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Vanadium Chloroperoxidase as a Catalyst for Hydrogen Peroxide Disproportionation to Singlet Oxygen in Mildly Acidic Aqueous Environment
| Content Provider | Semantic Scholar |
|---|---|
| Author | Renirie, Rokus Pierlot, Christel Aubry, Jean-Marie Hartog, Aloysius F. Schoemaker, Hans Egbert Alsters, Paul L. Wever, Ron |
| Copyright Year | 2003 |
| Abstract | Chemiluminescence studies show that the enzyme vanadium chloroperoxidase from the fungus Curvularia inaequalis is a highly efficient catalyst for the production of singlet oxygen from hydrogen peroxide in a mildly acidic aqueous environment, with a maximum turnover frequency of 100 s 1 with respect to H2O2 consumption. The enzyme studied here can be regarded as a supplementary catalyst to inorganic molybdate, which operates in basic aqueous media. The enzyme system is 10 3 ±1 0 4 times faster than the molybdate system when compared at their optimal pH. The enzyme is very stable against singlet oxygen, in contrast to heme-containing peroxidases which, due to inactivation by singlet oxygen, only produce a short burst, presumably by oxidation of the labile cofactor. The vanadium chloroperoxidase was compared with vanadium bromoperoxidase from the seaweed Ascophyllum nodosum and was found to be even more stable; it is stable towards a continuous flow of singlet oxygen for at least 1 hour and also it is not inactivated by 500 mM H2O2. An important difference with vanadium bromoperoxidase is that the vanadium chloroperoxidase is able to effectively use chloride as a cocatalyst (20 s 1 ) instead of bromide. This offers an important advantage from an application point of view; using chloride, no side products are observed when the chemical trap anthracene-9,10-bis(ethanesulphonate) is fully con- verted by singlet oxygen into its corresponding endoperoxide. By contrast, when bromide is used, 20% side product is formed. During the conversion the enzyme remains fully stable for 25,000 turnovers. |
| Starting Page | 849 |
| Ending Page | 858 |
| Page Count | 10 |
| File Format | PDF HTM / HTML |
| DOI | 10.1002/adsc.200303008 |
| Alternate Webpage(s) | http://www1.udel.edu/chem/polenova/VHPO/VCPO_H2O2_disproport_cat_AdvCatSynth2004.pdf |
| Alternate Webpage(s) | https://doi.org/10.1002/adsc.200303008 |
| Volume Number | 345 |
| Language | English |
| Access Restriction | Open |
| Content Type | Text |
| Resource Type | Article |