Synthesis and Characterization of Self-Assembling Block Copolymers Containing Bioadhesive End Groups

3,4-Dihydroxyphenyl-l-alanine (DOPA) is an unusual amino acid found in mussel adhesive proteins (MAPs) that is believed to lend adhesive characteristics to these proteins. In this paper, we describe a route for the conjugation of DOPA moieties to poly(ethylene oxide)−poly(propylene oxide)−poly(ethyl...

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Bibliographic Details
Published in:Biomacromolecules 2002-03, Vol.3 (2), p.397-406
Main Authors: Huang, Kui, Lee, Bruce P, Ingram, Dale R, Messersmith, Phillip B
Format: Article
Language:English
Subjects:
Calorimetry, Differential Scanning
Dihydroxyphenylalanine - chemistry
Hydrogels - chemistry
Molecular Structure
Poloxamer - chemistry
Polyethylene Glycols - chemistry
Polymers - chemistry
Propylene Glycols - chemistry
Solubility
Temperature
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Summary:3,4-Dihydroxyphenyl-l-alanine (DOPA) is an unusual amino acid found in mussel adhesive proteins (MAPs) that is believed to lend adhesive characteristics to these proteins. In this paper, we describe a route for the conjugation of DOPA moieties to poly(ethylene oxide)−poly(propylene oxide)−poly(ethylene oxide) (PEO−PPO−PEO) block copolymers. Hydroxyl end groups of PEO−PPO−PEO block copolymers were activated by N,N ‘-disuccinimidyl carbonate and then reacted with DOPA or its methyl ester with high coupling efficiencies from both aqueous and organic solvents. DOPA-modified PEO−PPO−PEO block copolymers were freely soluble in cold water, and dye partitioning and differential scanning calorimetry analysis of these solutions revealed that the copolymers aggregated into micelles at a characteristic temperature that was dependent on block copolymer composition and concentration in solution. Oscillatory rheometry demonstrated that above a block copolymer concentration of approximately 20 wt %, solutions of DOPA-modified PEO−PPO−PEO block copolymers exhibited sol−gel transitions upon heating. The gelation temperature could be tailored between ∼23 and 46 °C by changing the composition, concentration, and molecular weight of the block copolymer. Rheological measurement of the bioadhesive interaction between DOPA-modified Pluronic and bovine submaxillary mucin indicated that DOPA-modified Pluronic was significantly more bioadhesive than unmodified Pluronic.
ISSN:1525-7797
1526-4602
DOI:10.1021/bm015650p