Application of Fourier transform ion cyclotron resonance mass spectrometry to oligosaccharides

Electron detachment dissociation (EDD) has recently been shown by Amster and coworkers to constitute a valuable analytical approach for structural characterization of glycosaminoglycans. Here, we extend the application of EDD to neutral and sialylated oligosaccharides. Both branched and linear structures are examined, to determine whether branching has an effect on EDD fragmentation behavior. EDD spectra are compared to collisional activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD) spectra of the doubly and singly deprotonated species. Our results demonstrate that EDD of both neutral and sialylated oligosaccharides provides structural information that is complementary to that obtained from both CAD and IRMPD. In all cases, EDD resulted in additional cross-ring cleavages. In most cases, cross-ring fragmentation obtained by EDD is more extensive than that obtained from IRMPD or CAD. Our results also indicate that branching does not affect EDD fragmentation, contrary to what has been observed for electron capture dissociation (ECD). . Unlike most biomolecules, oligosaccharides often exist as several isomeric forms with diverse linkages, and may form linear or branched structures. Complete structural characterization of oligosaccharides requires the determination of constituent monosaccharides, their linkage, sequence, and branching patterns. Given their diversity and structural complexity, structural elucidation of oligosaccharides often relies upon a wide range of analytical methodologies, of which nuclear magnetic resonance spectroscopy and mass spectrometry are two vital techniques. Tandem mass spectrometry (MS/MS) is widely used for glycan structural characterization [5][6][7], due to the advent of instruments that provide high-quality spectra from even low-abundance molecular species.Tandem mass spectra of oligosaccharides consist mainly of glycosidic and cross-ring product ions. Glycosidic cleavage occurs between monosaccharide units and provides information regarding saccharide sequence and branching. Cross-ring cleavages can provide valuable information regarding saccharide linkage, particularly when occurring at branching residues. Several factors are known to affect oligosaccharide fragmentation and the degree of cross-ring fragmentation, such as the ionizing cation, the lifetime of the ion before detection, and the energy deposited into the ion.Typically, neutral oligosaccharides are analyzed in positive-ion mode, by their protonated forms or through metal ion adduction. In addition, chemical derivatization such as permethylation is widely used to increase sensitivity, reduce molecular ion lability, and produce structurally diagnostic product ions [8 -10]. Low-energy activation methods, such as collisional activated dissociation (CAD) and infrared multiphoton dissociation (IRMPD), applied to protonated oligosaccharides results in predominantly glycosidic cleavages. However, oligosaccharides ionized with alkali, alkaline earth, and transition metals often fragment to yield more cro...

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confidence: 99%

Electron detachment dissociation of neutral and sialylated oligosaccharides

Adamson

Håkansson

2007

“…Since nano-ESI requires only a small amount of sample, a number of experiments such as high-resolution and collision-induced dissociation (CID or MS/MS) determinations can be performed with 1 picomole [2]. Nano-ESI can be coupled to different mass analyzers such as quadrupole time-of-flight (qTOF,) ion trap, triple quad, and Fourier transform ion cyclotron resonance-mass spectrometry (FTICR-MS) [5][6][7][8][9].…”

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confidence: 99%

“…FTICR-MS is advantageous because it can analyze large compounds and is able to achieve high mass resolution with a mass error of less than 1.5 ppm [8,9]. Sustained off-resonance irradiation (SORI) is a CID method that is often used with FT-ICR [9,10]; SORI-CID involves irradiation of the ion slightly off its resonance frequency causing the acceleration and deceleration of ions during the RF pulse at a constant pressure of collision gas.…”

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confidence: 99%

“…Sustained off-resonance irradiation (SORI) is a CID method that is often used with FT-ICR [9,10]; SORI-CID involves irradiation of the ion slightly off its resonance frequency causing the acceleration and deceleration of ions during the RF pulse at a constant pressure of collision gas. At a frequency of several kilohertz, multiple low-energy collisions occur as ions are vibrationally excited for a sustained period (0.5-1 s).…”

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confidence: 99%

See 1 more Smart Citation

Structural analysis of κ-carrageenan sulfated oligosaccharides by positive mode Nano-ESI-FTICR-MS and MS/MS by SORI-CID

Aguilan

Dayrit

Zhang

et al. 2006

Self Cite

Structural analysis of sulfated oligosaccharides from -carrageenan of up to ten residues (MW Ͼ2 kDa) was successfully carried out by positive mode nano-ESI-FTICR-MS together with MS/MS using sustained off-resonance irradiation-collision induced dissociation (SORI-CID). Glycosidic bond cleavage reactions via the B-and Y-types of fragmentation were observed and enabled complete sequencing of the oligosaccharide samples. The positions of the labile sulfate substituents were observable using SORI-CID, enabling the determination of the sequence of the sulfated residues. (J Am Soc Mass Spectrom 2006, 17, 96 -103)

“…T andem mass spectrometry has been used with great success to elucidate the sequences of biomolecules such as nucleic acids [1], peptides [2][3][4][5], and oligosaccharides [6,7]. Both the well-explored dynamics and mechanisms of collision induced dissociation (CID) [8][9][10] and extensively developed computer algorithms that have facilitated spectral interpretation [11,12] have cemented the landmark status of CID for tandem mass spectrometry.…”

Section: Introductionmentioning

confidence: 99%

Enhanced Electron Transfer Dissociation of Peptides Modified at C-terminus with Fixed Charges

Brodbelt

2012

The impact of the conversion of carboxylates in peptides to basic or fixed charge sites on the outcome of electron transfer dissociation (ETD) is evaluated with respect to ETD efficiency and the number of diagnostic sequence ions. Four reagents, including benzylamine (BA), 1-benzylpiperazine (BZP), carboxymethyl trimethylammonium chloride hydrazide (GT), and (2-aminoethyl)trimethylammonium chloride hydrochloride (AETMA), were used for the carboxylate derivatization, with the first two replacing the acidic carboxylate groups with basic functionalities and the latter two introducing fixed charge sites. The ETD efficiencies and Xcorr scores were compared for both nonderivatized and derivatized tryptic and Glu-C peptides from cytochrome c. Derivatization of the carboxylate increases the average charge states, the number of fragment ions, and the dissociation efficiencies of peptides, especially for the fixed charge reagent, AETMA.