6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES in Java

Display Quick Response Code in Java 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
CHAPTER 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
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6.5. FACTORS INFLUENCING THE REVERSIBLE DISSOCIATION AND FORMATION
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The comparison of the results in Figs. 6.8a and c reveals the effect of BCP composition on the photoinduced processes. Presented in Fig. 6.8c are the results obtained with a different BCP sample, namely, P(tBA19-co-AA33)-b-PAzoMA31. As compared with P(tBA46-co-AA22)-b-PAzoMA74, this sample has a much shorter hydrophobic PAzoMA block and a more hydrophilic block because of the relative length and the higher ratio of the number of AA units to that of tBA units. Under the same conditions, the increase in the critical water content for the aggregation in the dioxane solution upon UV irradiation is much smaller. Indeed, no clear photoinduced dissociation and reformation of vesicles were observed for this sample. SEM observation found that only large micelle-like aggregates (B200 nm) coexisting with core shell micelles (B15 nm) were formed by adding water into the dioxane solution; UV and visible light irradiation only resulted in changes in the number of the aggregates (Wang et al., 2004). This result suggests that a large increase in dipole moment of azobenzene moieties on the hydrophobic block upon UV irradiation is necessary but may not be enough to lead to the dissociation of micellar aggregates. The same increase in dipole moment for azobenzene mesogens takes place in the two samples upon UV light irradiation, but for P(tBA19-co-AA33)-b-PAzoMA31, the resulting increase in polarity of the PAzoMA block is not important enough to alter signi cantly the hydrophilic hydrophobic balance because of the stronger hydrophilicity of the P(tBA-co-AA) block. Therefore, it appears that the prominent light-induced dissociation and reformation observed for the vesicles of P(tBA46-co-AA22)-b-PAzoMA74,were the result of an increase in polarity of the hydrophobic PAzoMA block in conjunction with the weakness of hydrophilicity of the hydrophilic block (the relative length and chemical nature). Under such a conjugation, the reversible trans cis isomerization of azobenzene moieties can alter reversibly the hydrophilic hydrophobic balance in the two directions, which determines the state of aggregation of the diblock copolymer. Strictly speaking, the origin of the observed effect is more complicated than it may appear to be. The difference between the two BCP samples may come not only from the difference in composition of the two blocks, but can also be contributed by the different compositions of the P(tBA-co-AA) blocks, which actually changes the chemical nature of the hydrophilic block. In order to disclose the effect of BCP composition, it would be more straightforward to utilize BCPs that differ only in the relative lengths of the two blocks, such as PAA-b-PAzoMA
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Figure 6.8. (a) Transmittance vs. water content added to the dioxane solution of P(tBA46-co-AA22)-b-PAzoMA74 (initial concentration, 1 mg mL 1) without and with UV irradiation. (b) Transmittance vs. water content added to the tetrahydrofuran solution of P(tBA46-co-AA22)-b-PAzoMA74 (initial concentration, 1 mg mL 1) without and with UV irradiation. (c) Transmittance vs. water content added to the dioxane solution of P(tBA19-co-AA33)-b-PAzoMA31 (initial concentration, 1 mg mL 1) without and with UV irradiation. Source: Tong et al., 2005.
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CHAPTER 6: AZOBENZENE CONTAINING BLOCK COPOLYMER MICELLES
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or PEO-b-PAzoMA. Moreover, the effect of BCP composition is related to the used solvent. The more the increase in polarity of the hydrophobic block due to the trans cis isomerization of azobenzene reduces the difference in solubility of the two blocks in a given solvent, the more ef cient the photoinduced dissociation of the micellar aggregates should be.
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6.6. OTHER LIGHT-RESPONSIVE AZOBENZENE-BASED POLYMER MICELLES
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The interest of using photoswitchable polarity of azobenzene to design lightresponsive polymer micelles goes beyond BCPs. A nice example can be found in a study of Liu and Jiang who designed light-controllable, noncovalently connected polymer micelles involving no block copolymers (Liu and Jiang, 2006). They showed that the hydrogen (H)-bonded complex between an azobenzene-containing random copolymer, poly(4-phenylazo-maleinanil-co-4-vinylpyridine) (AzoMIVPy), and carboxy group-terminated polybutadiene (CPB) was soluble in toluene, with azobenzene moieties in the trans form. Under UV light irradiation, the increase in polarity with cis azobenzene renders AzoMI-VPy insoluble, leading to the formation of micelles with the AzoMI-VPy core. The CPB shell, however, remains soluble in the solvent. Upon visible light irradiation, the micelles were dissociated. The change between the micellar and soluble polymer complex under UV and visible light was reversible. Moreover, when the AzoMI-VPy micelle core was chemically cross-linked to afford the structural integrity, visible light irradiation could no longer dissociate the micelles, instead the core shell micelles (B250 nm) were transformed into larger hollow spheres (B900 nm) due to the solubility of AzoMI-VPy with azobenzene in the trans form. As shown in Fig. 6.9, dynamic light scattering (DLS) measurements found that the large change in size between core shell micelles and hollow spheres is also reversible upon alternating UV and visible light irradiation. This striking optical switching of selfassembly displayed by H-bonded azobenzene-containing polymers is schematized in Fig. 6.10. Other interesting photoisomerization-induced phenomena were also reported with polymer micellar aggregates formed by azobenzene-containing amphiphilic BCPs. Using a diblock copolymer composed of PEO and poly{2-[ethyl(4-(4cyanophenylazo)-phenyl)amino]ethyl methacrylate} (PEO-b-PEPAEMA), Wang et al. showed photoinduced deformation of spherical micelles under linearly polarized Ar+ laser irradiation (488 nm) (Wang et al., 2007). Su et al. synthesized a diblock copolymer of poly(N-isopropylacrylamide) and poly6-[4-(4-methyl phenylazo)-phenoxyl] hexylacrylate (PNIPM-b-PMPHA) that can form giant vesicles (most having diameters of several micrometers) in a water THF mixture (Su et al., 2007). Deformation and fusion of the giant vesicles upon UV light irradiation (365 nm) was observed and investigated using an optical microscope. A change in polarity and LC order of azobenzene mesogenic groups related to the trans cis photoisomerization was suggested as the origin of the observed vesicle perturbation.
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