Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene.
Oxidation of C18 Hydroxy-Polyunsaturated Fatty Acids to Epoxide or Ketone by Catalase-Related Hemoproteins Activated with Iodosylbenzene.
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DOI：
10.1007/s11745-017-4271-0
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发表时间：
2017-07
期刊：
影响因子：
1.9
通讯作者：
Brash AR
中科院分区：
文献类型：
--
作者：
Teder T;Boeglin WE;Brash AR
小的过氧化氢酶相关的血红素蛋白与设施，以脂肪酸氢过氧化物的反应进行了检查，其潜在的单加氧酶活性时，使用碘酰苯激活。测试的蛋白质是禾谷镰刀菌41 kD过氧化氢酶血红素蛋白（Fg-cat，基因FGSG_02217）、荧光假单胞菌Pfl01过氧化氢酶（37.5 kD，登录号WP_011333788.1）和鸟分枝杆菌亚种（Mycobacterium avium ssp.副结核杆菌33 kD过氧化氢酶（基因MAP-2744c）。选择13-羟基-十八碳烯酸（其通常不反应）作为底物，因为这些酶与相应的13S-氢过氧化物特异性反应（Pakhomova等人，（2009）Protein Sci. 18：2559和Teder等人，2017，Biochim. Biophys. Acta，1862：706）。在碘酰苯存在下，Fg-cat将13 S-羟基脂肪酸转化为两种产物：13 S-羟基α-亚麻酸的15，16-双键立体专一性地氧化为15S，16R-顺式环氧化物或13-羟基氧化为13-酮。通过UV、HPLC、LC-MS、NMR以及与本研究制备的真实标准品进行比较，对产物进行鉴别。Pfl01-cat显示出类似的活性。MAP-2744c将13 S-羟基-亚油酸氧化为13-酮，并将双键环氧化形成9，10-环氧基-13-羟基、11，12-环氧基-13-羟基和9，10-环氧基-13-酮衍生物;以9S-羟基-亚油酸为底物时发生等效转化。在碘酰苯存在下的平行孵育中，人过氧化氢酶对13S-羟基亚油酸没有显示出活性，正如从其活性位点的高度受限访问所预期的那样。结果表明，在适当转化为化合物I的情况下，可以通过这些过氧化氢酶相关血红素蛋白与酪氨酸作为近端血红素配体来证明单加氧酶活性。
Small catalase-related hemoproteins with a facility to react with fatty acid hydroperoxides were examined for their potential mono-oxygenase activity when activated using iodosylbenzene. The proteins tested were a Fusarium graminearum 41 kD catalase hemoprotein (Fg-cat, gene FGSG_02217), a Pseudomonas fluorescens Pfl01 catalase (37.5 kD, accession number WP_011333788.1), and a Mycobacterium avium ssp. paratuberculosis 33 kD catalase (gene MAP-2744c). 13-Hydroxy-octadecenoic acids (which are normally unreactive) were selected as substrates because these enyzmes react specifically with the corresponding 13S-hydroperoxides (Pakhomova et al, (2009) Protein Sci. 18:2559, and Teder et al, 2017, Biochim. Biophys. Acta, 1862:706). In the presence of iodosylbenzene Fg-cat converted 13S-hydroxy-fatty acids to two products: the 15,16-double bond of 13S-hydroxy α-linolenic acid was oxidized stereospecifically to the 15S,16R-cis-epoxide or the 13-hydroxyl was oxidized to the 13-ketone. Products were identified by UV, HPLC, LC-MS, NMR and by comparison with authentic standards prepared for this study. The Pfl01-cat displayed similar activity. MAP-2744c oxidized 13S-hydroxy-linoleic acid to the 13-ketone, and epoxidized the double bonds to form the 9,10-epoxy-13-hydroxy, 11,12-epoxy-13-hydroxy, and 9,10-epoxy-13-keto derivatives; equivalent transformations occurred with 9S-hydroxy-linoleic acid as substrate. In parallel incubations in the presence of iodosylbenzene, human catalase displayed no activity towards 13S-hydroxy-linoleic acid, as expected from the highly restricted access to its active site. The results indicted that with suitable transformation to Compound I, monooxygenase activity can be demonstrated by these catalase-related hemoproteins with tyrosine as the proximal heme ligand.
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DOI：
10.1073/pnas.79.19.5758
发表时间：
1982-01-01
期刊：
PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA-BIOLOGICAL SCIENCES
影响因子：
--
作者：
GELB, MH;TOSCANO, WA;SLIGAR, SG
通讯作者：
SLIGAR, SG
影响因子：
5.6
作者：
Putnam, CD;Arvai, AS;Tainer, JA
通讯作者：
Tainer, JA
影响因子：
4.8
作者：
Boeglin, William E.;Brash, Alan R.
通讯作者：
Brash, Alan R.
DOI：
10.1016/0005-2760(86)90233-x
发表时间：
1986-12-05
期刊：
BIOCHIMICA ET BIOPHYSICA ACTA
影响因子：
--
作者：
HAMBERG, M;HERMAN, RP;JACOBSSON, U
通讯作者：
JACOBSSON, U
影响因子：
3.4
作者：
Cui, Pei H.;Duke, Rujee K.;Duke, Colin C.
通讯作者：
Duke, Colin C.