Side chain removal from corticosteroids by unspecific peroxygenase
Two unspecific peroxygenases (UPO, EC 1.11.2.1) from the basidiomycetous fungi Marasmius rotula and Marasmius wettsteinii oxidized steroids with hydroxyacetyl and hydroxyl functionalities at C17 - such as cortisone, Reichstein's substance S and prednisone - via stepwise oxygenation and final fi...
Published in: | Journal of Inorganic Biochemistry |
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Elsevier
2018
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fttudresden:oai:qucosa:de:qucosa:30987 2023-05-15T15:52:47+02:00 Side chain removal from corticosteroids by unspecific peroxygenase Ullrich, René Hofrichter, Martin Poraj-Kobielska, Marzena Pecyna, Marek Scheibner, Katrin Scholze, Steffi Sandvoss, Martin Halbout, Claire 2018-06-07 https://nbn-resolving.org/urn:nbn:de:bsz:14-qucosa-235595 https://tud.qucosa.de/id/qucosa%3A30987 https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-0/ https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-1/ eng eng Elsevier 10.1016/j.jinorgbio.2018.03.011 urn:nbn:de:bsz:14-qucosa-235595 https://tud.qucosa.de/id/qucosa%3A30987 https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-0/ https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-1/ info:eu-repo/semantics/openAccess Journal of Inorganic Biochemistry (2018), 183, S. 84-93 ISSN: 0162-0134. DOI:10.1016/j.jinorgbio.2018.03.011 info:eu-repo/classification/ddc/540 ddc:540 info:eu-repo/classification/ddc/570 ddc:570 Peroxygenierung Peroxide shunt P450 Häm-Thiolat Deacylierung Geminaler Alkohol Peroxygenation Heme-thiolate Deacylation Geminal alcohol doc-type:article info:eu-repo/semantics/article doc-type:Text 2018 fttudresden https://doi.org/10.1016/j.jinorgbio.2018.03.011 2022-01-01T19:04:08Z Two unspecific peroxygenases (UPO, EC 1.11.2.1) from the basidiomycetous fungi Marasmius rotula and Marasmius wettsteinii oxidized steroids with hydroxyacetyl and hydroxyl functionalities at C17 - such as cortisone, Reichstein's substance S and prednisone - via stepwise oxygenation and final fission of the side chain. The sequential oxidation started with the hydroxylation of the terminal carbon (C21) leading to a stable geminal alcohol (e.g. cortisone 21-gem-diol) and proceeded via a second oxygenation resulting in the corresponding α-ketocarboxylic acid (e.g. cortisone 21-oic acid). The latter decomposed under formation of adrenosterone (4-androstene-3,11,17-trione) as well as formic acid and carbonic acid (that is in equilibrium with carbon dioxide); fission products comprising two carbon atoms such as glycolic acid or glyoxylic acid were not detected. Protein models based on the crystal structure data of MroUPO (Marasmius rotula unspecific peroxygenase) revealed that the bulky cortisone molecule suitably fits into the enzyme's access channel, which enables the heme iron to come in close contact to the carbons (C21, C20) of the steroidal side chain. ICP-MS analysis of purified MroUPO confirmed the presence of magnesium supposedly stabilizing the porphyrin ring system. Article in Journal/Newspaper Carbonic acid Dresden University of Technology: Qucosa Journal of Inorganic Biochemistry 183 84 93 |
institution |
Open Polar |
collection |
Dresden University of Technology: Qucosa |
op_collection_id |
fttudresden |
language |
English |
topic |
info:eu-repo/classification/ddc/540 ddc:540 info:eu-repo/classification/ddc/570 ddc:570 Peroxygenierung Peroxide shunt P450 Häm-Thiolat Deacylierung Geminaler Alkohol Peroxygenation Heme-thiolate Deacylation Geminal alcohol |
spellingShingle |
info:eu-repo/classification/ddc/540 ddc:540 info:eu-repo/classification/ddc/570 ddc:570 Peroxygenierung Peroxide shunt P450 Häm-Thiolat Deacylierung Geminaler Alkohol Peroxygenation Heme-thiolate Deacylation Geminal alcohol Ullrich, René Hofrichter, Martin Poraj-Kobielska, Marzena Pecyna, Marek Scheibner, Katrin Scholze, Steffi Sandvoss, Martin Halbout, Claire Side chain removal from corticosteroids by unspecific peroxygenase |
topic_facet |
info:eu-repo/classification/ddc/540 ddc:540 info:eu-repo/classification/ddc/570 ddc:570 Peroxygenierung Peroxide shunt P450 Häm-Thiolat Deacylierung Geminaler Alkohol Peroxygenation Heme-thiolate Deacylation Geminal alcohol |
description |
Two unspecific peroxygenases (UPO, EC 1.11.2.1) from the basidiomycetous fungi Marasmius rotula and Marasmius wettsteinii oxidized steroids with hydroxyacetyl and hydroxyl functionalities at C17 - such as cortisone, Reichstein's substance S and prednisone - via stepwise oxygenation and final fission of the side chain. The sequential oxidation started with the hydroxylation of the terminal carbon (C21) leading to a stable geminal alcohol (e.g. cortisone 21-gem-diol) and proceeded via a second oxygenation resulting in the corresponding α-ketocarboxylic acid (e.g. cortisone 21-oic acid). The latter decomposed under formation of adrenosterone (4-androstene-3,11,17-trione) as well as formic acid and carbonic acid (that is in equilibrium with carbon dioxide); fission products comprising two carbon atoms such as glycolic acid or glyoxylic acid were not detected. Protein models based on the crystal structure data of MroUPO (Marasmius rotula unspecific peroxygenase) revealed that the bulky cortisone molecule suitably fits into the enzyme's access channel, which enables the heme iron to come in close contact to the carbons (C21, C20) of the steroidal side chain. ICP-MS analysis of purified MroUPO confirmed the presence of magnesium supposedly stabilizing the porphyrin ring system. |
format |
Article in Journal/Newspaper |
author |
Ullrich, René Hofrichter, Martin Poraj-Kobielska, Marzena Pecyna, Marek Scheibner, Katrin Scholze, Steffi Sandvoss, Martin Halbout, Claire |
author_facet |
Ullrich, René Hofrichter, Martin Poraj-Kobielska, Marzena Pecyna, Marek Scheibner, Katrin Scholze, Steffi Sandvoss, Martin Halbout, Claire |
author_sort |
Ullrich, René |
title |
Side chain removal from corticosteroids by unspecific peroxygenase |
title_short |
Side chain removal from corticosteroids by unspecific peroxygenase |
title_full |
Side chain removal from corticosteroids by unspecific peroxygenase |
title_fullStr |
Side chain removal from corticosteroids by unspecific peroxygenase |
title_full_unstemmed |
Side chain removal from corticosteroids by unspecific peroxygenase |
title_sort |
side chain removal from corticosteroids by unspecific peroxygenase |
publisher |
Elsevier |
publishDate |
2018 |
url |
https://nbn-resolving.org/urn:nbn:de:bsz:14-qucosa-235595 https://tud.qucosa.de/id/qucosa%3A30987 https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-0/ https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-1/ |
genre |
Carbonic acid |
genre_facet |
Carbonic acid |
op_source |
Journal of Inorganic Biochemistry (2018), 183, S. 84-93 ISSN: 0162-0134. DOI:10.1016/j.jinorgbio.2018.03.011 |
op_relation |
10.1016/j.jinorgbio.2018.03.011 urn:nbn:de:bsz:14-qucosa-235595 https://tud.qucosa.de/id/qucosa%3A30987 https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-0/ https://tud.qucosa.de/api/qucosa%3A30987/attachment/ATT-1/ |
op_rights |
info:eu-repo/semantics/openAccess |
op_doi |
https://doi.org/10.1016/j.jinorgbio.2018.03.011 |
container_title |
Journal of Inorganic Biochemistry |
container_volume |
183 |
container_start_page |
84 |
op_container_end_page |
93 |
_version_ |
1766387874982264832 |