Fast and Sensitive Detection of Oligosaccharides Using Desalting Paper Spray Mass Spectrometry (DPS-MS)

Document Type

Article

Publication Date

10-7-2020

Abstract

Conventional mass spectrometry (MS)-based analytical methods for small carbohydrate fragments (oligosaccharides, degree of polymerization 2-12) are time-consuming due to the need for an offline sample pretreatment such as desalting. Herein, we report a new paper spray ionization method, named desalting paper spray (DPS), which employs a piece of triangular filter paper for both sample desalting and ionization. Unlike regular paper spray ionization (PSI) and nanoelectrospray ionization (nanoESI), DPS-MS allows fast and sensitive detection of oligosaccharides in biological samples having complex matrices (e.g., Tris, PBS, HEPES buffers, or urine). When an oligosaccharide sample is loaded onto the filter paper substrate (10 × 5 mm, height × base) made mostly of cellulose, oligosaccharides are adsorbed on the paper via hydrophilic interactions with cellulose. Salts and buffers can be washed away using an ACN/H2O (90/10v/v) solution, while oligosaccharides can be eluted from the paper using a solution of ACN/H2O/formic acid (FA) (10/90/1v/v/v) and directly spray-ionized from the tip of the paper. Various saccharides at trace levels (e.g., 50 fmol) in nonvolatile buffer can be quickly analyzed by DPS-MS (<5 min per sample). DPS-MS is also applicable for direct detection of oligosaccharides from glycosyltransferase (GT) reactions, a challenging task that typically requires a radioactive assay. Quantitative analysis of acceptor and product oligosaccharides shows increased product with increased GT enzymes used for the reaction, a result in line with the radioactivity assay. This work suggests that DPS-MS has potential for rapid oligosaccharide analysis from biological samples.

Identifier

85092682386 (Scopus)

Publication Title

Journal of the American Society for Mass Spectrometry

External Full Text Location

https://doi.org/10.1021/jasms.0c00310

e-ISSN

18791123

ISSN

10440305

PubMed ID

32910855

First Page

2226

Last Page

2235

Issue

10

Volume

31

Grant

CHE-1915878

Fund Ref

National Science Foundation

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