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Fig. 4.2 Electrocapillary curves of 0.1 M aqueous solutions of KF, KC1, KBr, KI and K2SO4 obtained by means of the drop-time method (page 233). The slight deviation of the right-hand branch of the SO42" curve is caused by a higher charge number of sulphate. (By courtesy of L. Novotny)

The orientation and reorientation of LC domains has already been outlined. The azo chromophores act as mesogens and their photoalignment becomes transferred to the LC host. A very small azo content (a few mol% [Ikeda et al., 1990]) can lead to orientational control of LC domains. This is an excellent example of ampli cation of the azomolecular motion. The phase of a liquid crystal can also be switched with light. Irradiation produces cis isomers, which are poor mesogens and destabilize the nematic phase, thereby inducing a phase transition to the isotropic state. There are comparatively few examples of phototriggered increases in LC ordering. In one case, a nanoscale phase separation of the cis isomers led to a net increase in the order parameter of the LC phase (Prasad and Nair, 2001). In another system, a chiral azo was found to induce a cholesteric phase when it was in the cis state (Ruslim and Ichimura, 2001). With LC (Nikolova et al., 1997) or preoriented amorphous samples (Ivanov et al., 2000), one can photoinduce a chiral domain structure. Incident circularly polarized light becomes elliptically polarized because of the rst oriented layer. This ellipse subsequently reorients deeper chromophores, which in turn modify the ellipticity of the light. This reorientation continues throughout the lm depth. Overall, a chiral ordering of the chromophore domains is established (Nikolova et al., 2000). Remarkably, one can switch between a right- and left-handed

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Further, the concept of the integral capacity K will be introduced:

supramolecular helix at will, by changing the incident light handedness. There are many other examples of photocontrol of supramolecular order. The pitch of a cholesteric LC can be modi ed by isomerization (Sackmann, 1971). Biomacromolecular variants abound (Willner and Rubin, 1996). Azo-modi ed polypeptides can be photoswitched between ordered states (a-helix or b-sheet) and a random coil (Everlof and Jaycox, 2000; Fissi et al., 1996; Yamamoto and Nishida, 1991). The duplex of modi ed DNA can be reversibly switched (Asanuma et al., 2001), and the catalytic activity of histidine can be controlled (Lee and Ueno, 2001). Photoisomerization can also affect self-assembly behavior at the domain level. On irradiation, one can induce a phase change (Aoki et al., 2000), a solubility change (Arai and Kawabata, 1995; Yamamoto et al., 1990), crystallization (Ebralidze and Mumladze, 1990), or even reversal of phase separation (Ef ng and Kwak, 1995). The critical micelle concentration (cmc) and surface activity can also be modi ed (Yang et al., 1995). In an amphiphilic polypeptide system, selfassembled micelles were formed in the dark and could be disaggregated with light (Higuchi et al., 1994). When allowed to assemble as a transmembrane structure, the aggregate could be reversibly formed and destroyed using light, which allowed for reversible photoswitching of ion transport (Higuchi et al., 1995a). Related experiments on methacrylates (Chen et al., 1997a; Angiolini et al., 1995) and polypeptides (Sisido et al., 1991b) showed that a polymer s chiral helix could be reversibly suppressed on irradiation. In a series of polyisocyanate polymers, it could be selected whether irradiation would suppress or increase chirality (Muller and Zentel, 1996; Maxein and Zentel, 1995).

(4.2.26)

2 2 2 2

(Deff,dark) and under UV irradiation (Deff,UV) were estimated to be 9.5 10 17 m2 s 1 and 1.7 10 16 m2 s 1, respectively. These values are much smaller than the effective diffusivity of FDM in Brij 56 templated photoresponsive nanocomposite membranes (Deff,dark = 1.1 10 14 m2 s 1, Deff,UV = 1.6 10 14 m2 s 1). As the pore size and probing molecule size are comparable in the two cases, the pore accessibility plays a major role. It was demonstrated that the photoresponsive nanocomposite membrane had a BCC mesostructure whereas the photoresponsive nanocomposite particles had an onionlike lamellar structure. Only the defects located on the particle surfaces could provide the pathway for uptake and release of OBN probe molecules, which lowered the effective diffusivity considerably.

The differential capacity is given by the slope of the tangent to the curve of the dependence of the electrode charge on the potential, while the integral capacity at a certain point on this dependence is given by the slope of the radius vector of this point drawn from the point Ep = Epzc.

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13.3.5. Reversible Photoswitching Liquid-Adsorption of Azobenzene-Modi ed Mesoporous Silica Materials