Elucidating the Fragmentation Mechanism of Protonated Lewis A Trisaccharide using MSn CID

2021 ◽  
pp. 146906672110690
Author(s):  
Volker Iwan ◽  
Jürgen Grotemeyer
Keyword(s):  
Gas Phase ◽  
Main Product ◽  
Bond Cleavage ◽  
Mass Analyzer ◽  
Blood Group Antigens ◽  
Fragmentation Mechanism ◽  
Esi Ms ◽  
Fragment Ions ◽  
Glycosidic Bond Cleavage ◽  
Lewis A

Lewis blood group antigens are a prominent example of isomeric oligosaccharides with biological activity. Understanding the fragmentation mechanism in the gas phase is essential for their identification and assignment by mass spectrometric methods such as ESI-MS. In this work, the [M + H]+ species of Lewis A trisaccharide and Lewis A trisaccharide methyl glycoside were studied by ESI-MS with FT-ICR as mass analyzer with respect to their fragmentation mechanism. The comparison between the underivatized and the methylated species has shown that the reducing end plays a key role in this mechanism. The results of this study question the existence of Z-type fragment ions after activation of the protonated species. The main product of the fragmentation are Y-type fragment ions and a combination of Y-type fragmentation and the loss of water at the reducing end instead of Z-type fragmentation. C-type fragment ions could not be detected. MS3 measurements also reveal that each fragment ion only occurs with the participation of a mobile proton and the possibility of glycosidic bond cleavage after fragmentation has already occurred at the reducing end as B2 fragment ion.

Evidence of gas-phase pyranose-to-furanose isomerization in protonated peptidoglycans

2021 ◽  
Author(s):  
Shanshan Guan ◽  
Benjamin J. Bythell
Keyword(s):  
Gas Phase ◽  
Bond Cleavage ◽  
Glycosidic Bond ◽  
Glycosidic Bond Cleavage

Protonated peptidoglycans isomerize prior to glycosidic bond cleavage.

Characterization of Oligosaccharides of the Lactosamine Series Derived from Keratan Sulfates by Tandem Mass Spectrometry

2000 ◽  
Vol 6 (2) ◽  
pp. 193-203 ◽  
Author(s):  
Masayuki Kubota ◽  
Keiichi Yoshida ◽  
Akira Tawada ◽  
Mamoru Ohashi
Keyword(s):  
Mass Spectrometry ◽  
Tandem Mass Spectrometry ◽  
Bond Cleavage ◽  
The Other ◽  
Negative Ion ◽  
Ring Cleavage ◽  
Tandem Mass ◽  
Fragment Ions ◽  
Glycosidic Bond Cleavage

Positive- and negative-ion fast-atom bombardment tandem mass spectrometry with collision-induced dissociation (FAB-CID-MS/MS) has been used in the characterization of di-and tetra-saccharides of the lactosamine series from keratan sulfates. FAB-CID-MS/MS of Galβ1-4GlcNAc (L1) exhibited strong fragment ions originating from ring cleavage at the reducing-terminal sugar moiety together with glycosidic bond-cleavage ions, whereas GlcNAcβ1-3Gal (K1) showed strong glycosidic bond-cleavage ions but no ring-cleavage ions. A series of ring-cleavage fragment ions was observed with members of the L-series which have free hydroxyl groups at the C1 and C3 positions. CID-MS/MS spectra of the [M + Na – SO3]+ ion ( m/z 406) from L2 and the [M + Na − 2SO3]+ ion ( m/z 406) from L4 were almost identical with the CID-MS/MS spectrum of the [M + Na]+ ion ( m/z 406) from L1, which indicated that the sugar skeletons of L2 and L4 are the same as that of L1. On the other hand, the CID-MS/MS spectrum of the [M + Na – SO3]+ ion ( m/z 508) from L4 did not resemble that of the [M + Na]+ ion ( m/z 508) from L2. The former showed peaks that were additional to the peaks in the latter. Since these extra peaks were accounted for on the basis of the structure of L3 [Galβ1(6S)-4GlcNAc, S = sulfate], the in-source loss of sulfate groups by ester exchange upon FAB ionization takes place in a dual manner; one reaction at the non-reducing terminal sugar to give L2 and the other at the reducing-terminal sugar to give L3. The CID-MS/MS spectra were characteristic for the tetrasaccharides L1-L1, L2-L2 and L4-L4 while in-source fragmentation confirms the component disaccharides of each tetrasaccharide. The structure of a tetrasaccharide trisulfate was confirmed as L2–L4 and not L4–L2 by CID-MS/MS. Negative-ion FAB-CID-MS/MS spectra of the sulfated di-and tetra-saccharides showed a pattern similar to that of the positive-ion spectra. Subtraction of the CID-MS/MS spectrum of the [M – H]− ion of L2 [Galβ1-4GlcNAc(6S)] from that of the [M – H – SO3]− ion of L4 [Gal(6S)β1-4GlcNAc(6S)] gave several specific ions whose origins were nicely explained on the basis of the structure of L3. The structure of a pentasaccharide consisting of N-acetylneuraminic acid and a tetrasaccharide trisulfate was confirmed, on the basis of FAB-CID-MS/MS, as NeuNAcα2-6L2-L4.

Production and Characterization of Beams of Polystyrene Ions

1986 ◽  
Vol 39 (9) ◽  
pp. 1421 ◽  
Author(s):  
AG Craig ◽  
PJ Derrick
Keyword(s):  
Gas Phase ◽  
Bond Cleavage ◽  
Molecular Ions ◽  
Emitter Temperature ◽  
Charge Delocalization ◽  
Mass Fragment ◽  
Fragment Ions ◽  
Efficient Charge ◽  
Low Mass

The formation of gaseous polystyrene molecular ions [M]+ by means of the technique of field desorption is proposed to involve creation of a charged sample/gas interface and subsequent field evaporation of ions. The molecular ions so formed fragment spontaneously in the gas phase, provided the emitter temperature is sufficiently high. The polystyrene chains rupture near their ends rather than in their centres, which is proposed to be a consequence of efficient charge delocalization. Following collisional activation, the polystyrene chains break up to give low-mass fragment ions. The low-mass fragment ions are proposed to be the result of successive depolymerization steps, following initial direct bond cleavage within the polymer chain.

Hydrogen atom attachment to histidine and tryptophan containing peptides in the gas phase

2019 ◽  
Vol 21 (22) ◽  
pp. 11633-11641 ◽  
Author(s):  
Daiki Asakawa ◽  
Hidenori Takahashi ◽  
Shinichi Iwamoto ◽  
Koichi Tanaka
Keyword(s):  
Hydrogen Atom ◽  
Gas Phase ◽  
Bond Cleavage ◽  
Tryptophan Residue ◽  
Side Chains ◽  
Hydrogen Atoms ◽  
Fragment Ions ◽  
Gas Phase Fragmentation

In this study, we focus on the gas-phase fragmentation induced by the attachment of hydrogen atoms to the histidine and tryptophan residue side-chains in the peptide that provides the fragment ions due to Cα–Cβ bond cleavage.

Formation of polynuclear copper complexes of guanine-based nucleobases in the gas phase studied by ESI-MS

2013 ◽  
Vol 354-355 ◽  
pp. 303-311 ◽  
Author(s):  
Daniela Ascenzi ◽  
Pietro Franceschi ◽  
Graziano Guella ◽  
Paolo Tosi
Keyword(s):  
Gas Phase ◽  
Copper Complexes ◽  
Esi Ms

Radiolysis of methylcyclopentane. III. Liquid phase mechanism and comparison of cycloalkanes

1968 ◽  
Vol 46 (20) ◽  
pp. 3235-3240 ◽  
Author(s):  
Gordon R. Freeman ◽  
E. Diane Stover
Keyword(s):  
Liquid Phase ◽  
Gas Phase ◽  
Bond Cleavage ◽  
Open Chain ◽  
Methyl Substitution ◽  
Product Yields ◽  
Total Ionization ◽  
Gamma Radiolysis ◽  
G Value

The initial yields of the major products of the gamma radiolysis of liquid methylcyclopentane (MCP) at 25° are: G(H2) = 4.2, G(1-methylcyclopentene plus methylenecyclopentane) = 2.7, G(3- plus 4-methyl-cyclopentene) = 1.0, G(open chain hexene) = 1.0, and G(bimethylcyclopentyl) = 0.9. The effects of scavengers on the product yields are reported and the mechanism is discussed.The liquid phase radiolytic decompositions of cyclohexane (CH), methylcyclohexane (MCH), cyclopentane (CP), and MCP are compared. The net amount of C—C bond cleavage is much greater in the five-membered than in the six-membered rings. Methyl substitution on the ring reduces G(H2) by about one unit, mainly because of the formation of a type of ion (QH+) that does not yield hydrogen when neutralized by an electron. The QH+ type ions are formed in MCH and MCP, but not in CH and CP. In all the systems, another type of ion (N+) that does not yield hydrogen when neutralized by an electron is formed with a G value of about unity. The type of ion (PH+) that does yield hydrogen when neutralized by an electron has a G value of 3.4 in CH and CP, but only 2.0 in MCP. It is concluded that G(total ionization) is in the vicinity of 4.4 in the liquid compounds, virtually the same as the gas phase values.

scholarly journals The effect of adenine protonation on RNA phosphodiester backbone bond cleavage elucidated by deaza-nucleobase modifications and mass spectrometry

2019 ◽  
Vol 47 (14) ◽  
pp. 7223-7234 ◽  
Author(s):  
Elisabeth Fuchs ◽  
Christoph Falschlunger ◽  
Ronald Micura ◽  
Kathrin Breuker
Keyword(s):  
Mass Spectrometry ◽  
Gas Phase ◽  
Vibrational Excitation ◽  
Bond Cleavage ◽  
Low Energy ◽  
Biological Processes ◽  
Phosphodiester Backbone ◽  
Collisionally Activated Dissociation ◽  
Rna Backbone ◽  
Ionic Hydrogen Bonds

Abstract The catalytic strategies of small self-cleaving ribozymes often involve interactions between nucleobases and the ribonucleic acid (RNA) backbone. Here we show that multiply protonated, gaseous RNA has an intrinsic preference for the formation of ionic hydrogen bonds between adenine protonated at N3 and the phosphodiester backbone moiety on its 5′-side that facilitates preferential phosphodiester backbone bond cleavage upon vibrational excitation by low-energy collisionally activated dissociation. Removal of the basic N3 site by deaza-modification of adenine was found to abrogate preferential phosphodiester backbone bond cleavage. No such effects were observed for N1 or N7 of adenine. Importantly, we found that the pH of the solution used for generation of the multiply protonated, gaseous RNA ions by electrospray ionization affects phosphodiester backbone bond cleavage next to adenine, which implies that the protonation patterns in solution are at least in part preserved during and after transfer into the gas phase. Our study suggests that interactions between protonated adenine and phosphodiester moieties of RNA may play a more important mechanistic role in biological processes than considered until now.

Study of the Gas-Phase Intramolecular Aryltrifluoromethylation of Phenyl(Trifluoromethyl)Iodonium by ESI-MS/MS

2013 ◽  
Vol 24 (5) ◽  
pp. 761-767 ◽  
Author(s):  
Hao-Yang Wang ◽  
Zhang Xiang ◽  
Guo-Sheng Liu ◽  
Yin-Long Guo
Keyword(s):  
Gas Phase ◽  
Esi Ms
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