CHLOROPHYLL CATABOLISM. PART 3. STRUCTURE ELUCIDATION AND PARTIAL SYNTHESIS OF A NEW RED BILIN DERIVATIVE FROM <i>Chlorella protothecoides</i>*

Ituttaspe, Josf; Engel, Norbert; Matzinger, Peter K.; Mooser, Véronique; Gossauer, Albert

doi:10.1111/j.1751-1097.1993.tb04911.x

Cited by 16 publications

(6 citation statements)

References 4 publications

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“…In addition to an absorption maximum at 316 nm, the spectrum of RCC is distinguished by a peak at ca. Because acidic conditions were originally used for extraction, the red pigments were obtained as pyro derivatives [52,53], but later it was confirmed that in the RCCs produced during Chlorella degreening the methoxycarbonyl function at C(13 2 ) is demethylated [24]. Red derivatives of Chl corresponding to RCC are also known to be produced in Chlorella protothecoides [24, 50 -52] and C. kessleri [4] during enforced degreening under N-deficiency and heterotrophic metabolism.…”

Section: Red Chl Catabolitesmentioning

confidence: 99%

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Chlorophyll breakdown in higher plants and algae

Hörtensteiner¹

1999

Cellular and Molecular Life Sciences (CMLS)

136

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Leaf senescence is accompanied by the metabolism of chlorophyll (Chl) to nonfluorescent catabolites (NCCs). The pathway of Chl degradation comprises several reactions and includes the occurrence of intermediary catabolites. After removal of phytol and the central Mg atom from Chl by chlorophyllase and Mg dechelatase, respectively, the porphyrin macrocycle of pheophorbide (Pheide) a is cleaved. This two-step reaction is catalyzed by Pheide a oxygenase and RCC reductase and yields a primary fluorescent catabolite (pFCC). After hydroxylation and additional species-specific modifications, FCCs are tautomerized nonenzymically to NCCs inside the vacuole. Different subcellular compartments participate in Chl catabolism and, thus, transport processes across membranes are required. This review focuses on the catabolites and the individual reactions of Chl breakdown in higher plants. In addition, the pathway is compared to Chl conversion to red catabolites in an alga, Chlorella protothecoides. Finally, the significance and regulation of Chl degradation are discussed.

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Section: Red Chl Catabolitesmentioning

confidence: 99%

“…In rape, the major NCC, Bn-NCC-1, is the malonyl ester of Bn-NCC-3 [57,58]. In Chlorella, these catabolites were originally isolated as the respective decarboxylated pyro forms [52,53]. Malonyltransferase activity has been demonstrated in protein extracts of rape cotyledons with malonyl coenzyme A as the cosubstrate.…”

Section: Transition Of Pfcc Into Nccmentioning

confidence: 99%

Chlorophyll breakdown in higher plants and algae

Hörtensteiner¹

1999

Cellular and Molecular Life Sciences (CMLS)

136

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“…Alternatively, this product of an apparent loss of the entire methyl ester group of Pheo a may result from a two‐step sequence via spontaneous decarboxylation of the first‐formed 13 2 ‐carboxyl‐pyro‐pheophorbide a . Likewise, a red pyro‐RCC (pyRCC) was described as an adventitious decarboxylation product of its endogenous β‐keto‐carboxylic acid precursor, secreted by the bleached green alga Auxenachlorella protothecoides . By chemical means this pyRCC was converted into incompletely characterized colorless linear tetrapyrroles devoid of the carboxylic acid group…”

Section: Introductionmentioning

confidence: 99%

“… Chemical formulas of pyro‐pheophorbide a , of the known red pyro‐RCC and of the here introduced two types of pyro‐phyllobilins (pyPBs), the pyro‐type 1‐formyl‐19‐oxobilins pyro‐NCC 3 and pyro‐YCC 4 .…”

Section: Introductionmentioning

confidence: 99%

Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Wurst

Berghold

et al. 2018

Chemistry A European J

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A β‐keto ester grouping is a characteristic of ring E of the chlorophylls (Chls). Its presence has also reinforced the original identification of nonfluorescent Chl catabolites (NCCs) as colorless, amphiphilic phyllobilins (PBs). Polar NCCs were also detected in higher plants, in which a free carboxyl group replaced the ring E ester group. Such NCCs are surprisingly resistant to loss of this carboxyl unit, and NCCs lacking the latter, that is, pyro‐NCCs (pyNCCs), have not been reported. Intrigued by the question of the natural occurrence of pyro‐phyllobilins (pyPBs), we have prepared a representative pyNCC by decarboxylation of a natural NCC. We also converted the pyNCC into its yellow oxidation product, a pyro‐YCC (pyYCC). The solution structures of pyNCC and of pyYCC, and a crystal structure of the pyYCC methyl ester (pyYCC‐Me) were obtained. pyYCC‐Me features the same remarkable H‐bonded and π‐stacked dimer structure as the corresponding natural yellow Chl catabolite (YCC) with the ring E methyl ester group. Indeed, the latter substituent has little effect on the structure, as well as on the unique self‐assembly and photoswitch behavior of yellow PBs.

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“…The red tetrapyrrole 5 was characterized spectroscopically as the stereoisomer with M configuration at C(13') on the basis of a strong NOE between H-C(l3,) and CH,(17') of the side chain at C (17), which, in turn, is bound at the B-face. On the other hand, the minor isomer (8-5) was assigned to have P-configuration at C(13') based on a strong NOE between H-C(l3,) and H-C(17), rather than, alternatively, to be a geometric isomer of 5 (formed by (152)/(15E) isomerism, as discussed in [20]). Furthermore, 5 was identical with a dimethyl-ester isolate of the red pigment from Chlorella protothecoides, when compared by its reported UVjVIS, 'H-NMR, and FAB mass spectra [16].…”

Section: R=ch3mentioning

confidence: 99%

Breakdown of Chlorophyll: Partial synthesis of a putative intermediary catabolite. Preliminary communication

Kräutler

Mühlecker

Anderl

et al. 1997

Helvetica Chimica Acta

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Dedicated to Professor Philippe Matile on the occasion of his 65th birthday (14.111.97) The partial synthesis of 10,22-dihydro-4,5-dioxo-4,5-secopheophorbide a (1) from pheophorbide a methyl ester (2) is described. A regioselective, photooxygenolytic reaction of (pheophorbidato a methyl ester)cadmium(II) (3) provides the entry to the crucial 4,5-secoporphinoid structure in form of the (10,22-dihydro-4,5-dioxo-4,5-secopheophorbidato a methyl ester)cadmium(II) (4). The hydride reduction of this 4,5-dioxo-4,5-secophytoporphyrin ester occurs selectively at the 'eastern' meso-position to lead (after demetallation) to 10,22-dihydro-4,5-dioxo-4,5-secopheophorbide a methyl ester (5). This oxobilin-carbaldehyde has the structure assigned earlier to an ester of an isolation form of the red pigment(s) from Chlot-elluprotothecoides. Hydrolysis of the propanoate ester function of 5, selectively catalyzed by pig liver esterase, then yields the title compound 1. The red tetrapyrrole 1 may represent an intermediary chlorophyll catabolite in degreening plants.

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CHLOROPHYLL CATABOLISM. PART 3. STRUCTURE ELUCIDATION AND PARTIAL SYNTHESIS OF A NEW RED BILIN DERIVATIVE FROM *Chlorella protothecoides**

Abstract: The structure of a new red pigment produced during the “bleaching” of Chlorella protorhecoides cells has been elucidated by analytical methods as well as by in vitro isomerization into the new compound of a synthetic sample of a previously characteriLed chlorophyll a catabolite.

Cited by 16 publications

References 4 publications

Chlorophyll breakdown in higher plants and algae

Chlorophyll breakdown in higher plants and algae

Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Breakdown of Chlorophyll: Partial synthesis of a putative intermediary catabolite. Preliminary communication

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CHLOROPHYLL CATABOLISM. PART 3. STRUCTURE ELUCIDATION AND PARTIAL SYNTHESIS OF A NEW RED BILIN DERIVATIVE FROM Chlorella protothecoides*

Abstract: The structure of a new red pigment produced during the “bleaching” of Chlorella protorhecoides cells has been elucidated by analytical methods as well as by in vitro isomerization into the new compound of a synthetic sample of a previously characteriLed chlorophyll a catabolite.

Cited by 16 publications

References 4 publications

Chlorophyll breakdown in higher plants and algae

Chlorophyll breakdown in higher plants and algae

Pyro‐Phyllobilins: Elusive Chlorophyll Catabolites Lacking a Critical Carboxylate Function of the Natural Chlorophylls

Breakdown of Chlorophyll: Partial synthesis of a putative intermediary catabolite. Preliminary communication

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CHLOROPHYLL CATABOLISM. PART 3. STRUCTURE ELUCIDATION AND PARTIAL SYNTHESIS OF A NEW RED BILIN DERIVATIVE FROM *Chlorella protothecoides**