Investigation of the Experimental Parameters of Ultraviolet Photodissociation for the Structural Characterization of Chondroitin Sulfate Glycosaminoglycan Isomers
| Autor: | Dustin R. Klein, Jennifer S. Brodbelt, Lauren E. Pepi, I. Jonathan Amster, Franklin E. Leach |
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| Rok vydání: | 2021 |
| Předmět: |
Glycan
biology 010401 analytical chemistry Chondroitin sulfate B Uronic acid 010402 general chemistry Tandem mass spectrometry 01 natural sciences Article Dermatan sulfate 0104 chemical sciences Glycosaminoglycan chemistry.chemical_compound Sulfation chemistry Structural Biology biology.protein Biophysics Chondroitin sulfate Spectroscopy |
| Zdroj: | J Am Soc Mass Spectrom |
| ISSN: | 1879-1123 1044-0305 |
| DOI: | 10.1021/jasms.1c00119 |
| Popis: | Glycosaminoglycans (GAGs) are linear polysaccharides that participate in a broad range of biological functions. Their incomplete biosynthesis pathway leads to nonuniform chains and complex mixtures. For this reason, the characterization of GAGs has been a difficult hurdle for the analytical community. Recently, ultraviolet photodissociation (UVPD) has emerged as a useful tool for determining sites of modification within a GAG chain. Here, we investigate the ability for UVPD to distinguish chondroitin sulfate epimers and the effects of UVPD experimental parameters on fragmentation efficiency. Chondroitin sulfate A (CS-A) and chondroitin sulfate B (CS-B), commonly referred to as dermatan sulfate (DS), differ only in C-5 uronic acid stereochemistry. This uronic acid difference can influence GAG-protein binding and therefore can alter the specific biological function of a GAG chain. Prior tandem mass spectrometry methods investigated for the elucidation of GAG structures also have difficulty differentiating 4-O from 6-O sulfation in chondroitin sulfate GAGs. Preliminary data using UVPD to characterize GAGs showed a promising ability to characterize 4-O sulfation in CS-A GAGs. Here, we look in depth at the capability of UVPD to distinguish chondroitin sulfate C-5 diastereomers and the role of key experimental parameters in making this distinction. Results using a 193 nm excimer laser and a 213 nm solid-state laser are compared for this study. The effect of precursor ionization state, the number of laser pulses (193 or 213 nm UVPD), and the use of the low-pressure versus high-pressure trap are investigated. |
| Databáze: | OpenAIRE |
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