Limits...
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: 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.Still, a thorough investigation of the common fragmentation behavior of these ubiquitous, naturally occurring chlorophyll breakdown products is lacking.

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.
© Copyright Policy - CC BY-NC-ND
Related In: Results  -  Collection

License
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).


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: 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.Still, a thorough investigation of the common fragmentation behavior of these ubiquitous, naturally occurring chlorophyll breakdown products is lacking.

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