Abstract

As a facile method to prepare hydrophilic polymeric microspheres, reflux precipitation polymerization has been widely used for preparation of polymer nanogels. In this article, we synthesized a phthalamide-protected N-aminooxy methyl acrylamide (NAMAm-p) for preparation of alkoxyamine-functionalized polymer composite microspheres via reflux precipitation polymerization. The particle size and functional group density of the composite microspheres could be adjusted by copolymerization with the second monomers, N-isopropyl acrylamide, acrylic acid or 2-hydroxyethyl methacrylate. The resultant microspheres have been characterized by TEM, FT-IR, TGA and DLS. The experimental results showed that the alkoxyamine group density of the microspheres could reach as high as 1.49 mmol/g, and these groups showed a great reactivity with ketone/aldehyde compounds. With the aid of magnetic core, the hybrid microspheres could capture and magnetically isolate glycopeptides from the digested mixture of glycopeptides and non-glycopeptides at a 1:100 molar ratio. After that, we applied the composite microspheres to profile the glycol-proteome of a normal human serum sample, 95 unique glycopeptides and 64 glycoproteins were identified with these enrichment substrates in a 5 μL of serum sample.

Highlights

  • In the past decades, multi-functional polymeric microspheres have attracted great attention because of their broad applications in modern science and technology [1]

  • The monomer N-Aminooxy Methylacylimde-p (NAMAm-p) was synthesized via Mitsunobu reaction (Scheme 1a) and its molecular structure was confirmed by 1 H NMR (Figure S1a, Supplementary Material)

  • The PNAMAm was prepared by traditional free radical polymerization of NAMAm-p and one-step deprotection (Scheme 1b)

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Summary

Introduction

Multi-functional polymeric microspheres have attracted great attention because of their broad applications in modern science and technology [1]. The particle size and functional groups of polymeric microspheres both play an important role in practical applications. In order to fulfil different requirements, more and more hybrid microspheres with inorganic cores and polymeric shells have been prepared with different methods, including emulsion polymerization [6,7], surface initiated living polymerization (e.g., SI-ATRP [8,9,10,11], SI-RAFT [12,13]), and so on. The functional microspheres show great potentials in protein enrichment [14,15,16], drug delivery [17,18,19], imaging [20,21], and diagnosis [22,23].

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