Modern developments in mass spectrometry of chondroitin and dermatan sulfate glycosaminoglycans

Abstract

Chondroitin sulfate (CS) and dermatan sulfate (DS) are special types of glycosaminoglycan (GAG) oligosaccharides able to regulate vital biological functions that depend on precise motifs of their constituent hexose sequences and the extent and location of their sulfation. As a result, the need for better understanding of CS/DS biological role called for the elaboration and application of straightforward strategies for their composition and structure elucidation. Due to its high sensitivity, reproducibility, and the possibility to rapidly generate data on fine CS/DS structure determinants, mass spectrometry (MS) based on either electrospray ionization (ESI) or matrix-assisted laser desorption/ionization (MALDI) brought a major progress in the field. Here, modern developments in MS of CS/DS GAGs are gathered in a critical review covering the past 5 years. The first section is dedicated to protocols for CS/DS extraction from parent proteoglycan, digestion, and purification that are among critical prerequisites of a successful MS experiment. The second part highlights several MALDI MS aspects, the requirements, and applications of this ionization method to CS/DS investigation. An ample chapter is devoted to ESI MS strategies, which employ either capillary- or advanced chip-based sample infusion in combination with multistage MS (MS(n)) using either collision-induced (CID) or electron detachment dissociation (EDD). At last, the potential of two versatile separation techniques, capillary electrophoresis (CE), and liquid chromatography (LC) in off- and/or on-line coupling with ESI MS and MS(n), is discussed, alongside an assessment of particular buffer/solvent conditions and instrumental parameters required for CS/DS mixture separation followed by on-line mass analysis of individual components.

Improvement of the Digestibility of Sulfated Hyaluronans by Bovine Testicular Hyaluronidase: A UV Spectroscopic and Mass Spectrometric Study

“…Soft ionization mass spectrometric techniques such as MALDI or ESI are convenient methods to investigate the molecular weights of oligosaccharides [28]. We will focus here on MALDI MS because this method is influenced to a lesser extent by sample impurities, particularly the salt content.…”

High‐performance separation techniques hyphenated to mass spectrometry for ganglioside analysis

“…Taking place in narrow-bore capillaries, CE allows application of a high electric field, which leads to an unsurpassed separation efficiency and resolution, a high analysis speed, reproducibility of experiments, ease of automation, and miniaturization. CE performance in glycomics was lately significantly improved by online coupling to ESI MS. By online CE/ESI MS technique, employing modern high-resolution MS instruments, molecular masses of glycoforms separated by CE can be directly measured with excellent accuracy and sensitivity; hence, a straightforward identification of single components in complex mixtures originating from biological matrices is possible [83][84][85][86]. Several reports [87][88][89] and reviews [85,82,[90][91][92][93][94] demonstrated that an effective transfer of the sample from the CE capillary into MS without affecting the separation requires an adequate optimization of the CE/ ESI interface and online working conditions in terms of: (i) the choice of an electrolyte compatible with the electrospray process; (ii) the range of the applied CE and ESI voltages; (iii) electrolyte type, concentration, and pH; (iv) sample preparation prior to analysis; (v) injection time and pressure; and (vi) capillary temperature.…”

Combining size‐exclusion chromatography and fully automated chip‐based nanoelectrospray quadrupole time‐of‐flight tandem mass spectrometry for structural analysis of chondroitin/dermatan sulfate in human decorin

“…However, numerous difficulties encountered in the MS analysis of CS/DS [21][22][23][24][25][26][27] limit the benefits of this technique when applied to complex mixtures, if no separation is employed prior to MS. When the depolymerization is performed by lyases, chains of variable lengths and degrees of sulfation are formed.…”