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1 Electronic Supplementary Information (ESI) for the article entitled: ICP-S-assisted nanohplc-electrospray /time-of-flight S/S selenopeptide mapping in Brazil nuts by ihaly Dernovics, Pierre Giusti and Ryszard Lobinski* Journal of Analytical Atomic Spectrometry, DOI:.39/b41c Figure-ESI 1: a) ESITOF S spectrum of the Se-peptide with m/z 2619 (detected as triply charged). b) Corresponding S/S spectra on the Se isotope, along with the sequence of the Se-peptide detected. Fragments indicated with masses in Italics were not detected. Figure-ESI 2: a) ESITOF S spectrum of the Se-peptide with m/z 25 (detected as triply charged). b) Corresponding S/S spectra on the Se isotope, along with the sequence of the Se-peptide detected. Fragments indicated with masses in Italics were not detected. Figure-ESI 3: a) ESITOF S spectrum of the Se-peptide with m/z 1424 (detected as double charged). b) Corresponding S/S spectra on the Se isotope. c) The sequence of the Se-peptide detected. Figure-ESI 4: a) ESITOF S spectrum of the Se-peptide with m/z 1224 (detected as double charged). b) Corresponding S/S spectra on the Se isotope along with the sequences of the isomers detected. Figure-ESI 5: a) ESITOF S spectrum of the Se-peptide with m/z 965 (detected as double charged). b) Corresponding S/S spectrum on the Se isotope along with the sequence identified. Figure-ESI 6: a) ESITOF S spectrum of the Se-peptide with m/z 1354 (detected as double charged). b), c): Corresponding S/S spectra on the Se isotope along with the sequences of the isomers detected. The analyte was fragmented two times with the difference of.15 min, revealing the presence of different isomers. Figure-ESI 7: a) ESITOF S spectrum of the Se-peptide with m/z 17 (detected as double charged). b) Corresponding S/S spectrum on the Se isotope along with the sequence identified. Figure-ESI 8: ESITOF S spectrum of the Se-peptide with m/z (detected as double charged). Figure-ESI 9: ESITOF S spectrum of the Se-peptide with m/z 8. Figure-ESI : a) ESITOF S spectrum of the Se-peptide with m/z 747. b), c): Corresponding S/S spectra on the Se and 82 Se isotopes, respectively, along with the sequences of the isomers detected. The analyte was fragmented two times with the difference of.21 min, revealing the presence of different isomers. Figure-ESI 11: ESITOF S spectrum of the Se-peptide with m/z 485. Please note that background subtraction was required because of a spectral overlap; therefore the Se-pattern is partly off the theoretical one. Figure-ESI 12: ESITOF S spectrum of the Se-peptide with m/z 641. This species partly co-elutes with the Se-peptide with m/z 632, therefore the same ESITOF S spectrum is shown. Please note the inset was background corrected. Figure-ESI 13: ESITOF S spectrum of the Se-peptide with m/z 632. This species partly co-elutes with the Se-peptide with m/z 641, therefore the same ESITOF S spectrum is shown. Figure-ESI 14: a) ESITOF S spectrum of the Se-peptide with m/z 616. b): Corresponding S/S spectrum on the 78 Se isotope along with the sequences of the isomers detected. Please note the inset was background corrected. Figure-ESI 15: ESITOF S spectrum of the Se-peptide with m/z 648. This species is partly overlapped with another peptide; therefore the correct isotopic pattern of Se can not be seen. Please note the inset was background corrected. Figure-ESI 16: a) ESITOF S spectrum of the Se-peptide with m/z 795 (detected as double charged). b): Corresponding S/S spectrum on the Se isotope along with the sequences of the isomers detected.

2 7 ESI Fig (a)

3 (b)

4 (c) Pyr E E C* R E B R

5 ESI Fig. 2 (a)

6 (b) B E E P R E E B P R

7 9 8 ESI Fig (a)

8 B A E N L P S R (b)

9 ESI Fig (a)

10 B E P R B E P R (b)

11 B E B E P R B E P P R R (c)

12 ESI Fig (a)

13 B L S H C* R (b)

14 ESI Fig

15 ESI Fig

16 526 ESI Fig (a)

17 B R B R Se B R (b)

18 B R B R B R B R Se (c)

19 ESI Fig

20 ESI Fig

21 ESI Fig

22 ESI Fig (a)

23 B B R R B R Se (b)

24 ESI Fig

25 ESI Fig (a)

26 B B R B B R B B R B B R B B R Se (b)

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