Synthesis and Characterization of Clickable Cytocompatible Poly(Ethylene Glycol)-Grafted Polyoxetane Brush Polymers

Abstract

We report a new family of clickable poly(ethylene glycol) (PEG)-grafted polyoxetane brush polymers as a potential modular platform for delivery of drugs and imaging agents. 3-Ethyl-3-hydroxymethyloxetane (EHMO) monomer reacted with propargyl benzenesulfonate in the presence of sodium hydride to yield alkyne-substituted monomer (EAMO). Subsequently, cationic ring-opening polymerization using boron trifluoride diethyl etherate catalyst and 1,4-butanediol initiator produced P(EAMO) homopolymer with a DP of ∼30 (30 alkynes per chain). Methoxypoly(ethylene glycol) azide (mPEG750-azide) prepared from mPEG750 (750 g mol-1) was grafted to P(EAMO) via copper(I)-catalyzed alkyne-azide cycloaddition (CuAAC) click chemistry. Water-soluble cytocompatible P(EAMO)-g-PEG brush polymers with controlled degrees of PEGylation were synthesized by varying the feed molar ratio of mPEG750-azide to alkyne (25:100, 50:100, 75:100, and 100:100). 1H NMR, GPC, end-group analysis, FTIR, and DSC were applied for polymer characterization. The utility of P(EAMO)-g-PEG for carrying imaging agents was demonstrated by preparing fluorescently labeled P(EAMO)-g-PEG. 5-(Aminoacetamido)fluorescein (AAF) was used as a model compound. Fluorescein-carrying P(EAMO)-g-PEG was synthesized by click coupling bifunctional spacer 6-azidohexanoic acid (AHA) to P(EAMO)-g-PEG and subsequently coupling of AAF to AHA with EDC/NHS chemistry.

Department(s)

Chemical and Biochemical Engineering

Keywords and Phrases

1 ,4-Butanediol; Bifunctional; Boron trifluoride diethyl etherate; Cationic ring opening polymerization; Click chemistry; End-group analysis; Feed molar ratio; FTIR; Imaging agent; Model compound; Modular platform; PEgylation; Polymer characterization; Propargyl; Sodium hydrides, Acetylene; Boron; Brushes; Dyes; Ethylene glycol; Grafting (chemical); Monomers; Polyethylene oxides; Polymers; Sodium compounds, Polyethylene glycols

International Standard Serial Number (ISSN)

0024-9297; 1520-5835

Document Type

Article - Journal

Document Version

Citation

File Type

text

Language(s)

English

Rights

© 2013 American Chemical Society (ACS), All rights reserved.

Publication Date

08 Jan 2013

Link to Full Text

Share

 
COinS