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Structure elucidation of chlorophyll catabolites (phyllobilins) by ESI-mass spectrometry-Pseudo-molecular ions and fragmentation analysis of a nonfluorescent chlorophyll catabolite (NCC).

Müller T, Vergeiner S, Kräutler B - Int J Mass Spectrom (2014)

Bottom Line: The hyphenation of high performance chromatography with modern mass spectrometric techniques providing high-resolution data as well as structural information from MS/MS experiments has become a versatile tool for rapid natural product identification and characterization.A recent application of this methodology concerned the investigation of the annually occurring degradation of green plant pigments.Since the first structural elucidation of a breakdown product in the early 1990s, a number of similarly structured, tetrapyrrolic catabolites have been discovered with the help of chromatographic, spectroscopic and spectrometric methods.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, 6020 Innsbruck, Austria.

ABSTRACT

The hyphenation of high performance chromatography with modern mass spectrometric techniques providing high-resolution data as well as structural information from MS/MS experiments has become a versatile tool for rapid natural product identification and characterization. A recent application of this methodology concerned the investigation of the annually occurring degradation of green plant pigments. Since the first structural elucidation of a breakdown product in the early 1990s, a number of similarly structured, tetrapyrrolic catabolites have been discovered with the help of chromatographic, spectroscopic and spectrometric methods. A prerequisite for a satisfactory, manually operated or database supported analysis of mass spectrometric fragmentation patterns is a deeper knowledge of the underlying gas phase chemistry. Still, a thorough investigation of the common fragmentation behavior of these ubiquitous, naturally occurring chlorophyll breakdown products is lacking. This study closes the gap and gives a comprehensive overview of collision-induced fragmentation reactions of a tetrapyrrolic nonfluorescent chlorophyll catabolite, which is intended to serve as a model compound for the substance class of phyllobilins.

No MeSH data available.


Related in: MedlinePlus

Diagnostic fragmentations of (+)-ions of NCC 1 (R1 = H+, Na+ or K+). Loss of MeOH.
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fig0030: Diagnostic fragmentations of (+)-ions of NCC 1 (R1 = H+, Na+ or K+). Loss of MeOH.

Mentions: The suggested mechanism is delineated for the [M + H]+ ion in Scheme 2 and gives rise to the formation of a ketene functionality. This is in accordance with a mechanism proposed for CH3OH loss from chlorophyll derivatives using fast atom bombardment (FAB) mass spectrometry [23]. The loss of MeOH is a characteristic attribute for many structurally characterized, naturally occurring chlorophyll degradation products [1], having the methyl ester functionality of the original chlorophylls. However, in some higher plants (e.g. in the Brassicaceae Arabidopsis thaliana[11,24] or oilseed rape [10,25]) this methyl ester function is hydrolyzed in the course of chlorophyll breakdown by a methyl esterase [26], giving rise to a β-keto acid functionality, which decarboxylates readily (see also Section 3.4).


Structure elucidation of chlorophyll catabolites (phyllobilins) by ESI-mass spectrometry-Pseudo-molecular ions and fragmentation analysis of a nonfluorescent chlorophyll catabolite (NCC).

Müller T, Vergeiner S, Kräutler B - Int J Mass Spectrom (2014)

Diagnostic fragmentations of (+)-ions of NCC 1 (R1 = H+, Na+ or K+). Loss of MeOH.
© Copyright Policy - CC BY-NC-ND
Related In: Results  -  Collection

License
Show All Figures
getmorefigures.php?uid=PMC4375672&req=5

fig0030: Diagnostic fragmentations of (+)-ions of NCC 1 (R1 = H+, Na+ or K+). Loss of MeOH.
Mentions: The suggested mechanism is delineated for the [M + H]+ ion in Scheme 2 and gives rise to the formation of a ketene functionality. This is in accordance with a mechanism proposed for CH3OH loss from chlorophyll derivatives using fast atom bombardment (FAB) mass spectrometry [23]. The loss of MeOH is a characteristic attribute for many structurally characterized, naturally occurring chlorophyll degradation products [1], having the methyl ester functionality of the original chlorophylls. However, in some higher plants (e.g. in the Brassicaceae Arabidopsis thaliana[11,24] or oilseed rape [10,25]) this methyl ester function is hydrolyzed in the course of chlorophyll breakdown by a methyl esterase [26], giving rise to a β-keto acid functionality, which decarboxylates readily (see also Section 3.4).

Bottom Line: The hyphenation of high performance chromatography with modern mass spectrometric techniques providing high-resolution data as well as structural information from MS/MS experiments has become a versatile tool for rapid natural product identification and characterization.A recent application of this methodology concerned the investigation of the annually occurring degradation of green plant pigments.Since the first structural elucidation of a breakdown product in the early 1990s, a number of similarly structured, tetrapyrrolic catabolites have been discovered with the help of chromatographic, spectroscopic and spectrometric methods.

View Article: PubMed Central - PubMed

Affiliation: Institute of Organic Chemistry and Center for Molecular Biosciences, University of Innsbruck, 6020 Innsbruck, Austria.

ABSTRACT

The hyphenation of high performance chromatography with modern mass spectrometric techniques providing high-resolution data as well as structural information from MS/MS experiments has become a versatile tool for rapid natural product identification and characterization. A recent application of this methodology concerned the investigation of the annually occurring degradation of green plant pigments. Since the first structural elucidation of a breakdown product in the early 1990s, a number of similarly structured, tetrapyrrolic catabolites have been discovered with the help of chromatographic, spectroscopic and spectrometric methods. A prerequisite for a satisfactory, manually operated or database supported analysis of mass spectrometric fragmentation patterns is a deeper knowledge of the underlying gas phase chemistry. Still, a thorough investigation of the common fragmentation behavior of these ubiquitous, naturally occurring chlorophyll breakdown products is lacking. This study closes the gap and gives a comprehensive overview of collision-induced fragmentation reactions of a tetrapyrrolic nonfluorescent chlorophyll catabolite, which is intended to serve as a model compound for the substance class of phyllobilins.

No MeSH data available.


Related in: MedlinePlus