Pyrrolic and Dipyrrolic Chlorophyll Degradation Products in Plants and Herbivores

Ritter, Marcel; Oetama, Vincensius Surya; Schulze, Daniel J.; Muetzlaff, Katrin; Meents, Anja K.; Seidel, Raphael A.; Görls, Helmar; Westerhausen, Matthias; Boland, Wilhelm; Pohnert, Georg

doi:10.1002/chem.201905236

Cited by 12 publications

(12 citation statements)

References 53 publications

(120 reference statements)

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“…CrOYE3, in contrast, did only convert maleimides, which might point toward its physiological role. Maleimides and maleimide‐like compounds have been detected as degradation products of Chl and heme, both in living organisms and in sediments (Gaubert et al, 2019 ; Naeher et al, 2013 ; Ritter et al, 2020 ; Suzuki & Shioi, 1999 ). Maleimides are toxic to cells because they react readily with the thiol groups of cysteines (Gunnoo & Madder, 2016 ; Scholtissek et al, 2018 ).…”

Section: Discussionmentioning

confidence: 99%

Chlamydomonas reinhardtii mutants deficient for Old Yellow Enzyme 3 exhibit increased photooxidative stress

Böhmer

Marx²,

Goss

et al. 2023

Plant Direct

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Old Yellow Enzymes (OYEs) are flavin-containing ene-reductases that have been intensely studied with regard to their biotechnological potential for sustainable chemical syntheses. OYE-encoding genes are found throughout the domains of life, but their physiological role is mostly unknown, one reason for this being the promiscuity of most ene-reductases studied to date. The unicellular green alga Chlamydomonas reinhardtii possesses four genes coding for OYEs, three of which we have analyzed biochemically before. Ene-reductase CrOYE3 stood out in that it showed an unusually narrow substrate scope and converted N-methylmaleimide (NMI) with high rates. This was recapitulated in a C. reinhardtii croye3 mutant that, in contrast to the wild type, hardly degraded externally added NMI. Here we show that CrOYE3-mediated NMI conversion depends on electrons generated photosynthetically by photosystem II (PSII) and that the croye3 mutant exhibits slightly decreased photochemical quenching in high light. Non-photochemical quenching is strongly impaired in this mutant, and it shows enhanced oxidative stress. The phenotypes of the mutant suggest that C. reinhardtii CrOYE3 is involved in the protection against photooxidative stress, possibly by converting reactive carbonyl species derived from lipid peroxides or maleimides from tetrapyrrole degradation.

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Section: Discussionmentioning

confidence: 99%

Chlamydomonas reinhardtii mutants deficient for Old Yellow Enzyme 3 exhibit increased photooxidative stress

Böhmer

Marx²,

Goss

et al. 2023

Plant Direct

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“…Needless to say, the formation of hematinic acid in neutrophils or in vivo under inflammatory conditions has never been demonstrated before. Interestingly, hematinic acid has been extensively demonstrated to be formed in the H 2 O 2 -mediated degradation of hemoglobin, heme, ferriprotoporphyrin IX, and chlorophyll a [ 41 , 42 , 43 , 44 ], or in BR photooxidation [ 45 , 46 ].…”

Section: Discussionmentioning

confidence: 99%

A New Product of Bilirubin Degradation by H2O2 and Its Formation in Activated Neutrophils and in an Inflammatory Mouse Model

Yuan

et al. 2022

Biomolecules

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Bilirubin (BR) is a tetrapyrrolic compound stemming from heme catabolism with diverse physiological functions. It can be oxidized by H2O2 to form several degradation products, some of which have been detected in vivo and may contribute to the pathogenesis of certain diseases. However, the oxidative degradation of BR is complex and the conditions that BR degradation occurs pathophysiologically remain obscure. Neutrophils are known to generate large amounts of reactive oxygen species, including H2O2, upon activation and they are mobilized to inflammatory sites; therefore, we hypothesized that activated neutrophils could cause BR degradation, which could occur at inflammatory sites. In the present study, we investigated BR degradation by H2O2 and identified hematinic acid (BHP1) and a new product BHP2, whose structure was characterized as 2,5-diformyl-4-methyl-1H-pyrrole-3-propanoic acid. An LC-MS/MS method for the quantitation of the two compounds was then established. Using the LC-MS/MS method, we observed the concentration-dependent formation of BHP1 and BHP2 in mouse neutrophils incubated with 10 and 30 μM of BR with the yields being 16 ± 3.2 and 31 ± 5.9 pmol/106 cells for BHP1, and 25 ± 4.4 and 71 ± 26 pmol/106 cells for BHP2, respectively. After adding phorbol 12-myristate 13-acetate, a neutrophil agonist, to 30 μM of BR-treated cells, the BHP1 yield increased to 43 ± 6.6 pmol/106 cells, whereas the BHP2 one decreased to 47 ± 9.2 pmol/106 cells. The two products were also detected in hemorrhagic skins of mice with dermal inflammation and hemorrhage at levels of 4.5 ± 1.9 and 0.18 ± 0.10 nmol/g tissue, respectively, which were significantly higher than those in the non-hemorrhagic skins. BHP2 was neurotoxic starting at 0.10 μM but BHP1 was not, as assessed using Caenorhabditis elegans as the animal model. Neutrophil-mediated BR degradation may be a universally pathophysiological process in inflammation and can be particularly important under pathological conditions concerning hemorrhage.

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“…Indeed, there have been occasional reports on mono-pyrrolic isolates from senescent leaves [19]. Likewise, mono-and di-pyrrolic compounds originating from chemical destruction of Chl-like precursors were proposed (with little further experimental support) to represent model structures for natural Chl-breakdown [20]. Here, we describe the discovery of the readily occurring cleavage of the natural PrB 1 at its characteristic Chl-derived ring E in methanol [21].…”

Section: Introductionmentioning

confidence: 87%

Facile retro-Dieckmann cleavage of a pink phyllobilin: new type of potential downstream steps of natural chlorophyll breakdown

Kräutler

2022

Monatsh Chem

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In senescent leaves of higher plants, colourless chlorophyll (Chl) catabolites typically accumulate temporarily, and undergo natural oxidation, in part, to yellow- and pink-coloured phyllobilins (PBs). The latter, also classified as phylloroseobilins (PrBs), represent the final currently established products of Chl-breakdown, possibly playing important roles in metabolism. However, PrBs, themselves, do not accumulate in the leaves. Indeed, the original PrB identified, then classified as a pink Chl-catabolite (PiCC), is remarkably instable in methanolic solution. As reported here, PiCC readily converts at room temperature into yellow tetrapyrroles. The deduced main process, a retro-Dieckmann reaction, cleaves open its ring E moiety, the α-methoxycarbonyl-cyclopentanone unit characteristic of the Chls and of the natural Chl-derived PBs. This readily occurring reaction of the PiCC represents an unprecedented skeletal transformation of a PB, furnishing a cross-conjugated biladiene with a basic structure more similar to the heme-derived bilins. Graphical abstract

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Pyrrolic and Dipyrrolic Chlorophyll Degradation Products in Plants and Herbivores

Cited by 12 publications

References 53 publications

Chlamydomonas reinhardtii mutants deficient for Old Yellow Enzyme 3 exhibit increased photooxidative stress

Chlamydomonas reinhardtii mutants deficient for Old Yellow Enzyme 3 exhibit increased photooxidative stress

A New Product of Bilirubin Degradation by H2O2 and Its Formation in Activated Neutrophils and in an Inflammatory Mouse Model

Facile retro-Dieckmann cleavage of a pink phyllobilin: new type of potential downstream steps of natural chlorophyll breakdown

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