This PDF file includes:

• Synthetic procedures
  
• fig. S1. Determination of fluorescence quantum yield of the oxyluciferin.
  
• fig. S2. Determination of the chemiluminescence and singlet quantum yields of the luciferin/luciferase reaction.
  
• fig. S3. Dependence of the chemiluminescence intensity from luciferin/luciferase reaction on the concentration of luciferin (76 to 760 nM) and phosphate buffer (pH 6 to 8).
  
• fig. S4. Photocathode spectral response curve provided by Berthold Detection Systems (PMT type 9107).
  
• fig. S5. Dynamics of the reaction between substrate and luciferase microsomal preparation of N. nambi.
  
• fig. S6. Chemiluminescence spectra of 1 (orange curve) and 3 (green curve) and the fluorescence spectrum of 4 in acetone (dotted curve).
  
• fig. S7. Chemiluminescence from the reaction of 1,4-dimethylnaphthalene endoperoxide (DMNO₂) with 3-hydroxyhispidin (luciferin).
  
• fig. S8. Collision-induced dissociation spectrum (ESI-MS/MS) of the labeled oxyluciferin—compound 4.
  
• fig. S9. Absorption (blue) and fluorescence emission (red) spectra of compounds 2, 3, and 5 to 9.
  
• fig. S10. Isolation and identification of compounds in peaks 2 and 4 of the luciferin 1/luciferase reaction.
  
• fig. S11. Proposed mechanisms for oxyluciferin degradation.
  
• fig. S12. Synthesis of the fungal luciferin 1.
  
• fig. S13. Synthesis of 3,4-dihydroxy-6-methyl-2H-pyran-2-one 13.
  
• fig. S14. Synthesis of compounds 14 to 16.
  
• fig. S15. Synthesis of fungal luciferin analogs 3 and 5 to 9.
  
• fig. S16. Synthesis of fungal oxyluciferins 2 and 4.
  
• fig. S17. NMR spectra chemical shifts of compounds 18 to 23.
  
• fig. S18. NMR spectra chemical shifts of luciferin analogs 3 and 5 to 9.
  
• table S1. Observed decay rate constants (k_obs), the total light emitted (Q) by the reaction of luciferin/luciferase reaction, and chemiluminescence and singlet quantum yields (Φ_CL and Φ_S) at different pH and substrate concentrations.
  
• table S2. Dependence of chemiluminescence quantum yield (Φ_CL) and singlet quantum yield (Φ_S) on the pH of luciferin-luciferase reaction.
  
• table S3. Spectral characteristics of compounds 1 to 3 and 5 to 9.
  
• table S4. Observed decay rate constant (k_obs), the total of light emission (Q), photomultiplier sensitivity correction factor (fPMT), and the chemiluminescence quantum yield (Φ_CL) obtained from the reaction between the crude extract of N. gardneri and compounds 1, 3, and 5 to 9.

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