6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES in Java

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CHAPTER 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
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Figure 6.7. Transmittance vs. time for the vesicle solution of P(tBA46-co-AA22)-bPAzoMA74 at the same stirring rate of about 200 rpm: (a) under UV irradiation of different intensities (for the dissociation of vesicles), and (b) under visible irradiation of different intensities (for the reformation of vesicles). For comparison, also shown in (b) are changes in transmittance for the solution under only the probe light (He Ne laser, 633 nm) illumination with no visible light applied. Source: Tong et al., 2005. Reprinted with permission.
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6.5. FACTORS INFLUENCING THE REVERSIBLE DISSOCIATION AND FORMATION
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6.5.3. Effects of Solvent and Block Copolymer Composition
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Like P(tBA-co-AA)-b-PAzoMA, most amphiphilic BCPs are not soluble in water, in contrast to small-molecule surfactants. As aforementioned, to prepare their micelles or vesicles, the BCP needs to be dissolved rst in an organic solvent that is good for both blocks and then by adding water into the solution. The aggregation of the hydrophobic blocks can occur at a critical water content, leading to the formation of the micellar aggregates. A convenient way to investigate the effect of solvent on the photoinduced processes is to measure and compare the change in transmittance of the BCP solution as a function of added water content in the absence of and under UV irradiation. Using a same solvent, such experiment can also be carried out to reveal the effect of the BCP composition by comparing the behaviors of two BCP samples subjected to the same experimental conditions. Fig. 6.8 shows an example of the results. Figures 6.8a and b compare P(tBA46-co-AA22)-b-PAzoMA74 dissolved in dioxane and tetrahydrofuran (2 mL, 1 mg mL 1), respectively, prior to the addition of water (% in volume with respect to the volume of the organic solvent). With and without UV irradiation (18 mW cm 2), the polymer solution following each addition of water was stirred for 3 min before the transmittance was measured. In the case of the dioxane solution, without UV irradiation, the transmittance starts to decrease signi cantly after addition of about 13% of water, which corresponds to the formation of polymer vesicles. Under UV light, the polymer aggregation process begins at a much higher water content of about 21%, and the transmittance drops more quickly than the solution without UV irradiation. This result shows that in the mixed solvent of dioxane water, the increase in polarity of the PAzoMA block accompanying the conversion of transazobenzene onto cis-azobenzene has shifted the hydrophilic hydrophobic balance in such a way that the critical water content for the aggregation of PAzoMA block forming the vesicle is increased from 13% to 21%. And the magnitude of the change determines the window in which the photoinduced dissociation and reformation of the vesicles can be observed. In other words, only the vesicles formed at water content between about 15% and 20% could display a clear lightcontrolled dissociation and reformation. Vesicles formed at higher water content cannot be disrupted by UV light because of the aggregation of this BCP under UV irradiation (with azobenzene moieties in the cis form). Now, using tetrahydrofuran (THF) as the solvent instead of dioxane (all other experimental conditions were kept the same), upon UV irradiation, the increase in the critical water content for the formation of vesicles is even greater, from 15% to 30%. This means a larger window for the photoinduced dissociation and reformation of polymer vesicles. The effect of solvent can be understood by the fact that different solvents have different interactions with the two blocks forming the BCP. In the present case, mixed THF water seems to be a better solvent (less block selective) for P(tBA46-co-AA22)-b-PAzoMA74, especially with azobenzene moieties in the cis form (under UV light) so that a larger amount of water is required to make the mixed solvent block selective for the BCP aggregation.
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