Optimisation of an HPLC Selected Reaction Monitoring Electrospray Tandem Mass Spectrometry Method for the Detection of 50 Arsenic Species
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1 Electronic upplementary Information for the Paper ptimisation of an HPL elected Reaction Monitoring Electrospray Tandem Mass pectrometry Method for the Detection of 5 Arsenic pecies Volker Nischwitz* and piros A. Pergantis University of rete, Department of hemistry, Environmental hemical Processes Laboratory, 713 Voutes-Heraklion, rete, Greece * orresponding author; Tel.: ; Fax.: ; vnischwitz@chemistry.uoc.gr ontents: tructures and names of the investigated arsenic species 2-3 The abbreviations for the arsenosugars are composed of 4 parts [Nischwitz, V., Pergantis,.A., Anal. hem., 25, 77, ]: 1. The number of methyl-groups bound to the arsenic atom: DM for Dimethyl, TM for Trimethyl 2. nly for the thio-arsenosugars: Thio 3. The common core for all β-ribofuranosides: ugar 4. The characteristic functional group in the aglycone: e.g. Glycol ollision induced dissociation (ID) breakdown curves for 14 arsenic species 4-8 1
2 TMugar- DMugar- DMThiougar- R H H R + H H R H H R Adenine N N NH 2 Amino- ulfonate arbamate NH N NH 2 N H H arboxyl H arboxyl-2 Glycol H H H Hydroxy Mannitol Methoxy Phosphate H H H H H H H H P H H H H ulfate ulfonate ulfonate-2 (proposed structure in analogy to arboxyl-2) H H H H Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species H H 2
3 TMArsonio- DMArsinoyl- DMThioArsinoyl- acetic acid (acetate) H + - H Dimethylarsinoylacetic acid (DMAA) Arsenobetaine (B) Dimethylthioarsinoylacetic acid ethanol H + H H Dimethylthioarsinoylethanol Dimethylarsinoylethanol (DMAE) Arsenocholine () Tetramethylarsonium ion (TMA) + Trimethylarsine oxide (TMA) Trimethylarsoniopropionate (B-2) + - Trimethylarsoniobutyrate (B-3) H H Dimethylarsinic acid (DMA) H Monomethylarsonic acid (MMA) H H 5-Dimethylarsinoyl-2,3,4- trihydroxypentanoic acid (DMArsinoylTrihydroxypentanoic acid) H H H H Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 3
4 4 3 M TMugarAdenine Intensity m/z 37 [cps] ollision energy [ev] M TMugarAminoulfonate Intensity m/z 39 [cps] ollision energy [ev] 9 [M+H] DMThiougarAminoulfonate Intensity m/z 48 [cps] ollision energy [ev] Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 4
5 4 3 M TMugararbamate Intensity m/z 354 [cps] ollision energy [ev] TMugararboxyl M Intensity m/z 341 [cps] ollision energy [ev] M TMugararboxyl Intensity m/z 311 [cps] ollision energy [ev] Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 5
6 7 6 [M+H] DMThiougararboxyl Intensity m/z 329 [cps] ollision energy [ev] 7 6 [M+H] DMThiougarHydroxy Intensity m/z 271 [cps] ollision energy [ev] 18 DMThiougarMethoxy [M+H] Intensity m/z 285 [cps] ollision energy [ev] Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 6
7 16 TMugarulfonate [M+H] Intensity m/z 361 [cps] ollision energy [ev] [M+H] DMThiougarulfonate Intensity m/z 379 [cps] ollision energy [ev] [M+H] DMArsinoylethanol (DMAE) Intensity m/z 167 [cps] ollision energy [ev] Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 7
8 4 DMThioArsinoylethanol (DMTAE) [M+H] Intensity m/z 183 [cps] ollision energy [ev] [M+H] DMThioArsinoylacetic acid Intensity m/z 1 [cps] ollision energy [ev] Nischwitz, V., Pergantis,.A., ptimisation of an HPL-E-RM method for 5 Arsenic species 8
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