Structural Characterization of Chlorophyll-a by High Resolution Tandem Mass Spectrometry

Overview

Journal J Am Soc Mass Spectrom

Specialty Chemistry

Date 2013 Mar 19

PMID 23504642

Citations 12

Authors

Juan Wei

Huilin Li

Mark P Barrow

Peter B OConnor

Affiliations

Soon will be listed here.

Abstract

A high resolution Fourier transform ion cyclotron resonance (FTICR) mass spectrometer is used for characterizing the fragmentation of chlorophyll-a. Three tandem mass spectrometry (MS/MS) techniques, including electron-induced dissociation (EID), collisionally activated dissociation (CAD), and infrared mutiphoton dissociation (IRMPD) are applied to the singly protonated chlorophyll-a. Some previously unpublished fragments are identified unambiguously by utilizing high resolution and accurate mass value provided by the FTICR mass spectrometer. According to this research, the two long aliphatic side chains are shown to be the most labile parts, and favorable cleavage sites are proposed. Even though similar fragmentation patterns are generated by all three methods, there are much more abundant peaks in EID and IRMPD spectra. The similarities and differences are discussed in detail. Comparatively, cleavage leading to odd electron species and H(•) loss both seem more common in EID experiments. Extensive loss of small side groups (e.g., methyl and ethyl) next to the macrocyclic ring was observed. Coupling the high performance FTICR mass spectrometer with contemporary MS/MS techniques, especially IRMPD and EID, proved to be very promising for the structural characterization of chlorophyll, which is also suitable for the rapid and accurate structural investigation of other singly charged porphyrinic compounds.

Citing Articles

Matrix Selection Strategies for MALDI-TOF MS/MS Characterization of Cyclic Tetrapyrroles in Blood and Food Samples.

Bianco M, Ventura G, Calvano C, Losito I, Cataldi T, Monopoli A Molecules. 2024; 29(4).

PMID: 38398620 PMC: 10891649. DOI: 10.3390/molecules29040868.

Advancing PROTAC Characterization: Structural Insights through Adducts and Multimodal Tandem-MS Strategies.

Rahman M, Marzullo B, Holman S, Barrow M, Ray A, OConnor P J Am Soc Mass Spectrom. 2024; 35(2):285-299.

PMID: 38197777 PMC: 10853971. DOI: 10.1021/jasms.3c00342.

Infrared Ion Spectroscopic Characterization of the Gaseous [Co(15-crown-5)(HO)] Complex.

Munshi M, Berden G, Oomens J J Phys Chem A. 2023; 127(34):7256-7263.

PMID: 37595154 PMC: 10476210. DOI: 10.1021/acs.jpca.3c04241.

Analysis of Chlorophylls/Chlorophyllins in Food Products Using HPLC and HPLC-MS Methods.

Mandal B, Ling Y Molecules. 2023; 28(10).

PMID: 37241753 PMC: 10220893. DOI: 10.3390/molecules28104012.

Electron-transfer MALDI MS methodology for microalgae/phytoplankton pigments analysis.

Diaz-Sanchez L, Blanco-Tirado C, Combariza M MethodsX. 2023; 10:102140.

PMID: 37007620 PMC: 10050785. DOI: 10.1016/j.mex.2023.102140.

References

Lioe H, OHair R . Comparison of collision-induced dissociation and electron-induced dissociation of singly protonated aromatic amino acids, cystine and related simple peptides using a hybrid linear ion trap-FT-ICR mass spectrometer. Anal Bioanal Chem. 2007; 389(5):1429-37. DOI: 10.1007/s00216-007-1535-1. View

Eckardt N . A new chlorophyll degradation pathway. Plant Cell. 2009; 21(3):700. PMC: 2671716. DOI: 10.1105/tpc.109.210313. View

Suzuki T, Midonoya H, Shioi Y . Analysis of chlorophylls and their derivatives by matrix-assisted laser desorption/ionization-time-of-flight mass spectrometry. Anal Biochem. 2009; 390(1):57-62. DOI: 10.1016/j.ab.2009.04.005. View

Khairallah G, OHair R, Bruce M . Gas-phase synthesis and reactivity of binuclear gold hydride cations, (R3PAu)2H+ (R = Me and Ph). Dalton Trans. 2006; (30):3699-707. DOI: 10.1039/b604404b. View

Grese R, Cerny R, Gross M, Senge M . Determination of structure and properties of modified chlorophylls by using fast atom bombardment combined with tandem mass spectrometry. J Am Soc Mass Spectrom. 2013; 1(1):72-84. DOI: 10.1016/1044-0305(90)80008-B. View

Zhao C, Sethuraman M, Clavreul N, Kaur P, Cohen R, OConnor P . Detailed map of oxidative post-translational modifications of human p21ras using Fourier transform mass spectrometry. Anal Chem. 2006; 78(14):5134-42. PMC: 3098383. DOI: 10.1021/ac060525v. View

Hanson 3rd C, Thaler E . Electronic nose prediction of a clinical pneumonia score: biosensors and microbes. Anesthesiology. 2004; 102(1):63-8. DOI: 10.1097/00000542-200501000-00013. View

Domingues M, Nemirovskiy O, Marques M, Neves M, Cavaleiro J, Ferrer-Correia A . High- and low-energy collisionally activated decompositions of octaethylporphyrin and its metal complexes. J Am Soc Mass Spectrom. 1998; 9(8):767-74. DOI: 10.1016/s1044-0305(98)00048-8. View

Dale M, Costello K, Jones A, Langridge-Smith P . Investigation of porphyrins and metalloporphyrins using two-step laser mass spectrometry. J Mass Spectrom. 1996; 31(6):590-601. DOI: 10.1002/(SICI)1096-9888(199606)31:6<590::AID-JMS308>3.0.CO;2-C. View

10.

Bjorn L, Papageorgiou G, Blankenship R, Govindjee . A viewpoint: why chlorophyll a?. Photosynth Res. 2009; 99(2):85-98. DOI: 10.1007/s11120-008-9395-x. View

11.

Zubarev R, Horn D, Fridriksson E, Kelleher N, Kruger N, Lewis M . Electron capture dissociation for structural characterization of multiply charged protein cations. Anal Chem. 2000; 72(3):563-73. DOI: 10.1021/ac990811p. View

12.

Mayer P, Poon C . The mechanisms of collisional activation of ions in mass spectrometry. Mass Spectrom Rev. 2009; 28(4):608-39. DOI: 10.1002/mas.20225. View

13.

Qi Y, Thompson C, Van Orden S, OConnor P . Phase correction of Fourier transform ion cyclotron resonance mass spectra using MatLab. J Am Soc Mass Spectrom. 2011; 22(1):138-47. DOI: 10.1007/s13361-010-0006-7. View

14.

Mauzerall D . Multiple excitations in photosynthetic systems. Biophys J. 1976; 16(1):87-91. PMC: 1334816. DOI: 10.1016/S0006-3495(76)85665-2. View

15.

Wolff J, Laremore T, Aslam H, Linhardt R, Jonathan Amster I . Electron-induced dissociation of glycosaminoglycan tetrasaccharides. J Am Soc Mass Spectrom. 2008; 19(10):1449-58. PMC: 2716736. DOI: 10.1016/j.jasms.2008.06.024. View

16.

de Paula J, Robblee J, Pasternack R . Aggregation of chlorophyll a probed by resonance light scattering spectroscopy. Biophys J. 1995; 68(1):335-41. PMC: 1281692. DOI: 10.1016/S0006-3495(95)80192-X. View

17.

Kao T, Chen C, Chen B . An improved high performance liquid chromatography-photodiode array detection-atmospheric pressure chemical ionization-mass spectrometry method for determination of chlorophylls and their derivatives in freeze-dried and hot-air-dried Rhinacanthus.... Talanta. 2011; 86:349-55. DOI: 10.1016/j.talanta.2011.09.027. View

18.

Mosely J, Smith M, Prakash A, Sims M, Bristow A . Electron-induced dissociation of singly charged organic cations as a tool for structural characterization of pharmaceutical type molecules. Anal Chem. 2011; 83(11):4068-75. DOI: 10.1021/ac200045n. View

19.

HOLT A, Jacobs E . Infra-Red Absorption Spectra of Chlorophylls and Derivatives. Plant Physiol. 1955; 30(6):553-9. PMC: 540707. DOI: 10.1104/pp.30.6.553. View

20.

Fiedor L, Kania A, Mysliwa-Kurdziel B, Orzel L, Stochel G . Understanding chlorophylls: central magnesium ion and phytyl as structural determinants. Biochim Biophys Acta. 2008; 1777(12):1491-500. DOI: 10.1016/j.bbabio.2008.09.005. View