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Self-Assembly of Synthetic and Biological Polymeric Systems of ...

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e detected by a given method. Thermodynamically, for copolymers with a narrow block-<br />

length, the association process corresponds to equilibrium between molecules (unimers), A,<br />

<strong>and</strong> micelles, AN, containing N molecules. This can be written as:<br />

If the association number is large <strong>and</strong> independent <strong>of</strong> the temperature then <strong>and</strong><br />

the st<strong>and</strong>art Gibbs energy <strong>of</strong> association is:<br />

Under this condition, for molecules <strong>and</strong> micelles in equilibrium just above the cmc<br />

Figure 3.3. Schematic representation <strong>of</strong> block copolymer micelles in aqueous solution, dense<br />

hydrophobic core is constituted by the hydrophobic block, while the micellar shell is formed by<br />

the hydrophilic block.<br />

The micellization process <strong>of</strong> amphiphilic block copolymers has been studied in a wide range <strong>of</strong><br />

selective solvents: from water to organic polar solvents <strong>and</strong> non-polar solvents, as well as<br />

ecological solvents like supercritic fluids <strong>and</strong> ionic liquids (72). The simplest structural<br />

aggregates formed by block copolymer are called micelles, by the analogy that exists with the<br />

structure <strong>of</strong> common micelle formed by the convectional surfactants in aqueous media (Figure<br />

3.3) (73).<br />

3.1<br />

3.2<br />

94

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