SUPPLEMENTARY MATERIAL

Enzymatic synthesis of bromo- and chlorocarbazoles and elucidation of their structures by molecular modeling

John Mumbo 1,2,3,4*, Dieter Lenoir1, Bernhard Henkelmann1, Karl-Werner Schramm1,2**

1.  Helmholtz Zentrum München-German Research Center for Environmental Health (GmbH),
Molecular EXposomics, Ingolstädter Landstraße 1, 85764 Neuherberg, Germany
email: * , **

2.  Department für Biowissenschaftliche Grundlagen, TUM-Technische Universität München,
Weihenstephaner Steig 23, 85350 Freising, Germany
email: *, **

3.  Department of Chemistry, Maseno University, Private Bag, Maseno, Kenya

4.  National Environment Management Authority, P.O. Box 67839-00200, Nairobi, Kenya

Supplementary Material

Page Material

S-2 Figure S1. Gas chromatogram of (A) bromocarbazoles and (B) chlorocarbazoles
detected during halogenation of carbazole by chloroperoxidase of Caldariomyces
fumago.

S-3 to S-6 Figure S2 to Figure S5. Mass spectra of mono-, di-, tri- and tetra-bromocarbazoles

S-7 to S-9 Figure S6 to Figure S8. Mass spectra of di-, tri- and tetra-chlorocarbazoles

S-10 Table S1 Substrate concentrations in environmental water samples

S-11 Table S2. Log Kow values of carbazole, bromo- and chlorocarbazoles

A
/ /
B
/ /

Fig. S1 Gas chromatograms of bromocarbazoles (A) from left to right and chlorocarbazoles (B) also from left to right. The synthesis followed the same trend with the mono- and dihalogenated carbazoles formed in the 2:2:1 and 1:10:3 reaction ratio treatments while mono-, di-, tri- and tetrahalogenated carbazoles were all formed in 1:1000:50 reaction ratio treatments.

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Fig. S2 Mass spectrum of monobromocarbazole

Fig. S3 Mass spectrum of dibromocarbazole

Fig. S4 Mass spectrum of tribromocarbazole

Fig. S5 Mass spectrum of tetrabromocarbazole

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Fig. S6 Mass spectrum of dichlorocarbazole

Fig. S7 Mass spectrum of trichlorocarbazole

Fig. S8 Mass spectrum of tetrachlorocarbazole

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Table S1 Substrate concentrations in environmental water samples

Substrate / Source / Environmental concentrations (mg/L) / Reference
Carbazole / Wastewater effluents / 66 to 1080 / Bursey and Pellizzari 1982
Municipal waste water treatment sludge / 0.52 to 2.77 / Constable et al. 1986
Oil / 0.13 to 2.0 / Bakr 2009
Creosote / 9000 / Krone et al. 1986
Bromide / Seawater / 65 to 71 / Flury and Papritz 1993
Chloride / River / 11to 42 / Brooker 1984
Oceans / 19,000 / Stumm and Morgan 1996
Waste water / 30 to 1000 / Metcalf and Eddy 1991
Hydrogen peroxide / Freshwater / 0.001 to 0.109 / Cooper et al. 1989, Moore et al. 1993
seawater / 0.001 to 0.0136 / Moore et al. 1993, Fujiwara et al. 1993

Table S2 Log Kow values of carbazole, bromo- and chlorocarbazoles

Compound / Log Kow / Compound / Log Kow
1,3,6,8-tetrabromocarbazole / 6.2 / 1,3,6,8-tetrachlorocarbazole / 5.9
1,3,6-tribromcarbazole / 5.5 / 1,3,6-trichlorocarbazole / 5.3
3,6-dibromocarbazole / 4.8 / 3,6-dichlorocarbazole / 5.4
3-bromocarbazole / 4.4 / 3-chlorocarbazole / 4.3
Carbazole / 3.7

Source: National Centre for Biotechnology Information (NCBI), US National library of medicine

References

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