Analysis of two new degradation products of arsenic triglutathione in aqueous solution

doi:10.1007/s11705-012-1208-2

Front Chem Sci Eng

2012, Vol. 6

Issue (3) : 292-300 https://doi.org/10.1007/s11705-012-1208-2

RESEARCH ARTICLE

Analysis of two new degradation products of arsenic triglutathione in aqueous solution

Feng ZHAO, Yuchen CHEN, Bin QIAO, Jing WANG, Ping NA(

)

School of Chemical Engineering and Technology, Tianjin University, Tianjin 300072, China

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Abstract

Inorganic arsenicals, including arsenite (As^III) and arsenate (As^V), are well-known human carcinogens. Recently, studies have indicated that arsenic triglutathione (As(GS)₃) is unstable in an aqueous solution. The present study was designed to evaluate the degradation mechanism of As(GS)₃ in an aqueous solution using high-performance liquid chromatography-electrospray ionisation mass spectrometry (HPLC-ESI-MS). Based on the fragments obtained from MS² and MS³, we identified two new compounds: one was an isomer of glutathione (GSH), and the other was a product from the cleavage of the glutamyl of oxidised glutathione (GSSG). The isomerization of GSH resulted in the loss of its function such as detoxification of many reactive metabolites. The formation of the two new compounds affected the ratio of GSH/GSSG, and thus may affect the antioxidant and detoxification of GSH/GSSG in mammalian cells.

Keywords arsenic triglutathione glutathione HPLC-ESI-MS

Corresponding Author(s): NA Ping,Email:naping@tju.edu.cn

Issue Date: 05 September 2012

Cite this article:

Feng ZHAO,Yuchen CHEN,Bin QIAO, et al. Analysis of two new degradation products of arsenic triglutathione in aqueous solution[J]. Front Chem Sci Eng, 2012, 6(3): 292-300.

URL:

https://academic.hep.com.cn/fcse/EN/10.1007/s11705-012-1208-2
https://academic.hep.com.cn/fcse/EN/Y2012/V6/I3/292

Fig.1 (A) HPLC profile of synthesized As(GS). (B) ESI-MS of the protonated ions of As(GS). The chromatogram was obtained with Waters Atlantis T column at 25°C, using water (0.1% formic acid, v/v) and acetonitrile (0.1% formic acid, v/v) as mobile phases in gradient mode with the injection volume of 20 μL

Tab.1 Molecular ion peaks obtained by ESI-MS

Fig.2 The chromatograms obtained by HPLC-ESI-MS at different times during the reaction: (A) the total ion chromatogram (TIC) of As(GS) at beginning; (a) the RIC of As(GS) at beginning; (B) the TIC of As(GS) after reacting for 24 h; (b) the RIC of As(GS) after reacting for 24 h; (C) ESI-MS of X; (D) ESI-MS of Y

Fig.3 The chromatograms obtained by HPLC-ESI-MS at different reaction times: (A) the TIC of GSH at beginning; (a) the RIC of GSH at beginning; (B) the TIC of GSH after reacting for 24 h; (b) the RIC of GSH after reacting for 24 h; (C) ESI-MS of GSSG

Fig.4 The reaction step and the structure of -GSH

Fig.5 The reaction step of GSSG and the structure of the new compound formed

Fig.6 MS spectrum of / = 308.3

Fig.7 The characteristic cleavage of -GSH

Fig.8 (a) MS of / = 484.5 and (b) MS of / = 354.9

Fig.9 The characteristic cleavage of GSSCys-Gly-OH

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