Supplementary Material
Detailed Study of Cyanobacterial Microcystins using High Performance Tandem Mass Spectrometry
Yulin Qi, Stella Bortoli, Dietrich A. Volmer*
Institute of Bioanalytical Chemistry, Saarland University, Campus B2.2, 66123 Saarbrücken, Germany
*Correspondence to: Dietrich A. Volmer; E-mail:
Figure S1. The fragments assigned from CID (a) and ECD (b) spectra of MC-RR. The full peak list is available in Supplementary Tables S1 and S2.
Figure S2. Spectrum of the MC-LR/Mg complex ([M+Mg(II)]2+) with the simulation of its isotope pattern. The magnified inset is the x-axis expansion around of m/z 507.8-509.2.
Table S1. CID fragments of MC-RR, [M+2H]2+ m/z 519.79018
Proposed formula / Fragment cleavage / Theoretical m/z / Experimental m/z / Mass error (ppm)▲C9H11O / a-H / 135.08044 / 135.08044 / 0.00
C7H11O2N2 / bc / 155.08150 / 155.08142 / -0.54
C9H13N2O4 / de / 213.08698 / 213.08696 / -0.11
C9H18N5O2 / fg / 228.14550 / 228.14551 / 0.04
C10H11N2O5 / he-H2 / 239.06625 / 239.06625 / 0.00
C11H20N5O4 / ij or kl / 286.15098 / 286.15102 / 0.14
C24H43N11O7 / [bl]2+ / 298.66680 / 298.66665 / -0.50
C11H23N6O4 / km+H2 / 303.17753 / 303.17758 / 0.16
▲C13H23N6O3 / bg / 311.18262 / 311.18262 / 0.00
C20H27N2O5 / eon-H / 375.19145 / 375.19152 / 0.19
C18H30N7O6 / dg or bi / 440.22521 / 440.22522 / 0.03
C44H70N12O9 / [pg]2+ / 455.26889 / 455.26898 / 0.20
C46H72N12O11 / [ej]2+ / 484.27163 / 484.27147 / -0.32
▲C48H73N13O11 / [M-CH3O]2+ / 503.77708 / 503.77709 / 0.02
C49H77N13O12 / [M+2H]2+ / 519.79018 / 519.79031 / 0.24
C24H42N11O7 / bl / 596.32632 / 596.32633 / 0.02
C31H47N6O6 / pq / 599.35516 / 599.35518 / 0.03
C29H47N8O7 / cpn+H / 619.35622 / 619.35588 / -0.55
C35H52N7O7 / ep / 682.39227 / 682.39242 / 0.22
C29H49N12O10 / dl / 725.36891 / 725.36882 / -0.13
C34H51N8O10 / oin-H / 731.37227 / 731.37220 / -0.09
C38H57N8O8 / cp / 753.42939 / 753.42953 / 0.19
▲C40H66N13O11 / n+H / 904.49993 / 904.49985 / -0.08
Std. Dev. / 0.24
Table S2. ECD fragments of MC-RR, [M+2H]2+ m/z 519.79018
Proposed formula / Fragm. cleavage / Theoret. m/z / Experim. m/z / Error (ppm)▲C11H23N6O4 / ab+H2 / 303.17753 / 303.17752 / -0.03
C15H28N7O4 / cd+H2 / 370.21973 / 370.21968 / -0.14
C16H28N7O4 / ed / 382.21973 / 382.21984 / 0.29
C16H30N7O4 / ed+H2 / 384.23538 / 384.23526 / -0.31
C18H30N7O6 / fd / 440.22521 / 440.22522 / 0.02
C21H34N7O7 / hg / 496.25142 / 496.25130 / -0.24
▲C49H77N13O12 / [M+2H]2+ / 519.79018 / 519.79026 / 0.15
C28H42N5O5 / ij / 528.31805 / 528.31809 / 0.08
C30H46N5O5 / jk / 556.34935 / 556.34927 / -0.14
▲C26H46N11O7 / el / 624.35762 / 624.35750 / -0.19
C27H47N12O8 / ae / 667.36343 / 667.36355 / 0.18
C34H54N9O6 / im / 684.41916 / 684.41911 / -0.07
C33H54N13O8 / nop-H / 760.42128 / 760.42113 / -0.20
C33H51N10O11 / qr / 763.37333 / 763.37296 / -0.48
C32H54N13O9 / st or su / 764.41620 / 764.41624 / 0.05
C33H56N13O9 / enq+H or dvq+H / 778.43185 / 778.43191 / 0.08
C38H62N13O11 / p+H / 876.46863 / 876.46879 / 0.18
C43H67N12O8 / xw-H2 / 879.51993 / 879.52006 / 0.15
C43H69N12O9 / ny+H2 / 897.53050 / 897.53070 / 0.22
▲C40H66N13O11 / z+H / 904.49993 / 904.49986 / -0.08
C44H68N13O9 / dw-H2 / 922.52575 / 922.52536 / -0.42
C46H73N12O9 / AB / 937.56180 / 937.56193 / 0.14
C45H68N10O12 / D+H2 / 940.50127 / 940.50137 / 0.11
C42H70N13O12 / E+H / 948.52614 / 948.52627 / 0.14
C46H69N10O12 / F+H / 953.50909 / 953.50898 / -0.12
C47H72N13O9 / Gt or Gu / 962.55705 / 962.55701 / -0.04
C47H74N13O9 / Gt+H2 or Gu+H2 / 964.57270 / 964.57293 / 0.24
C47H69N10O12 / r-H / 965.50909 / 965.50928 / 0.20
C47H71N10O12 / r+H / 967.52474 / 967.52480 / 0.06
C46H71N12O11 / Rm / 967.53598 / 967.53544 / -0.56
C48H72N10O12 / J / 980.53257 / 980.53277 / 0.20
C47H74N13O10 / ne or dv / 980.56761 / 980.56746 / -0.15
C48H72N13O10 / t-H2 or u-H2 / 990.55196 / 990.55183 / -0.13
C48H76N13O10 / t+H2 or u+H2 / 994.58326 / 994.58322 / -0.04
C48H74N11O12 / L+H / 996.55129 / 996.55119 / -0.10
C48H72N13O11 / G-H / 1006.54688 / 1006.54695 / 0.07
▲C48H74N13O11 / G+H / 1008.56253 / 1008.56260 / 0.07
C49H75N13O11 / M-(H2O) / 1021.57035 / 1021.57044 / 0.09
C49H74N12O12 / N / 1022.55437 / 1022.55457 / 0.20
C48H74N13O12 / P+H or Q+H / 1024.55744 / 1024.55758 / 0.14
▲C49H76N13O12 / M+H / 1038.57309 / 1038.57302 / -0.07
Std. Dev. / 0.20
Table S3. CID fragments of [D-Asp3]MC-LR, [M+2H]2+ m/z 491.27384
Proposed formula / Fragment cleavage / Theoretical m/z / Experimental m/z / Mass error (ppm)▲C9H11O / a-H / 135.08044 / 135.08044 / 0.00
C7H11O2N2 / bc / 155.08150 / 155.08144 / -0.41
C6H16N5O / de+H2 / 174.13494 / 174.13492 / -0.10
C9H13N2O4 / fg / 213.08698 / 213.08697 / -0.06
C10H18N5O4 / hi+H / 272.13533 / 272.13534 / 0.03
C12H18N3O5 / fc / 284.12410 / 284.12405 / -0.17
▲C10H21N6O4 / hj+H3 / 289.16188 / 289.16188 / 0.00
C17H27N4O6 / bi / 383.19251 / 383.19254 / 0.08
C18H29N4O6 / fk / 397.20816 / 397.20853 / 0.93
C19H34N7O6 / lm / 456.25651 / 456.25664 / 0.29
C19H37N8O6 / le+H2 / 473.28306 / 473.28313 / 0.15
C47H70N10O11 / [m]2+ / 475.26073 / 475.26101 / 0.59
C23H39N8O7 / bm / 539.29362 / 539.29366 / 0.07
▲C29H41N6O5 / opn-H / 553.31330 / 553.31329 / -0.01
C23H42N9O7 / be+H2 / 556.32017 / 556.32018 / 0.02
C34H48N7O8 / oqn-H / 682.35589 / 682.35582 / -0.10
C38H57N8O7 / lpn-H / 737.43447 / 737.43429 / -0.25
▲C39H63N10O11 / r+H / 847.46723 / 847.46735 / 0.14
Std. Dev. / 0.30
Table S4. CID fragments of [D-Asp3]MC-RR, [M+2H]2+ m/z 512.78236
Proposed formula / Fragment cleavage / Theoretical m/z / Experimental m/z / Mass error (ppm)▲C9H11O / a-H / 135.08044 / 135.08044 / 0.01
C7H11O2N2 / bc / 155.08150 / 155.08153 / 0.17
C9H13N2O4 / fg / 213.08698 / 213.08695 / -0.15
C10H18N5O4 / hi / 272.13533 / 272.13529 / -0.15
▲C10H21N6O4 / eo+H2 / 289.16188 / 289.16187 / -0.03
C23H41N11O7 / [bm]2+ / 291.65897 / 291.65899 / 0.06
C13H23N6O3 / bo / 311.18262 / 311.18259 / -0.08
▲C17H28N7O6 / bi / 426.20956 / 426.20956 / 0.00
C18H30N7O6 / fk / 440.22521 / 440.22520 / -0.02
C44H70N12O9 / [io]2+ / 455.26889 / 455.26896 / 0.16
C48H74N13O12 / [M+2H]2+ / 512.78236 / 512.78235 / -0.02
C23H40N11O7 / bm / 582.31067 / 582.31072 / 0.09
C23H43N12O7 / be+H2 / 599.33722 / 599.33739 / 0.29
C35H52N7O9 / oq / 714.38210 / 714.38218 / 0.11
C33H49N8O10 / isr-H / 717.35662 / 717.35678 / 0.23
▲C39H63N13O11 / r / 890.48428 / 890.48466 / 0.43
Std. Dev. / 0.16
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