Fragmentation of Oligosaccharides from Sodium Adduct Molecules Depends on the Position of <i>N</i>-Acetyl Hexosamine Residue in Their Sequences in Mass Spectrometry

Abstract

Six different sequences of hexasaccharides, pyridylaminated malto-hexaoses containing one -acetyl hexosamine (HexNAc) residue, were analyzed using matrix-assisted laser desorption/ionization (MALDI) tandem time-of-flight (TOF) mass spectrometry (MS). Based on the product ion spectra of sodium adducts [M+Na], the chemical species of the observed product ions contained a HexNAc residue and had high ion abundance, indicating that the HexNAc residue had a higher affinity to sodium atom than glucopyranose. The acetamide group coordinated easily to sodium atom. This general rule of product ion generation was useful to predict the structure of the oligosaccharides based on the MS/MS product ion spectra.

Safety of 3‐fucosyllactose (3‐FL) produced by a derivative strain of Escherichia coli BL21 (DE3) as a Novel Food pursuant to Regulation (EU) 2015/2283

“…The molecular structure of 3‐FL has been determined by high‐performance liquid chromatography – electrospray ionisation – tandem mass spectrometry (HPLC‐ESI‐MS/MS), based on its collision‐induced decay (CID) fragmentation pattern and multiple reaction monitoring (MRM) analysis, by comparison with high purity in‐house and commercially available standards, which allowed to differentiate between 3‐FL α‐(1‐3) and 2’‐FL α‐(1‐2’). The mass fragmentation pattern is consistent with that reported in the literature (Zaia, 2004 ; Kailemia et al., 2014 ; Wang et al., 2016 ; Yamagaki and Makino, 2017 ; Mank et al., 2019 ).…”

Safety of 3‐fucosyllactose (3‐FL) produced by a derivative strain of Escherichia coli K‐12 DH1 as a novel food pursuant to Regulation (EU) 2015/2283

“…The molecular structure of 3‐FL (non‐crystalline and crystalline) was corroborated by high‐performance liquid chromatography – electrospray ionisation – tandem mass spectrometry (HPLC–ESI–MS/MS) based on its collision‐induced dissociation (CID) fragmentation pattern, by comparison to a commercially available high‐purity analytical standard, which allowed to differentiate between 3‐FL α‐(1″‐3) and 2’‐FL α‐(1″‐2′). The mass fragmentation pattern is consistent with that reported in the literature (Zaia, 2004 ; Kailemia et al., 2014 ; Wang et al., 2016 ; Yamagaki and Makino, 2017 ; Mank et al., 2019 ).…”

ESI‐QTof‐MS characterization of hirsutinolide and glaucolide sesquiterpene lactones: Fragmentation mechanisms and differentiation based on Na+/H+ adducts interactions in complex mixture

“…The adduct ion [M+Na] + is commonly formed in ESI‐MS analyses because of the presence of Na + in the mobile phase (0.01–0.1 mM) as solvent impurities . This cation usually shows high affinity to hydrophobic groups and to compounds rich in atoms with lone pairs of electrons (O and N) . Sodium adducts might lead to some inconveniences during the tandem mass analyses with respect to its intensity variation and its poor fragmentation (even with collision energy greater than 40 eV) .…”