Additional file 1 of Phototransformation kinetics of cyanobacterial toxins and secondary metabolites in surface waters
Creators: name: Regiane Natumi
name: Marcotullio, Sandro
name: Janssen, Elisabeth M.-L.
Publisher: name: figshare
Year: 2021
Subjects: subject: Biochemistry
subject: Medicine
subject: Microbiology
subject: FOS: Biological sciences
subject: FOS: Biological sciences
subject: 59999 Environmental Sciences not elsewhere classified
subject: FOS: Earth and related environmental sciences
subject: FOS: Earth and related environmental sciences
subject: 69999 Biological Sciences not elsewhere classified
subject: Inorganic Chemistry
subject: FOS: Chemical sciences
subject: FOS: Chemical sciences
subject: Plant Biology

description: Additional file1: Figure S1. Absorbance spectra for extracts of cyanobacteria pooled from Dolichospermum flos aquae, Microcystis aeruginosa PCC7806, Microcystis aeruginosa UV006 and Planktothrix rubescens before (dark green upper line) and after (light green lower line) purification by liquid-liquid extraction. The absorbance spectra were corrected by extract volume analysed. Figure S2. Light spectrum comparison of the solar simulator Heraeus Suntest CPS+(black) versus natural sunlight measured in Zurich on July 2013 (blue) showing the absolute light flux (A) and relative light intensities (B). Figure S3. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Aerucyclamide A bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S4. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Anabaenopeptin A bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S5. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Anabaenopeptin B bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S6. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Cyanopeptolin A bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S7. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Cyanopeptolin D bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S8. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin LA standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S9. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin LF standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S10. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin LR standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S11. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin LW standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S12. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin LY standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S13. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Microcystin YR standard (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S14. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between Oscillamide Y bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the HCD collision energy are noted in the title line. Figure S15. Comparison of relative intensity over m/z range for mass spectrometry fragmentation spectra between [D-Asp3,E-Dhb7]-MC-RR bioreagent (top, orange) and cyanobacterial extract spiked in lake matrix (bottom, blue) as head to tail plots. The m/z value, the retention time (RT in min) and the CID collision energy are noted in the title line. The head to tail plot suggests that the compound present in the cyanobacterial extract is a different structural isomer from the Microcystin-Group-1024. Figure S16. Cyanopeptide degradation during exposure to simulated sunlight at pH 9 in lake Greifensee water as the natural log-transformed peak areas versus irradiation time (min) for seven anabaenopeptins, two aeruginosins, three cyanopeptolins and 18 microcystins. The filled symbols represent dark controls, the error bars represent one standard deviation, the dark red line represent the linear model and the dashed red lines represent the 95% confidence interval. Figure S17. Change of concentration of [D-Asp-3]MC-MR and its oxidated variant [DAsp- 3]MC-M(O)R, which was present in the starting material but increased during photochemical exposure indicating that it was formed, potentially from oxidation of [D-Asp-3]MC-MR. Figure S18. Comparison of cyanopeptide degradation during exposure to simulated sunlight at pH 9 in lake Greifensee water (full line) and in buffered water (dashed line) as the natural log-transformed peak area versus irradiation time (min) for microcystins: MC-LR (A), MC-LA (B), MC-RR-variant group 1024 (C), MC-LM (D), MC-MR (E) and MC-YR (F); The filled symbols represents dark controls and the error bars represents one standard deviation. The first-order degradation rate constants, kobs (s-1) for lake matrix and buffered water and the p-value of the t-test of the slope between conditions for each cyanopeptide are listed. Figure S19. Observed decay rate (kobs, s-1) for the 37 cyanopeptides that presented first-order decay relative to the presence of selected amino acid moieties: no photolabile moiety (“none”, coral), methionine (yellow), oxidized tryptophan (green), tyrosine variant (blue), and phenylalanine (pink). P-values of Tukey pairwise ANOVA from comparison to cyanopeptides with no photolabile amino acids are listed as **p-value &lt;0.001 and *p-value&lt;0.05. Figure S20. Observed decay rate (kobs, s-1) for the 37 cyanopeptides that presented first-order decay relative to the cyanopeptide class of microcystin (coral), cyclamide (yellow), aeruginosin (green), anabaenopeptin (blue), and cyanopeptolin (pink). One-way ANOVA did not indicate any significance difference between classes (p-value = 0.501). Figure S21. MS/MS annotation at HCD30 for Anabaenopeptin F. Figure S22. MS/MS annotation at HCD20 for Microcystin-LM. Text S1. Additional Materials. Text S2. Photon fluence rate. Table S1. Composition of modified WC growth medium (Guillard 1972). Table S2. Standard analytical information including: limit of detection (LOD) and limit of quantification (LOQ) for the reference standards and bioreagents in lake matrix experiment and buffered nanopure water for pH range experiments. Table S3. List of compounds and their respective bioreagent or reference standard used for quantification as class equivalents by external calibration curve. Table S4. List of all tentatively identified cyanopeptides in cell extracts of Dolichopermum flos aquae, Microcystis aeruginosa PCC7806, Microcystis aeruginosa UV006 and Planktothrix rubescens. Only the peptides that could be classified as tentative candidate (level 3), probable structure (level 2) or confirmed structure (level 1) are reported. Cyanopeptide references can be found at CyanometDB (Jones et al.). Only compounds above LOQ are reported. Table S5. Isobaric compound group name (cyanopeptide class-group-MW) and individual compounds within each group with the same molecular formula. Only compounds above LOQ are reported.