Table S1: Fragment ions of actinomycin D species

obtained by PSD-MALDI-TOF mass spectrometry

actinomycin D demethylact didemethylact
D D
fragments m/z
calc. found found found
Fragment ions of the peptide lactone moieties:
VP 197.2 197.5 197.4 197.3
PMeG 169.1 169.2(1) 169.4 169.2
MeGMeV 185.1 185.3 185.3 185.1
VPMeG 268.2 268.5 268.5 268.3
PMeGMeV 282.2 282.2 (2) 282.4 282.1
H-PMeGMeV-OH 300.2 300.3 (3) 300.6 300.3
VPMeGMeV 381.3 381.4 (4) 381.7 381.6
H-VPMeGMeV-OH 399.3 399.4 (5) 399.7 399.3
TVPMeGMeV 482.3 482.4 482. 7 482.3
Fragment ions generated by elimination of parts of the peptide lactone moieties
from actinomycin D species:
Loss of:
V 1157.3 1157.8 1143.6 n.f.
P 1159.3 1159.8 1145.7 1131.8
MeVal 1143.3 1143.7 1129.5 1115.5
2V 1058.2 1058.5 1044.5 1030.5
PMeGMeV 975.2 975.8 961.5 947.3
H-PMeGMeV-OH 957.2 957.4 (11) 943.4 929.6
H-VPMeGMeV-OH 858.1 858.6 (10) 844.4 830.6
TVPMeGMeV 775.1 775.4 (9) 761.6 747.5
H-PMeGMeV-OH 658.0 658.5 (8) 644.4 n.f.
from both rings
H-PMeGMeV-OH 558.9 559.4 (7) 544.6 530.2
from one ring and
H-VPMeGMeV-OH
from the other
H-VPMeGMeV-OH 459.8 460.2 (6) 446.6 432.4
from both rings
VPMeGMeV + H2O 531.0 531.4 517.4 504.1
from both rings
All mass numbers represent an average of the data obtained from at least 5 PSD-
fragment spectra. The numbers set in parenthesis behind the masses of actinomycin
D - fragments correspond to the numbers indicating prominent mass peaks in the
PSD-MALDI-TOF mass spectrum of actinomycin D shown in Fig. S2.