Generation of primary amide glucosides from cyanogenic glucosides

Sendker, Jandirk; Nahrstedt, Adolf

doi:10.1016/j.phytochem.2008.11.008

Cited by 21 publications

(27 citation statements)

References 24 publications

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“…The conversion of nitriles into amides in plants can be explained either by: (1) the in vivo occurrence of a Radziszweski process, driven by the presence of hydrogen peroxide evolved upon oxidative stress such as air-drying, light exposure, senescence, or as a result of the oxidative burst caused by a fungal infection [1,56]; or by (2) the endogenous turnover of cyanogenic glucosides catalysed by specific turnover enzymes probably bifunctional nitrilase (EC 3.5.5.1) / nitrile hydratase (EC 4.2.1.84) enzymes that can form amides as major products from nitriles [5,57]. The formation of amides might be followed by the enzymatic hydrolysis of the amide function into a carboxylic acid function, and thereby release ammonia.…”

Section: Accepted Manuscriptmentioning

confidence: 99%

A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species

Pičmanová

Neilson

Motawia

et al. 2015

Biochemical Journal

119

126

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N. (2015). A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species. Biochemical Journal, 469(3), 375-389. DOI: 10.1042/BJ20150390 1 A RECYCLING PATHWAY FOR CYANOGENIC GLYCOSIDES EVIDENCED BY THE COMPARATIVE METABOLIC PROFILING IN THREE CYANOGENIC PLANT SPECIES ABSTRACTCyanogenic glycosides are phytoanticipins involved in plant defence against herbivores by virtue of their ability to release toxic HCN upon tissue disruption. In addition, endogenous turnover of cyanogenic glycosides without the liberation of HCN may offer plants an important source of reduced nitrogen at specific developmental stages. To investigate the presence of putative turnover products of cyanogenic glycosides, comparative metabolic profiling using LC-MS/MS and HR-MS complemented by ion-mobility mass spectrometry was carried out in three cyanogenic plant species: cassava, almond and sorghum. In total, the endogenous formation of 36 different chemical structures related to the cyanogenic glucosides linamarin, lotaustralin, prunasin, amygdalin and dhurrin was discovered, including di-and triglycosides derived from these compounds. The relative abundance of the compounds was assessed in different tissues and developmental stages. Based on results common to the three phylogenetically unrelated species, a potential recycling endogenous turnover pathway for cyanogenic glycosides is described in which reduced nitrogen and carbon are recovered for primary metabolism without the liberation of free HCN. Glycosides of amides, carboxylic acids and anitriles derived from cyanogenic glycosides appear as common intermediates in this pathway and may also have individual functions in the plant. The recycling of cyanogenic glycosides and the biological significance of the presence of the turnover products in cyanogenic plants open entirely new insights into the multiplicity of biological roles cyanogenic glycosides may play in plants.Abbreviations: HR-MS, high-resolution mass spectrometry; EIC, extracted ion chromatogram; IM-MS, ionmobility mass spectrometry; ATD, arrival time distribution; CID, collision-induced dissociation 2 SUMMARY STATEMENTA potential recycling pathway for cyanogenic glycosides is presented wherein reduced nitrogen and carbon are recovered for primary metabolism without HCN liberation. Common types of glycosylated pathway intermediates were found in three cyanogenic plant species: cassava, almond and sorghum.

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Section: Accepted Manuscriptmentioning

confidence: 99%

A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species

Pičmanová

Neilson

Motawia

et al. 2015

Biochemical Journal

119

126

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“…the generation of sennosides in leaves of Cassia angustifolia Vahl or generation of primary amide glucosides in Prunus laurocerasus L.) or direct enzymatic activity (e.g. the generation of secondary glycosides in Digitalis purpurea L.) until further loss of water stabilises the material (Lemli and Cuveele, 1978;Sendker and Nahrstedt, 2009). A very interesting aspect can be found with regard to pàozhì processing: there are several examples where the same raw drug material is processed by different methods to yield products that are claimed to have improved pharmacological and/or toxicological properties.…”

Section: Metabolomic Approaches For Extract Optimisationmentioning

confidence: 99%

The potential of metabolic fingerprinting as a tool for the modernisation of TCM preparations

Sheridan

Krenn

Jiang

et al. 2012

Journal of Ethnopharmacology

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A vast majority Chinese herbal medicines (CHM) are traditionally administered as individually prepared water decoctions (tang) which are rather complicated in practice and their dry extracts show technological problems that hamper straight production of more convenient application forms. Modernised extraction procedures may overcome these difficulties but there is lack of clinical evidence supporting their therapeutic equivalence to traditional decoctions and their quality can often not solely be attributed to the single marker compounds that are usually used for chemical extract optimisation. As demonstrated by the example of the rather simple traditional TCM formula Danggui Buxue Tang, both the chemical composition and the biological activity of extracts resulting from traditional water decoction are influenced by details of the extraction procedure and especially involve pharmacokinetic synergism based on co-extraction. Hence, a more detailed knowledge about the traditional extracts' chemical profiles and their impact on biological activity is desirable in order to allow the development of modernised extracts that factually contain the whole range of compounds relevant for the efficacy of the traditional application. We propose that these compounds can be identified by metabolomics based on comprehensive fingerprint analysis of different extracts with known biological activity. TCM offers a huge variety of traditional products of the same botanical origin but with distinct therapeutic properties, like differentially processed drugs and special daodi qualities. Through this variety, TCM gives an ideal field for the application of metabolomic techniques aiming at the identification of active constituents.

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“…Two prominent groups of senescence-related metabolites were identified tentatively on the basis of these data: (i) abscisic acid-related megastigmane glycosides; such compounds previously have been detected in several plant species, including Prunus spp. ( Figure S1, Supporting Information); 6−8 (ii) the concentrations of compounds related to 1 [prunasin amide (2), prunasin acid (3), and especially 4] were increased strongly in senescent leaves (Figure 1). The consistent detection of 2 and 3 also in freeze-dried green leaves is in accordance with a study on Prunus dulcis (Mill.)…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Compound 1 was isolated from fresh green leaves of P. laurocerasus as described previously. 2 Compound 2 was obtained from 1 based on a prior investigation. 11 Compound 3 was obtained as a mixture of 2S-and 2R-epimers after boiling 2 for 1 h in 0.1 M sodium hydroxide, acidifying with 10% trifluoroacetic acid to pH 2−3, and repeatedly extracting this solution with a water-saturated mixture of two parts 1-butanol and one part 2-propanol.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

“…It has been shown that 2 results from decomposition of 1 in the nonenzymatic, hydrogen-peroxide-consuming Radziszewski reaction, especially when strong illumination has bleached fresh green leaves during air drying. 2,3 In contrast, 4 has been suggested to accumulate under conditions of senescence, as leaves containing this compound as the main constituent are very easily detachable, thus indicating the formation of a petiolar abscission layer, which is a well-known indication for leaf senescence. 4 The present study aimed at providing further insight into the decomposition of 1 in the leaves of P. laurocerasus by identifying possible catabolites and providing additional evidence for the interrelation of leaf senescence with the accumulation of 4.…”

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Occurrence of Benzoic Acid Esters as Putative Catabolites of Prunasin in Senescent Leaves of Prunus laurocerasus

2016

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Prunus laurocerasus is an evergreen shrub containing large quantities of the cyanogenic glycoside prunasin (1) in its leaves, which decomposes to prunasin amide (2) or glucose-1-benzoate (4) when the leaves become chlorotic as a result of senescence or pseudosenescence. This study was aimed at the systematic identification of senescence-associated metabolites to contribute further insight into the catabolism of 1. LC-ESIMS profiles of senescent and green leaves were analyzed by principal component analysis. In senescent leaves, the concentrations of 36 compounds were increased significantly including several benzoic acid derivatives, of which prunasin amide-6'-benzoate (5) and prunasin acid-6'-benzoate (6) were isolated and identified. The observed metabolic changes were also induced by treatment of P. laurocerasus shrubs with exogenous ethylene. The data presented support an oxidative catabolism of 1 without release of hydrogen cyanide and the remobilization of its nitrogen in the course of senescence. The results are discussed in the context of functional diversification and drug discovery, where senescent plant material represents a widely unexplored source for the discovery of natural products.

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Generation of primary amide glucosides from cyanogenic glucosides

Cited by 21 publications

References 24 publications

A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species

A recycling pathway for cyanogenic glycosides evidenced by the comparative metabolic profiling in three cyanogenic plant species

The potential of metabolic fingerprinting as a tool for the modernisation of TCM preparations

Occurrence of Benzoic Acid Esters as Putative Catabolites of Prunasin in Senescent Leaves of Prunus laurocerasus

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