Chlorophyll breakdown—Regulation, biochemistry and phyllobilins as its products

Hörtensteiner, Stefan; Hauenstein, Mareike; Kräutler, Bernhard

doi:10.1016/bs.abr.2019.03.004

Cited by 30 publications

(68 citation statements)

References 207 publications

(473 reference statements)

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“…Bilin‐type Chl catabolites or phyllobilins (PBs) are generated in fall leaves as products of the degradation of chlorophyll (Chl) [1] . An enigma until about 30 years ago, [2] Chl‐breakdown in higher plants has meanwhile been elucidated to a large extent and revealed to follow the largely common ‘pheophorbide a oxygenase / phyllobilin’ (PAO/PB) pathway [1c,3] . In senescent leaves formyloxobilin‐type colorless ‘non‐fluorescent’ Chl catabolites (NCCs) accumulate, [2b,4] which are generated from the short lived corresponding fluorescent Chl catabolites (FCCs), [5] by a rapid acid‐induced isomerization (Scheme 1).…”

Section: Introductionmentioning

confidence: 99%

“…Originally, DNCCs were considered exotic and were classified as ‘urobilinogenoidic’ Chl catabolites, [9] but are now known to be abundant in some leaves, fruit and green vegetables [1b,7,10] . Thus, with NCCs and DNCCs, which were recently classified as type‐I and type‐II phyllobilanes (PBas) (Scheme 1), two important classes of the colorless and ‘nonfluorescent’ PBs occur in senescent angiosperm leaves [1b,c] …”

Section: Introductionmentioning

confidence: 99%

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A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

Podewitz

Kräutler

2021

Eur J Inorg Chem

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In senescent fall leaves and in ripening fruit, colorless phyllobilins (PBs) accumulate from breakdown of chlorophyll, from which yellow PBs (phylloxanthobilins) and pink colored PBs (phylloroseobilins) arise in some leaves. The first described PBs were formyloxobilin-type PBs, but dioxobilin-type PBs also occur naturally. Here we report the synthesis and characterization of the blue Zn(II) complex of a dioxobilin-type pink PB, which chelates a Zn(II) ion fast and tightly in an effectively tridentate manner. The optically active Zn complex featured bright chelation enhanced red fluorescence and exhibited strikingly differing spectral properties in methanol and in acetonitrile. Computational studies based on DFT-calculations gave detailed insights into low energy structures of the Zn complex in both solvents and provided support for the proposed role of solvent in the coordination sphere of the bound Zn(II) ion.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

Podewitz

Kräutler

2021

Eur J Inorg Chem

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“…1 ), and a second section that involves cytosolic and vacuolar processes that produce non-toxic linear tetrapyrroles, phyllobilins ( Fig. 2 ) ( Kuai et al , 2017 ; Hörtensteiner et al , 2019 ). The PAO/phyllobilin pathway is relatively well described in angiosperms ( Figs 1 , 2 ).…”

Section: Introductionmentioning

confidence: 99%

“…pFCCs are then modified further and exported from the chloroplast. While the first part of the pathway appears to be relatively straightforward, the fate of pFCCs outside the chloroplast appears to be more diverse and involves various detoxifying enzymes, with more than 40 phyllobilins having been described to date ( Hörtensteiner et al , 2019 ). For example, in Arabidopsis, CYP89A9 and MES16 were shown to catalyze C1 deformylation and O8 4 demethylation, respectively ( Christ et al , 2012 , 2013 , 2016 ).…”

Section: Introductionmentioning

confidence: 99%

An evergreen mind and a heart for the colors of fall

Aubry

Christ

Kräutler

et al. 2021

Journal of Experimental Botany

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With finest biochemical and molecular approaches, convincing explorative strategies and long-term vision, Stefan Hörtensteiner succeeded in elucidating the biochemical pathway responsible for chlorophyll degradation. After having contributed to the identification of key chlorophyll degradation products in the course of the last twenty-five years, he gradually identified and characterized most of the crucial players in the PAO/phyllobilin degradation pathway of chlorophyll. One of the brightest plant biochemists of his generation, his work opened doors to a better understanding of plant senescence, tetrapyrrole homeostasis and their complex regulation. He sadly passed away on 5 December 2020, aged 57.

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“…Notably, independent evidence for the suggested structure of 13-norcypera-1 (5),11(12)-diene(13) was provided by DFT B3LYP calculations with basis set 6-311G + (2d,p) which provided an excellent agreement with experimentally observed NMR data. Additionally, NOE correlations observed in 2D-H, H-ROESY spectrum proved relative configurations at C4, C7 and C10 (identical with those in cyperene) and stereochemical assignment of hydrogen atoms of the methylene groups.Autumnal leaf pigmentation of deciduous tree plants is one of the representative events in plant senescence 64,65. During this process,degradation of chlorophyll occurs by environmental changes including lower temperature and shortening of daylight, and then leaves turnF I G U R E 3 (Continued) brown, yellow, and red.…”

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confidence: 99%

Application of INADEQUATE NMR techniques for directly tracing out the carbon skeleton of a natural product

Ismail

Nahar

Sarker

2020

Phytochemical Analysis

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Introduction Nuclear magnetic resonance (NMR) measurement of 1JCC coupling by two‐dimensional (2D) INADEQUATE (incredible natural abundance double quantum transfer experiment), which is a special case of double‐quantum (DQ) spectroscopy that offers unambiguous determination of 13C–13C spin–spin connectivities through the DQ transitions of the spin system, is especially suited to solving structures rich in quaternary carbons and poor in hydrogen content (Crews rule). Objective To review published literature on the application of NMR methods to determine structure in the liquid‐state, which specifically considers the interaction of a pair of carbon‐13 (13C) nuclei adjacent to one another, to allow direct tracing out of contiguous carbon connectivity using 2D INADEQUATE. Methodology A comprehensive literature search was implemented with various databases: Web of Knowledge, PubMed and SciFinder, and other relevant published materials including published monographs. The keywords used, in various combinations, with INADEQUATE being present in all combinations, in the search were 2D NMR, 1JCC coupling, natural product, structure elucidation, 13C–13C connectivity, cryoprobe and CASE (computer‐assisted structure elucidation)/PANACEA (protons and nitrogen and carbon et alia). Results The 2D INADEQUATE continues to solve “intractable” problems in natural product chemistry, and using milligram quantities with cryoprobe techniques combined with CASE/PANACEA experiments can increase machine time efficiency. The 13C–13C‐based structural elucidation by dissolution single‐scan dynamic nuclear polarisation NMR can overcome disadvantages of 13C insensitivity at natural abundance. Selected examples have demonstrated the trajectory of INADEQUATE spectroscopy from structural determination to clarification of metabolomics analysis and use of DFT (density functional theory) and coupling constants to clarify the connectivity, hybridisation and stereochemistry within natural products. Conclusions Somewhat neglected over the years because of perceived lack of sensitivity, the 2D INADEQUATE NMR technique has re‐emerged as a useful tool for solving natural products structures, which are rich in quaternary carbons and poor in hydrogen content.

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Chlorophyll breakdown—Regulation, biochemistry and phyllobilins as its products

Abstract: pyNCC pyro-NCC pyPheide pyro-pheophorbide RCC red Chl catabolite RCCR RCC-reductase sFCC secondary FCC SGR stay-green (protein) TIC55 translocon at the inner chloroplast membrane 55 UV/Vis ultraviolet/visible (absorbance spectroscopy) YCC yellow (type-I) Chl catabolite

Cited by 30 publications

References 207 publications

A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

A Blue Zinc Complex of a Dioxobilin‐Type Pink Chlorophyll Catabolite Exhibiting Bright Chelation‐Enhanced Red Fluorescence

An evergreen mind and a heart for the colors of fall

Application of INADEQUATE NMR techniques for directly tracing out the carbon skeleton of a natural product

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