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Integrated Biomaterials Science

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Drug Delivery Systems 837<br />

exploitation of polymers is often dictated not only by the superiority of<br />

properties, but by marketing and patenting situations as well.<br />

29.4. Polymers for Controlled Release Applications<br />

Some of the most important biodegradable and nonbiodegradable<br />

polymers used in drug release technology are reported in this section<br />

(Chasin and Langer, 1990; Dumitru, 1994; Park et al., 1993). The former are<br />

preferred for internal application although some nonbiodegradable ones,<br />

such as polysiloxanes, are largely used both inside the body as well as in<br />

delicate body cavities.<br />

29.4.1. Polysiloxanes<br />

Polysiloxanes may be considered the first class of polymers employed<br />

in controlled drug release. They are also known as silicones, a historic name<br />

that originated from the old idea that they were ketones in structure. Their<br />

use in drug release came from the observation by Folkman and Lony while<br />

studying polysiloxane heart valves. These authors found that a lipid soluble<br />

dye like Sudan was adsorbed and could then diffuse in silicon elastomer<br />

membranes, unlike water-soluble dyes like methylene blue. A study with<br />

dyes and drugs of different structures demonstrated that this property is<br />

common to many substances and depends upon their hydrophilic/hydrophobic<br />

ratio; furthermore, penetration into the polymer matrix is due to<br />

hydrophobic interaction.<br />

From the structure reported below, which is at the basis of the most<br />

common products, one may understand the reason for the chemical inertness<br />

of polysiloxanes. They may be degraded, in fact, by a few chemicals<br />

such as ozone or nitrogen oxides. For this reason, heat or chemical means<br />

are much used methods of sterilization.<br />

Their special oligomeric properties are explained by the chemical<br />

structure (I). The Si–O length of 1.64 exhibits high rotation for lower<br />

intramolecular steric hindrance as compared to all the polymers based on<br />

carbon backbone in which the C–C distance is 1.53 Å. The very low torsion<br />

barrier for the rotation along the skeleton bonds is the reason for the high<br />

flexibility and low Tg.

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