6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES in Java

Encoding QR Code 2d barcode in Java 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
CHAPTER 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
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Figure 6.6. (a) Changes in transmittance of the vesicle solution of P(tBA46-coAA22)-b-PAzoMA74 subjected to UV irradiation (18 mW cm 2), the solution being still (with no stirring) and stirred by a magnetic bar at different speeds of rotation (about 50, 100, 200, and 300 rpm). (b) Changes in transmittance of the clear solution of P(tBA46-co-AA22)-b-PAzoMA74 (after UV-induced dissociation of vesicles) subjected to visible irradiation (24 mW cm 2), the solution being still and stirred by a magnetic bar at different speeds of rotation (about 100, 200, and 300 rpm). Data of transmittance for different stirring rates are shifted along the ordinate for the sake of clarity. 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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during the rst 20 s; then the transmittance increased gradually over the next 40 s or so to reach the plateau. The occurrence of UV light induced dissociation of polymer vesicles in the solution with no stirring, i.e., in the absence of any shear effect, clearly indicates that the main driving force for the dissociation of vesicles is the thermodynamic instability due to the shifted hydrophilic hydrophobic balance. A similar effect of the stirring rate on the opposite process, i.e., the photoinduced reformation of polymer vesicles upon visible light irradiation inducing the reverse cis trans isomerization of azobenzene mesogens, was observed for the same reason as helping the diffusion of polymer chains toward the surface region. The results in Fig. 6.6b were obtained by applying the visible light irradiation of the same intensity (24 mW cm 2) on the solution containing photodissociated BCP, with no stirring and under different stirring rates. Similar to the dissociation process, before visible light was turned on, the transmittance of the clear solution showed no change under the various stirring rates, while it decreased because of the reformation of the vesicles after visible light was applied on. The rate of the reformation process increases with increasing the stirring rate of the solution. Again, even in the still solution, polymer vesicles can reform, but it takes longer than in solutions under stirring.
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6.5.2. Effect of Irradiation Light Intensity
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It is no surprise that the intensity of UV and visible light is another parameter that can be used to control the rates of the dissociation and formation processes of the polymer vesicles. Figure 6.7 shows the results obtained with three different intensities of UV irradiation for the dissociation (Fig. 6.7a) and three different intensities of visible irradiation for the formation process (Fig. 6.7b), respectively, using a constant stirring rate (B200 rpm of the magnetic bar). For both processes, the kinetics becomes faster with increased irradiation intensity. This can easily be understood by the fact the number of azobenzene mesogens being excited and undergoing the trans cis or the reverse cis trans isomerization should increase when there are more photons available for absorption by increasing the irradiation intensity, which speeds up any changes associated with the photoisomerization process. In Fig. 6.7b, it is also interesting to note that in the absence of visible light irradiation while keeping the probe He Ne laser on the solution, no noticeable change in transmittance occurred over 160 s after the UV irradiation was turned off. This indicates that the probe light (633 nm) did not induce the reverse cis trans isomerization of azobenzene mesogens so that polymer chains, fallen apart from the vesicles upon UV irradiation, remained in the dissolved state. Even after 1 h of illumination with the He Ne laser, only B3% decrease in transmittance of the solution was observed, revealing the appreciable thermal stability of azobenzene moieties in the cis form. Signi cant decrease in transmittance was recorded only after much longer times as a result of thermally activated cis trans backisomerization (B50% decrease after 4 h). Of course, the stability of dissolved polymer chains in the solution depends on the substitution pattern on the azobenzene moiety and the solvent that determine the barrier of the thermal cis trans relaxation.
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