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Poly(dimethylsiloxane)-poly(ethylene oxide)-heparin block copolymers. III: Surface and bulk compositional

D W Grainger¹, T Okano, S W Kim

¹Department of Pharmaceutics, University of Utah, Salt Lake City 84112.

Journal of Biomedical Materials Research

|May 1, 1990

Summary

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Poly(dimethylsiloxane)-poly(ethylene oxide)-heparin (PDMS-PEO-Hep) copolymers exhibit surface restructuring in aqueous environments. Surface analysis reveals PDMS dominance, with PEO and heparin accessible upon hydration, enabling bioactivity.

Area of Science:

Polymer Science
Materials Science
Biomaterials

Background:

Poly(dimethylsiloxane)-poly(ethylene oxide)-heparin (PDMS-PEO-Hep) triblock copolymers show promising bioactivity.
Understanding their surface and bulk properties is crucial for applications.

Purpose of the Study:

To investigate the surface and bulk character of PDMS-PEO-Hep copolymers.
To explain surface restructuring in hydrated environments and heparin accessibility.

Main Methods:

Angular-dependent electron spectroscopy for chemical analysis (ADESCA)
Static secondary mass spectroscopy (SIMS)
Differential scanning calorimetry (DSC)
Thermogravimetric analysis (TGA)

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Main Results:

PDMS dominates the surface of solvent-cast copolymers under air/vacuum.
Hydration induces surface restructuring, increasing PEO and heparin accessibility.
DSC and TGA confirm phase-mixed and phase-separated regions, with annealing promoting phase separation and PEO enrichment.
ADESCA and SIMS show a PDMS-rich surface layer (outer 5 Å) with PEO detected deeper within the copolymer.

Conclusions:

PDMS-PEO-Hep copolymers exhibit complex phase behavior and surface restructuring.
Hydration is key to accessing bioactive heparin moieties at the surface.
Compositional models for desiccated and hydrated surfaces were developed based on experimental data.