Publications by authors named "Natalia V Lantsova"

3 Publications

  • Page 1 of 1

Detection of the First Epoxyalcohol Synthase/Allene Oxide Synthase (CYP74 Clan) in the Lancelet (, Chordata).

Int J Mol Sci 2021 Apr 29;22(9). Epub 2021 Apr 29.

Kazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, P.O. Box 30, 420111 Kazan, Russia.

The CYP74 clan cytochromes (P450) are key enzymes of oxidative metabolism of polyunsaturated fatty acids in plants, some Proteobacteria, brown and green algae, and Metazoa. The CYP74 enzymes, including the allene oxide synthases (AOSs), hydroperoxide lyases, divinyl ether synthases, and epoxyalcohol synthases (EASs) transform the fatty acid hydroperoxides to bioactive oxylipins. A novel CYP74 clan enzyme CYP440A18 of the Asian (Belcher's) lancelet (, Chordata) was biochemically characterized in the present work. The recombinant CYP440A18 enzyme was active towards all substrates used: linoleate and α-linolenate 9- and 13-hydroperoxides, as well as with eicosatetraenoate and eicosapentaenoate 15-hydroperoxides. The enzyme specifically converted α-linolenate 13-hydroperoxide (13-HPOT) to the oxiranyl carbinol (9,11,12,13,15)-11-hydroxy-12,13-epoxy-9,15-octadecadienoic acid (EAS product), α-ketol, 12-oxo-13-hydroxy-9,15-octadecadienoic acid (AOS product), and -12-oxo-10,15-phytodienoic acid (AOS product) at a ratio of around 35:5:1. Other hydroperoxides were converted by this enzyme to the analogous products. In contrast to other substrates, the 13-HPOT and 15-HPEPE yielded higher proportions of α-ketols, as well as the small amounts of cyclopentenones, -12-oxo-10,15-phytodienoic acid and its higher homologue, dihomo--12-oxo-3,6,10,15-phytotetraenoic acid, respectively. Thus, the CYP440A18 enzyme exhibited dual EAS/AOS activity. The obtained results allowed us to ascribe a name " EAS/AOS" (BbEAS/AOS) to this enzyme. BbEAS/AOS is a first CYP74 clan enzyme of Chordata species possessing AOS activity.
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http://dx.doi.org/10.3390/ijms22094737DOI Listing
http://www.ncbi.nlm.nih.gov/pmc/articles/PMC8124189PMC
April 2021

Lipoxygenase pathway in model bryophytes: 12-oxo-9(13),15-phytodienoic acid is a predominant oxylipin in Physcomitrella patens.

Phytochemistry 2020 Dec 12;180:112533. Epub 2020 Oct 12.

Kazan Institute of Biochemistry and Biophysics, FRC Kazan Scientific Center of RAS, P.O. Box 30, 420111, Kazan, Russia. Electronic address:

The model moss Physcomitrella patens and liverwort Marchantia polymorpha possess all enzymatic machinery responsible for the initial stages of jasmonate pathway, including the active 13(S)-lipoxygenase, allene oxide synthase (AOS) and allene oxide cyclase (AOC). At the same time, the jasmonic acid is missing from both P. patens and M. polymorpha. Our GC-MS profiling of oxylipins of P. patens gametophores and M. polymorpha tissues revealed some distinctive peculiarities. The 15(Z)-cis-12-oxo-10,15-phytodienoic acid (12-OPDA) was the major oxylipin in M. polymorpha. In contrast, the 12-OPDA was only a minor constituent in P. patens, while another cyclopentenone 1 was the predominant oxylipin. Product 1 was identified by its MS, H-NMR, H-H-COSY, HSQC and HMBC data as 15(Z)-12-oxo-9(13),15-phytodienoic acid, i.e., the iso-12-OPDA. The corresponding C homologue, 2,3-dinor-iso-12-OPDA (2), have also been detected as a minor component in P. patens and a prominent product in M. polymorpha. Besides, the 2,3-dinor-cis-12-OPDA (3) was also present in M. polymorpha. Apparently, the malfunction of cyclopentenone reduction by the 12-OPDA reductase in P. patens and (to a lesser extent) in M. polymorpha leads to the isomerization of 12-OPDA and formation of specific cyclopentenones 1 and 2, which are uncommon in flowering plants.
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http://dx.doi.org/10.1016/j.phytochem.2020.112533DOI Listing
December 2020

Novel allene oxide synthase products formed via Favorskii-type rearrangement: mechanistic implications for 12-oxo-10,15-phytodienoic acid biosynthesis.

Chembiochem 2011 Nov 16;12(16):2511-7. Epub 2011 Sep 16.

Kazan Institute of Biochemistry and Biophysics, Russian Academy of Sciences, Kazan, Russia.

The allene oxide synthase (AOS) pathway is widespread in plants. Its products, such as cyclopentenone 12-oxo-10,15-phytodienoic acid (12-oxo-PDA) and related jasmonates, play important biological roles in plants. We found that 12-oxo-PDA in some plant tissues co-occur with an unknown minor oxylipin 1. In vitro incubations of AOSs with α-linolenic acid 13(S)-hydroperoxide reliably afforded 1 along with 12-oxo-PDA and α-ketol. A similar oxylipin 3 was formed during the AOS conversions of γ-linolenic acid 9(S)-hydroperoxide. Linoleic acid hydroperoxides formed neither products similar to 1 and 3 nor cyclopentenones. Oxylipins 1 and 3 were purified and identified as the products of Favorskii-type rearrangement, (2'Z,4Z)-2-(2'-pentenyl)-4-tridecene-1,13-dioic acid and (2'Z,4Z)-2-(2'-octenyl)-4-decene-1,10-dioic acid, respectively. Detection of Favorskii products 1 and 3 demonstrates that cyclopropanones are short-lived AOS products along with allene oxides. The observed parallels between the Favorskii product 1 and 12-oxo-PDA formation suggests that cyclopropanone is either a byproduct or a precursor of 12-oxo-PDA.
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http://dx.doi.org/10.1002/cbic.201100346DOI Listing
November 2011