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resulting Onsager's expression (2.4.21) completed by the term 1 + BaVc in the denominator introduced by Falkenhagen (cf. Eq. (1.3.31)) takes both effects of interionic forces at higher concentrations into account: V = A'0-(B I A + 3 where B

(2.4.24)

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 67 shows the results obtained with three different intensities of UV irradiation for the dissociation (Fig 67a) and three different intensities of visible irradiation for the formation process (Fig 67b), 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.

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^ \2n{\ + V2)(eRT)3'2

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).

8

The validity of Eq. (2.4.24) for uni-univalent electrolytes has been verified up to a concentration of 0.1 mol dm"3. If the ionic radius is not involved in

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..

98 Eq. (2.4.24) (i.e. the product BaVc is cancelled), then the Onsager limiting law is obtained A = A0 - (B.A0 + B2)\fc (2.4.26) which is an analogy of the Debye-Hiickel limiting law. In the same way it is valid for rather dilute solutions (see Fig. 2.4, dashed line). The ratio of the molar conductivities at moderate and limiting dilutions is the conductivity coefficient given for rather dilute solutions by the relation yA = 1 - (fli + B2lA )Vc (2.4.27)

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400 UV 300 200 100 4s 0 100 2s 200 300 400 550 0s 10 s 8s 6s CD (mdeg)