Bromide peroxidase explained

Bromide peroxidase
Ec Number:	1.11.1.18

Bromide peroxidase (bromoperoxidase, haloperoxidase (ambiguous), eosinophil peroxidase) is a family of enzymes with systematic name bromide:hydrogen-peroxide oxidoreductase. These enzymes catalyse the following chemical reaction:^{[1] [2] [3]}

HBr + H₂O₂

\rightleftharpoons HOBr + H₂O

The HOBr is a potent brominating agent. The many organobromine compounds observed in marine environments are the products of reaction with this oxidized form of bromine.

Bromo peroxidases of red and brown marine algae (Rhodophyta and Phaeophyta) contain vanadate (vanadium bromoperoxidase). Otherwise vanadium is unusual cofactor in biology.^[4] By virtue of this family of enzymes, a variety of brominated natural products have been isolated from marine sources.

Related chloroperoxidase enzymes effect chlorination. In the nomenclature of haloperoxidase, bromoperoxidases classically are unable to oxidize chloride at all. For example, eosinophil peroxidase appears to prefer bromide over chloride, yet is not considered a bromoperoxidase because it is able to use chloride.

Muricidae (was Murex) spp. snails have a bromoperoxidase used to produce Tyrian purple dye. The enzyme is very specific to bromide and physically stable, but has not been characterized as to its active site metal., no specific gene has been assigned to such an enzyme in the snail genome.^[5] Such an activity is probably provided by symbiotic Bacillus bacteria instead.^[6] The identified enzyme belongs to the alpha/beta hydrolase superfamily; a structure for a similar bromoperoxidase is available as . It runs on a catalytic triad of Ser 99, Asp 229 and His 258 and does not require metal cofactors.^[7]

Additional reading

• Vanadium(v) as an essential element for haloperoxidase activity in marine brown-algae - purification and characterization of a vanadium(V)-containing bromoperoxidase from Laminaria saccharina . De Boer, E. . Tromp, M.G.M. . Plat, H. . Krenn, G.E. . Wever, R . Biochim. Biophys. Acta . 1986 . 872 . 1–2 . 104–115 . 10.1016/0167-4838(86)90153-6.
• Tromp MG, Olafsson G, Krenn BE, Wever R . Some structural aspects of vanadium bromoperoxidase from Ascophyllum nodosum . Biochimica et Biophysica Acta (BBA) - Protein Structure and Molecular Enzymology . 1040 . 2 . 192–8 . September 1990 . 2400770 . 10.1016/0167-4838(90)90075-q .
• Isupov MN, Dalby AR, Brindley AA, Izumi Y, Tanabe T, Murshudov GN, Littlechild JA . Crystal structure of dodecameric vanadium-dependent bromoperoxidase from the red algae Corallina officinalis . Journal of Molecular Biology . 299 . 4 . 1035–49 . June 2000 . 10843856 . 10.1006/jmbi.2000.3806 .
• Carter-Franklin JN, Butler A . Vanadium bromoperoxidase-catalyzed biosynthesis of halogenated marine natural products . Journal of the American Chemical Society . 126 . 46 . 15060–6 . November 2004 . 15548002 . 10.1021/ja047925p .
• Ohshiro T, Littlechild J, Garcia-Rodriguez E, Isupov MN, Iida Y, Kobayashi T, Izumi Y . Modification of halogen specificity of a vanadium-dependent bromoperoxidase . Protein Science . 13 . 6 . 1566–71 . June 2004 . 15133166 . 2279980 . 10.1110/ps.03496004 .

Notes and References

1. 10.1021/cr00021a014. Marine haloperoxidases. Chemical Reviews. 93. 5. 1937–1944. 1993. Butler. Alison.. Walker. J. V..
2. 10.1021/acs.chemrev.7b00032. 28466644. Development of Halogenase Enzymes for Use in Synthesis. Chemical Reviews. 118. 1. 232–269. 2018. Latham. Jonathan. Brandenburger. Eileen. Shepherd. Sarah A.. Menon. Binuraj R. K.. Micklefield. Jason.
3. 10.1021/cr050313i. 16895332. Nature's Inventory of Halogenation Catalysts: Oxidative Strategies Predominate. Chemical Reviews. 106. 8. 3364–3378. 2006. Vaillancourt. Frédéric H.. Yeh. Ellen. Vosburg. David A.. Garneau-Tsodikova. Sylvie . Sylvie Garneau-Tsodikova . Walsh. Christopher T..
4. Butler, A., "Vanadium haloperoxidases", Current Opinion in Chemical Biology, 1998, 2, 279-285.
5. Benkendorff . K . Natural product research in the Australian marine invertebrate Dicathais orbita. . Marine Drugs . 23 April 2013 . 11 . 4 . 1370–98 . 10.3390/md11041370 . 23612370. 3705410 . free .
6. Ngangbam . AK . Mouatt . P . Smith . J . Waters . DLE . Benkendorff . K . Bromoperoxidase Producing Bacillus spp. Isolated from the Hypobranchial Glands of a Muricid Mollusc Are Capable of Tyrian Purple Precursor Biogenesis. . Marine Drugs . 3 May 2019 . 17 . 5 . 264 . 10.3390/md17050264 . 31058830. 6562550 . free . Genbank AKQ77155.1.
7. Web site: Deposit 3FOB/IDP00046 . Center for Structural Genomics of Infectious Diseases . 31 May 2019.