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pH-switchable polymer that pulls down N-glycopeptides

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A soluble poly(acrylic acid-co-hydrazide) captures glycopeptides in homogeneous solution and precipitates them by dropping pH for MS.

Source

A pH-responsive soluble polymer-based homogeneous system for fast and highly efficient <i>N</i>-glycoprotein/glycopeptide enrichment and identification by mass spectrometry

Bai H, Fan C, Zhang W, et al. · Chemical science · 2015

doi.org/10.1039/c5sc00396bRead the full paper ↗33 citationscc by

Study at a glance

Design
Other — Homogeneous hydrazide polymer enrichment of periodate-oxidized N-glycopeptides for LC-MS
N
Method development; mouse-brain application identified 1,317 N-glycopeptides / 458 glycoproteins
Population
Model glycoproteins and mouse-brain digests
Outcome
Enrichment efficiency and N-glycoproteome identification performance

Structured fields used in claim comparison tables when every cited study has a complete layer.

What they did

Authors copolymerized methyl acrylate and acrylic acid (1:8), converted esters to hydrazides, periodate-oxidized glycans, captured aldehydes in solution, cycled pH to wash, released peptides with PNGase F, and identified sites by LC-MS/MALDI.

What they found

Homogeneous capture exceeds 95% within 1 h. Asialofetuin recovery is ~90%; a 1741.8 m/z glycopeptide gains 29× intensity and 325× S/N. Mouse brain gave 1317 non-redundant N-glycopeptides and 458 glycoproteins (80% in ≥2 replicates) with 1.46% FDR.

The limits

What it doesn't show

The method uses mouse brain, not a clinical plasma cohort; periodate chemistry destroys some glycan structural information, and false deamidation still occurs at 1.46%.

Key terms

pH-responsive polymer
A polyacid that dissolves at high pH and precipitates at low pH for capture/release.
Hydrazide enrichment
Covalent capture of periodate-oxidized glycan aldehydes as hydrazones.
PNGase F
Enzyme that releases N-glycans and converts Asn to Asp (+0.984 Da).
N-X-S/T sequon
Canonical N-glycosylation motif used to assign sites after deamidation.
Homogeneous enrichment
Capture in solution to avoid solid-phase mass-transfer limits.

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Homogeneous hydrazide enrichment is claimed to reach:

Common questions

Why homogeneous instead of beads?

Unrestricted mass transfer; >95% enrichment within 1 h.

How is the polymer recovered?

Low-pH precipitation and high-pH dissolution cycles.

What tissue was profiled?

Mouse brain.

How are sites assigned?

0.984 Da Asn→Asp shift on an N-X-S/T sequon after PNGase F.

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