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photooriented spincast lm of PDHS as mentioned earlier, and then oriented deposition of surfactant silica hybrid lm is performed (Fig. 8.2, left). The formation of uniaxially aligned mesochannels is con rmed by transmission electron microscopy (TEM) for the photoaligning layer of 6Az10-PVA PDHS. The two TEM photographs in Fig. 8.3 depict the cross-sectional structure of the as-synthesized surfactant silica hybrid lm observed in the two directions orthogonal to each other. Figure 8.3a shows the image when the lm is sliced parallel to the direction of the actinic polarized light. The hexagonal structure of the mesochannels is clearly visualized through the overall thickness of the lm. However, when the lm is sliced perpendicular to the direction of the actinic polarized light, the lines with a periodicity of 3 4 nm running parallel to the substrate are observed (Fig. 8.3b). The periodic length coincides well with that of the hexagonal spacing obtained by X-ray diffraction (XRD). The cylindrical structure of the mesochannels is fully stretched straight in the lm. Figure 8.3b shows the heterointerface regions composed of the Si wafer (the dark region at the bottom), Az monolayer (2 nm thickness, not clearly shown), PDHS lm (40 60 nm thickness, brighter region), and deposited mesochannels with parallel stripes. The orientational information possessed by the Az monolayer (almost invisible in the photograph) is transferred to the alignment of PDHS with a thickness of ca. 50 nm and then to the mesostructured channels with a thickness of ca. 400 500 nm. Thus, large ampli cations with respect to the controlled mass amounts are attained. An alternative simpler way is to use a photocross-linkable LC polymer lm containing a cinnamoyl unit and a mesogen in the side chain developed by

Fig. 6.14 A gramicidin channel consisting of two helical molecules in the head-to-head position. (According to V. I. Ivanov)

Figure 8.2. Photoalignment of silica mesochannels by photoreactive polymer layers based on the photoisomerization of Az (left) and photodimerization of cinnamoyl unit (right).

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If a small amount of gramicidin A is dissolved in a BLM (this substance is completely insoluble in water) and the conductivity of the membrane is measured by a sensitive, fast instrument, the dependence depicted in Fig. 6.15 is obtained. The conductivity exhibits step-like fluctuations, with a roughly identical height of individual steps. Each step apparently corresponds to one channel in the BLM, open for only a short time interval (the opening and closing mechanism is not known) and permits transport of many ions across the membrane under the influence of the electric field; in the case of the experiment shown in Fig. 6.15 it is about 107 Na+ per second at 0.1 V imposed on the BLM. Analysis of the power spectrum of these

50 nm (a) (b) (a) (b)

Fig. 6.15 Fluctuation of the conductivity of BLM in the presence of gramicidin A. (According to D. A. Haydon and B. S. Hladky)

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Figure 8.3. TEM images of photoaligned silica mesochannels. (a) and (b) indicate the directions of observation. Reprinted with permission from the Royal Chemical Society.

449 stochastic events (cf. page 373) has shown that the rate-detemining reaction of channel formation is the bimolecular reaction of two gramicidin molecules. A similar effect has been observed for alamethicin I and II, hemocyanin, antiamoebin I and other substances. Great interest in the behaviour of these substances was aroused by the fact that they represent simple models for ion channels in nerve cells. Some substances form pores in the membrane that do not exhibit ion selectivity and permit flow of the solution through the membrane. These include the polyene antibiotics amphotericin B, OH O HOOC OH OH OH OH O

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Kawatsuki (Kawatsuki et al., 2002) (Fig. 8.2, right). Morphological observations, X-ray diffraction measurements, and transmission electron microscopic observations indicate that the surface anisotropy imposed by LPL is transferred to the orientation of the rodlike micelle template; therefore, photoaligned mesochannels silica is obtained after removal of the organic component. Interestingly, even when the dip coating is applied, the channel orientation is predominantly controlled by the direction of photoaligning polymer layer and not by the lifting direction (Fukumoto et al., 2006). Thus the orienting power from the photoaligned polymer lm is stronger than that of the ow orientation during the lifting. In a micropatterning experiment, the resolution of ca. 10 mm is obtained (Fig. 8.4) (Fukumoto et al., 2006, 2005).