Thio arsenosugars identified as natural constituents of mussels by liquid chromatography-mass spectrometry

Schmeisser, Ernst; Raml, Reingard; Francesconi, Kevin A.; Kuehnelt, Doris; Lindberg, Anna‐Lena; Sörös, Csilla; Goessler, Walter

doi:10.1039/b406917j

Cited by 76 publications

(56 citation statements)

References 6 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…Second, identification of thioylated arsenicals such as dimethylarsinothioyl acetate (Fig. 4) or thioarsenosugars [34] has raised new analytical challenges and posed new questions about metabolism. For instance, arsinothioyls confound identification by HPLC, pH-selective HG-ICP-MS, or anionexchange chromatography.…”

Section: Problems and Prospects For Future Researchmentioning

confidence: 99%

Commonalities in Metabolism of Arsenicals

Adair¹,

Waters²,

Devesa³

et al. 2005

Environ. Chem.

View full text Add to dashboard Cite

Abstract. Elucidating the pathway of inorganic arsenic metabolism shows that some of methylated arsenicals formed as intermediates and products are reactive and toxic species. Hence, methylated arsenicals likely mediate at least some of the toxic and carcinogenic effects associated with exposure to arsenic. Trimethylarsonium compounds and arsenosugars are two other classes of arsenicals to which humans are routinely exposed and there is evidence that both classes are metabolized to produce methylated arsenicals. Here, we review evidence for production of methylated metabolism and consider the challenges posed in unraveling a complex web for metabolism of arsenicals in humans.

show abstract

Section: Problems and Prospects For Future Researchmentioning

confidence: 99%

Commonalities in Metabolism of Arsenicals

Adair¹,

Waters²,

Devesa³

et al. 2005

Environ. Chem.

View full text Add to dashboard Cite

show abstract

“…uoc.gr an altemative mechanism for the methylation of inorganic arsenic in biological systems [6]. According to this methylation mechanism, complexes of arsenic with glutathione (As-GSH) are believed to play an essential role in the metabolism and transport of inorganic arsenic within an organism.Arsenic has a strong affinity for sulfur as indicated by the numerous As-S compounds containing pentavalent arsenic that have been identified in biological samples recently [7][8][9][10]. However, most of these As-S species comprise small molecules that do not contain amino acids.…”

mentioning

confidence: 99%

“…Arsenic has a strong affinity for sulfur as indicated by the numerous As-S compounds containing pentavalent arsenic that have been identified in biological samples recently [7][8][9][10]. However, most of these As-S species comprise small molecules that do not contain amino acids.…”

mentioning

confidence: 99%

Development of mass spectrometric methods for detecting arsenic-glutathione complexes

Kanaki

Pergantis

2008

J. Am. Soc. Mass Spectrom.

View full text Add to dashboard Cite

It has been suggested recently that arsenic-glutathione (As-GSH) complexes play an important role in the methylation of arsenic. The present study describes the development of high-performance liquid chromatography (HPLC)-electrospray tandem mass spectrometry (ES-MS/MS), operated in the selected reaction monitoring (SRM) mode, and HPLCinductively coupled plasma mass spectrometry (ICP-MS) methods suitable for the sensitive and selective identification of four As-GSH complexes. Method optimization was carried out using a series of synthetically prepared standards, i.e., three As-GSH species containing trivalent arsenic: tri(glutamyl-cysteinyl-glycinyl)trithio-arsenite (ATG), di(glutamyl-cysteinyl-glycinyl)methy1-dithio-arsonite (MAOC), and (a-glutemyl-cysteinyl-glycinyl) dimethyl-thio-arsinite (DMAG), as well as one As-GSH species containing pentavalent As: dimethylthioarsinic acid-glutathione (DMTAv-GSH). The collision induced dissociation behavior of these compounds was investigated in detail to identify optimum SRM transitions for each complex. Both methods were based on reversed-phase chromatography using gradient elution with methanol, formic acid, and water as solvents. The amount of methanol that was used with this HPLC method (up to 12% vol/vol) was compatible with ICP-MS, without the need of a specially adapted interface. Subsequently, these analytical methods were applied to carry out a preliminary investigation about the role of As-GSH complexes in the methylation of arsenite by methy1cobalamin (CH 3Bu) in the presence of glutathione (GSH). For the first time, the complexes ATG, MADG, and trace amounts of DMAG were detected as products of this reaction. . The predominant forms of arsenic in drinking water are arsenite and arsenate (iAs III and iAs", respectively), the inorganic species which are regarded as human carcinogens [2,3]. Inorganic arsenic compounds are transformed in the body by repetitive reduction and oxidative methylation reactions, leading to the formation of organoarsenic species, the major of which are monomethylarsonic acid (MMAv) and dimethylarsinic acid (DMAV) [3,4].The precise pathway through which inorganic arsenic is metabolized in the organism is not yet known in sufficient detail. The generally accepted methylation mechanism involves the initial conversion of pentavalent arsenic species iAsv to trivalent species iAs IlI through a two-electron reduction, while oxidative addition of a methyl group follows [4,5]. Glutathione (GSH) can act as a reducing agent and 5-adenosylmethionine (SAM) as a methyl donor. The major site for the methylation seems to be the liver. However, Hayakawa et al. recently proposed Address reprint requests to Dr. S. A. Pergantis, Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes, Heraklion 71003, Crete, Greece. E-mail: spergantis@chemistry. uoc.gr an altemative mechanism for the methylation of inorganic arsenic in biological systems [6]. According to this methylation mechanism, complexes of arsenic with gluta...

show abstract

“…[4,5] Thioarsenoribosides have also been found in molluscs. [6][7][8] At low pH (∼1), arsenoribosides degrade to 5-dimethylarsinoyl-α/β-ribofuranose (OH-riboside) [9] whereas at high pH (∼11), they are stable. [10] Anaerobic decomposition of arsenoribosides produces 2-dimethylarsinoyl ethanol (Me 2 As(O)-CH 2 -CH 2 OH; DMAE), [11] whereas aerobic decomposition produces OH-riboside, dimethylarsinate (DMA) and inorganic arsenic.…”

Section: Introductionmentioning

confidence: 99%

Changes in proportions of arsenic species within an Ecklonia radiata food chain

2008

View full text Add to dashboard Cite

Environmental context. The present study examines arsenic species in kelp and associated grazing animals of an Ecklonia radiata food chain. The study focusses on the changes in proportions of arsenoribosides obtained from E. radiata and mechanisms are proposed to explain the transformations of arsenoribosides observed in the organisms that graze on it.Abstract. Total arsenic and arsenic species in the tissues of three growth stages of the macroalgae Ecklonia radiata and within organisms that feed on it are reported. Arsenic concentrations in E. radiata tissues varied from 40 to 153 µg g −1 . Growth stage did not influence arsenic concentrations or arsenic species. E. radiata contained glycerol arsenoriboside (1-8.5%), phosphate arsenoriboside (10-22%) and sulfonate arsenoriboside (73-91%). Arsenic concentrations varied significantly among animal species and between tissues (5-123 µg g −1 ). Animals contained variable quantities of arsenobetaine (14-83%). Haliotis rubra tissues contained high concentrations of glycerol trimethylarsonioriboside (0.7-22%) and the fish Odax cyanomelas contained large quantities of phosphate arsenoriboside (25-64%) with little arsenobetaine (1.5-15%).Arsenoribosides consumed from macroalgae are substantially converted or differentially accumulated as glycerol and phosphate arsenoribosides in animal tissues. In all animals, phosphate arsenoriboside would appear to be conserved or synthesised de novo. In gastropods, glycerol trimethylarsonioriboside and thio arsenic species are formed in the digestive system. Thus, the intermediate arsenic species that form a plausible pathway for the formation of arsenobetaine from dimethylarsenoribosides are present.

show abstract

Thio arsenosugars identified as natural constituents of mussels by liquid chromatography-mass spectrometry

Abstract: Two novel thio arsenosugars have been identified by liquid chromatography-mass spectrometry as significant arsenic constituents in samples of mussels.

Cited by 76 publications

References 6 publications

Commonalities in Metabolism of Arsenicals

Commonalities in Metabolism of Arsenicals

Development of mass spectrometric methods for detecting arsenic-glutathione complexes

Changes in proportions of arsenic species within an Ecklonia radiata food chain

Contact Info

Product

Resources

About