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Figure 5.18 gives the TEM images of the colloidal spheres after the light irradiation. The TEM images of the colloidal spheres before light irradiation have been given in Fig. 5.8. PEAPE colloids do not show observable deformation after being irradiated for 2 h (Fig. 5.18a). After being irradiated for 20 min, the BP-AZCA colloidal spheres can be signi cantly elongated along the light polarization direction (Fig. 5.18b), which has been discussed in Section 5.4.2. The hybrid colloids show unique morphologies after the light irradiation, which are characterized by the spindlelike or tadpolelike shapes with dark spherical cores (Fig. 5.18c). Figure 5.19 shows the TEM images of the hybrid colloids containing different amounts of BP-AZ-CA before (Fig. 5.19a d) and after the light irradiation of the linearly polarized Ar+ laser beam for 2 h (Fig. 5.19e h). After the light irradiation, the colloids show different deformation degrees related to the BP-AZ-CA content. The hybrid colloids containing 80 wt% of BP-AZ-CA show a similar shape deformation as BP-AZ-CA colloids (Fig. 5.19e), although the degree of deformation is less for the same irradiation time period. The hybrid colloids containing 20 wt% of BP-AZ-CA can only show an insigni cant deformation under the same light irradiation condition (Fig. 5.19h). For the hybrid colloids containing 40% and 60 wt% of BP-AZ-CA (Fig. 5.19f, g), the shape deformation degrees are between the two cases aforementioned. As discussed earlier, the colloidal spheres formed from BP-AZ-CA can exhibit signi cant deformation upon Ar+ laser irradiation, whereas PEAPE colloids do not show such deformation under the same condition. Since every hybrid colloidal sphere shows a very similar deformation upon the light irradiation, it indicates that the colloid spheres are all composed of both BP-AZ-CA and PEAPE components. The fact that the deformation degree is lower than that of the

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Figure 5.18. TEM images of the colloids after they are exposed to a linearly polarized Ar+ laser beam for different time periods: (a) PEAPE, 2 h; (b) BP-AZ-CA, 20 min; (c) PEAPE/BP-AZ-CA (1:1, wt:wt), 2 h. Source: From Deng et al., 2007.

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Figure 5.19. Typical TEM images of the PEAPE/BP-AZ-CA colloids containing a different percentage of PEAPE before and after the Ar+ laser irradiation for 2 h: (a) 20 wt%, before irradiation; (b) 40 wt%, before irradiation; (c) 60 wt%, before irradiation; (d) 90 wt%, before irradiation; (e) 20 wt%, after irradiation; (f) 40 wt%, after irradiation; (g) 60 wt%, after irradiation; (h) 90 wt%, after irradiation. Source: From Deng et al., 2007.

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BP-AZ-CA colloids can also lead to the same conclusion. It has been discussed in Section 5.3.4 that the hybrid colloids are formed by gradual assembly from the cores to shell, where the more hydrophobic PEAPE chains compose the inner parts and the BP-AZ-CA chains form the shells. The photoisomerization study is consistent with this core shell structure model. As the HEAZ moieties are con ned in the cores, the isomerization cannot have the same free volume as the HEAZ moieties in the shells. Compared with the PEAPE colloids, where a fraction of HEAZ chromophores is distributed in the shells, the free volume for the photoisomerization in hybrid colloids is reduced. This factor can cause the photoisomerization rate of the hybrid colloids to become obviously lower than that of the PEAPE colloids. Although the hybrid colloids can be deformed by the light irradiation, TEM observation shows that the deformed colloids re ect a morphology obviously different from that of the elongated BP-AZ-CA colloids. Typical appearance possesses a circle core with higher contrast and tails stretched from the core. Considering the photoresponsive behavior of both polymers, it can be concluded that the core and tails are composed of PEAPE and BP-AZ-CA components, respectively. The result implies an interesting effect that the light force can cause

the separation of PEAPE and BP-AZ-CA components in case they are not mixed with each at molecular level.

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