine, ergosine, ergocristine, ergocryptine (which is a mixture of a- and s- isomers), ergocornine, and the corresponding –inine epimers. The CONTAM Panel performed estimates of both chronic and acute exposure for various age groups across European countries. A BMDL10 of 0.33 mg/kg b.w. per day was calculated for the incidence of tail muscular atrophy in a 13-week rat feeding study of ergotamine. This effect was considered representative of the vasoconstrictive effects of EAs and provided a suitable reference point for establishment of a group acute reference dose of 1 µg/kg body weight (b.w.) and a group tolerable daily intake of 0.6 µg/kg b.w. per day. The Panel concluded that whilst the available data do not indicate a concern for any population subgroup, the dietary exposure estimates relate to a limited number of food groups and a possible unknown contribution from other foods cannot be discounted. Estimates of exposure for livestock based on example diets and levels of EAs in cereal grains reported suggest that under normal conditions the risk of toxicosis is low.
144 citations
Cites background from "Über Belichtungsprodukte von Mutter..."
...Under acid conditions the main reaction products promoted by UV-light are the so called “lumi”-derivatives, which are generated through the addition of water to the Δ9,10-double bond and are characterised by the loss of fluorescence (Stoll and Schlientz, 1955)....
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16 May 2008-Food Additives and Contaminants Part A-chemistry Analysis Control Exposure & Risk Assessment
TL;DR: The major focus of the present paper is to report on the latest developments for the determination of major ergot alkaloids and their epimers in cereals and cereal-derived products.
Abstract: The purpose of this paper is to summarize the most relevant and recent information available on ergot alkaloids. This includes information about their occurrence, toxicity, chemistry, statutory limits, and their significance in feed and food. Recently, in 2005, the European Food Safety Authority (EFSA) concluded that validated analytical methods for the quantification of ergot alkaloids in feed materials are needed. For that reason, the major focus of the present paper is to report on the latest developments for the determination of major ergot alkaloids and their epimers in cereals and cereal-derived products. Information about the stability and the availability of calibrants, sampling issues, extraction and clean-up strategies, and a variety of final separation and detection techniques is provided. The recently developed liquid chromatography-tandem mass spectrometric methods (LC-MS/MS) for the simultaneous quantification and identification of ergot alkaloids are given special consideration.
138 citations
Cites background from "Über Belichtungsprodukte von Mutter..."
...Analyses of agricultural commodities and foods for ergopeptide alkaloids should be carried out in subdued light to minimize the formation of ‘lumiergopeptines’, which are water-addition products (Stoll and Schlientz 1955)....
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TL;DR: In this paper, the authors showed that DSBP is photochemically degraded three times faster in summer noon terrestrial sunlight at 25 °C than DAS 1 and DAS 2 (t 1/2 = 278 and 313 min) because of a higher rate of sunlight absorption by the DBSP isomer mixture.
Abstract: Stilbene-type fluorescent whitening agents (FWAs), such as the distyryl biphenyl (DSBP) and the diaminostilbene types (DAS 1 and DAS 2), are commonly used in detergents and papers. They are not readily biodegradable, but due to their ability to absorb part of the terrestial sunlight, they can be photochemically degraded in natural surface waters. Following a fast preceding photoisomerization, the three compounds are degraded by direct photochemical processes yielding mainly aldehydes and alcohols. Their degradation quantum yields are similar, about 10-4. Nevertheless, in samples of a eutrophic Swiss lake water, DSBP is photochemically degraded three times faster (t1/2 = 87 min) in summer noon terrestrial sunlight at 25 °C than DAS 1 and DAS 2 (t1/2 = 278 and 313 min) because of a higher rate of sunlight absorption by the DSBP isomer mixture. All FWAs are degraded faster if the oxygen concentration is increased. Dissolved natural organic material partly inhibits the degradation of DSBP in the reaction with...
94 citations
TL;DR: The fact that ergovaline, the most predominate ergopeptine alkaloid, is present at biologically active concentrations in endophyte-infested (E+) tall fescue, has led to renewed scientific interest in these alkaloids as they relate to animal health and economic consequences.
81 citations
References
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82 citations
TL;DR: In this paper, aufhebung des Asymmetriezentrums am Kohlenstoffatom 8 durch β-Aminocarbonsaure-Spaltung ergibt ein identisches Lactam aus Lysergsaure and Isolysergsaure, was zur Formulierung dieser Isomeren als Diastereomere fuhrt.
Abstract: Die Aufhebung des Asymmetriezentrums am Kohlenstoffatom 8 durch β-Aminocarbonsaure-Spaltung ergibt ein identisches Lactam aus Lysergsaure und Isolysergsaure, was zur Formulierung dieser Isomeren als Diastereomere fuhrt. Ihre hydrierbare Doppelbindung wird auf Grund des Vergleichs der Absorptionsspektren in Δ9-10 festgelegt. Der Hofmann'sche Abbau, die Decarboxylierung und die Hydrierung von Lysergsaure und Isolysergsaure werden in Ubereinstimmung mit dieser Auffassung formuliert. Fur den Mechanismus der reversiblen Lysergsaure-Isolysergsaure-Umlagerung wird eine Erklarung gegeben.
64 citations
TL;DR: In this article, the vier isomeren Dihydro-lysergsaure and die entsprechenden Dihdro-norlysergauren Konfigurations-and Konformationsformeln angegeben.
Abstract: Auf Grund der chemischen und physikalisch-chemischen Eigenschaften werden fur die vier isomeren Dihydro-lysergsauren und die entsprechenden Dihydro-nor-lysergsauren Konfigurations- und Konformationsformeln angegeben. In der Dihydro-lysergsaure(I) und in der Dihydro-isolysergsaure(I) sind die Ringe C und D trans-, in der Dihydro-lysergsaure(II) und in der Dihydro-isolysergsaure(II) cisverknupft. Den Dihydro-lysergsauren(I) und (II) kommt die 5,8-cis-, den Dihydro-isolysergsauren(I) und (II) die 5,8-trans-Konfiguration zu, wobei die Carboxylgruppe in der Dihydro-lysergsaure(I) und in der Dihydro-isolysergsaure(II) aquatoriale, in der Dihydro-lysergsaure(II) und in der Dihydro-isolysergsaure(I) axiale Lage einnimmt.
52 citations
26 citations
TL;DR: In this paper, einer grossern Anzahl saureamidartiger Derivate der Lysergsaure, Isolysergaaure, Dihydro-lysergaure(I) and Díydroisolysergsaure (I) with primaren und sekundaren Aminen beschrieben.
Abstract: Es werden Darstellung und Eigenschaften einer grossern Anzahl saureamidartiger Derivate der Lysergsaure, Isolysergsaure, Dihydro-lysergsaure(I) und Dihydro-isolysergsaure(I) mit primaren und sekundaren Aminen beschrieben.
20 citations