Application of Sustained off-Resonance Irradiation Infrared Multiphoton Dissociation Tandem Mass Spectrometry to the Analysis of Biomolecules

2005 ◽  
Vol 11 (5) ◽  
pp. 483-487 ◽  
Author(s):  
Göran Hübner ◽  
Catharina Crone ◽  
Buko Lindner
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Laser Beam ◽  
Pulse Sequence ◽  
Irradiation Time ◽  
Infrared Multiphoton Dissociation ◽  
Ion Cyclotron Resonance ◽  
Tandem Mass ◽  
Cyclotron Motion ◽  
Multiphoton Dissociation

A modified pulse sequence for infrared multiphoton dissociation (IRMPD) experiments on a Fourier transform ion cyclotron resonance (ICR) mass spectrometer in conjunction with sidekick trapping is presented. For IRMPD tandem mass spectrometry experiments gated trapping is normally applied. It ensures that the ions remain on-axis and, thus, cross the laser beam which is aligned on-axis in commercially available instruments. Sidekick trapping is used to capture more ions in the ICR cell in order to increase the signal intensity. However, it may lead to off-axis ion motion, which reduces or even excludes interaction with the laser beam. In this contribution, sustained off-resonance irradiation (SORI) was applied to overcome this disadvantage of sidekick trapping. SORI is normally used in conjunction with collision-induced dissociation experiments to increase the kinetic energy of the ions. Here, SORI is used to influence the cyclotron motion during the laser irradiation time, which leads to a temporary intersection of the ion trajectory with the laser beam. With this easy-to-handle experimental set-up, IRMPD of ions captured with sidekick trapping again leads to the generation of fragment ions, as is demonstrated with several biologically relevant samples like peptides, lipids and glycolipids.

Profiling of Cyclic Hexadepsipeptides Roseotoxins Synthesized In Vitro and In Vivo: A Combined Tandem Mass Spectrometry and Quantum Chemical Study

2003 ◽  
Vol 9 (2) ◽  
pp. 105-116 ◽  
Author(s):  
Alexandr Jegorov ◽  
Béla Paizs ◽  
Martin Žabka ◽  
Marek Kuzma ◽  
Vladimír Havlíček ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Quantum Chemical ◽  
High Performance ◽  
Ion Trap ◽  
Quantum Chemical Study ◽  
Ion Cyclotron Resonance ◽  
Tandem Mass

High-performance liquid chromatography and tandem mass spectrometry (HPLC/MS/MS) was used for the detection of cyclic hexadepsipeptides roseotoxins produced by Trichothecium roseum. Roseotoxins were found in both submerged standard cultivation on Czapek–Dox medium and in vivo cultivation extract obtained from an apple. Roseotoxin chromatographic profiles from these two experiments were compared. Product-ion collision-induced dissociation (CID) spectra obtained on an ion trap (electrospray ionisation, ESI) were used for the identification of natural roseotoxins A, B, C and of minor destruxins A and B. The dissociation behavior of roseotoxins is discussed in terms of a fragmentation scheme proposed for describing the dissociation pathways of cyclic peptides. This scheme involves opening of the cyclopeptide ring via formation of oxazolone derivatives and fragmentation of the resulting linear species, which have a free N-terminus and an oxazolone ring at the C-terminus. Some aspects of this fragmentation scheme are underlined by modeling the dissociation channels of roseotoxin A using quantum chemical calculations. The structures of roseotoxin A and destruxin B were verified by nuclear magnetic resonance (NMR) spectroscopy. Structures of three new minor natural roseotoxins [Val4]RosA, [MeLxx4]RosA and [MeLxx4]RosB were deduced by ion cyclotron resonance Fourier transform mass spectrometry (ICR-FT-MS) and ion trap tandem mass spectrometry by examining the pre-separated roseotoxin fraction.

scholarly journals Diagnosis of Hemoglobinopathy and β-Thalassemia by 21 Tesla Fourier Transform Ion Cyclotron Resonance Mass Spectrometry and Tandem Mass Spectrometry of Hemoglobin from Blood

2019 ◽  
Vol 65 (8) ◽  
pp. 986-994 ◽  
Author(s):  
Lidong He ◽  
Alan L Rockwood ◽  
Archana M Agarwal ◽  
Lissa C Anderson ◽  
Chad R Weisbrod ◽  
...  
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Cyclotron Resonance ◽  
Abundance Ratio ◽  
Resolving Power ◽  
Ion Cyclotron Resonance ◽  
Tandem Mass ◽  
Hb Variant ◽  
Ft Icr Ms ◽  
Ft Icr

Abstract BACKGROUND Hemoglobinopathies and thalassemias are the most common genetically determined disorders. Current screening methods include cation-exchange HPLC and electrophoresis, the results of which can be ambiguous because of limited resolving power. Subsequently, laborious genetic testing is required for confirmation. METHODS We performed a top-down tandem mass spectrometry (MS/MS) approach with a fast data acquisition (3 min), ultrahigh mass accuracy, and extensive residue cleavage by use of positive electrospray ionization 21 Tesla Fourier transform ion cyclotron resonance–tandem mass spectrometry (21 T FT-ICR MS/MS) for hemoglobin (Hb) variant de novo sequencing and β-thalassemia diagnosis. RESULTS We correctly identified all Hb variants in blind analysis of 18 samples, including the first characterization of homozygous Hb Himeji variant. In addition, an Hb heterozygous variant with isotopologue mass spacing as small as 0.0194 Da (Hb AD) was resolved in both precursor ion mass spectrum (MS1) and product ion mass spectrum (MS2). In blind analysis, we also observed that the abundance ratio between intact δ and β subunits (δ/β) or the abundance ratio between intact δ and α subunits (δ/α) could serve to diagnose β-thalassemia trait caused by a mutation in 1 HBB gene. CONCLUSIONS We found that 21 T FT-ICR MS/MS provides a benchmark for top-down MS/MS analysis of blood Hb. The present method has the potential to be translated to lower resolving power mass spectrometers (lower field FT-ICR mass spectrometry and Orbitrap) for Hb variant analysis (by MS1 and MS2) and β-thalassemia diagnosis (MS1).

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