Photochemical Inversion of Helix in Java

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10.3.3. Photochemical Inversion of Helix
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An excess doping of chiral dopant into a compensated nematic phase breaks the compensated state, and consequently produces a helical structure again.
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Figure 10.19. (a) Gray mask and (b) Color patterning of the Ch LC containing E44, m-azo-8, and chiral obtained by UV irradiation for 10 s through the gray mask at 251C. Source: Yoshioka et al., 2005. See color insert.
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Compensated nematic phase
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Cholesteric phase
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Figure 10.20. Reversible photochemical phase transition between a compensated nematic phase and a Ch phase of E44:chiral:azo-1(80:9.8:10.2 wt%) by UV and visible light irradiation. Source: Yoshioka et al., 2005.
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Figure 10.21. Experimental setup for measuring photochemical change in transparency.
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Figure 10.24 shows an effect of UV and Vis light irradiation on the texture of E44/ R811/azo-1(80/8.4/11.6 wt%) mixture. R811 and azo-1 were found to induce right-handed and left-handed helical structure in E44, respectively. A ngerprint texture observed before UV irradiation indicates that the mixture exists in the lefthanded helical structure, because of the excess twisting ability of azo-1. The helical pitch increased and became in nite by UV irradiation, indicating transformation into a nematic phase. Then, the ngerprint texture appeared again by further UV irradiation. The reversal in the texture was caused by successive Vis light irradiation. Circular dichroic (CD) spectroscopy is one of the effective methods for characterizing helical structure of polymers, polypeptides, and so on (Berova et al., 2000). A cyanine dye, NK-529, shows positive- and negative-induced CD in the right-handed and left-handed helices (E44/R811 and E44/S811), respectively, as shown in Fig. 10.25. Figure 10.26 shows change in the induced CD spectra of NK-529 in the mixture of E44/R811/azo-1 (85/6/9 wt%) in a 5-mm homogeneous glass cell by UV irradiation. Comparison of induced CD spectra shown in Figs. 10.25 and 10.26 reveals that the transformation of the helical structure
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UV 100
80 Transmittance (%)
200 Time (s)
Figure 10.22. Changes in the transmittance of a light from a diode laser (670 nm) through the E44:chiral:m-azo-8 = 80:9.8:10.2 wt% mixture in a 25-mm homogeneous glass cell by UV (3.2 mW/cm2) and Vis (8.3 mW/cm2) light irradiation at 251C.
Nematic phase
Cholesteric phase
UV light
Vis light
Homeotropic texture (transparent state)
Focal conic texture (light-scattering state)
Figure 10.23. Textures of the nematic and the Ch phases in the homeotropic glass cell. Source: Alam et al., 2007.
Azo-1 R811
Azo-1 R811
Azo-1 R811
UV light Vis light
Figure 10.24. Polarized micrographs of the E44/R811/azo-1 (80:8.4:11.6 wt%) mixture in 5-mm glass cell without any alignment treatment upon UV and Vis light irradiation.
from the left-handed helix into the right-handed one is brought about upon UV irradiation (Kurihara et al., 2001). The transformation was reversible by irradiation of UV and Vis light.
10.3.4. Photochemical Control of Lasing
Recently, Ch LCs have attracted interest as tunable photonic band gap materials (Ozaki, 2007), because the Ch LCs possess photonic band gap properties as well as response to the external stimuli (John, 1987; Yablonovitch, 1987). A Ch mixture of E44/S811/m-azo-9/DCM (73.1/22.2/4.3/0.4 in wt%) was prepared (Fig. 10.27). DCM is a laser dye. This mixture showed a Ch phase above room temperature up to 621C; Ch621CI. m-azo-9 and S811 gave left-handed and right-handed helices when they were added in E44. The mixture was injected into a homogeneous glass cell with 25-mm cell gap to obtain a planar molecular orientation. The longer edge of the re ection band of the Ch LC was adjusted to the emission maximum of DCM as shown in Fig. 10.28
3 2 1 0 500
600 700 Wavelength (nm)
1000 CD (mdeg)
0 1000 2000 500 2 3 600 700 Wavelength (nm) 800
CH3 CH3 CH N CH3 NK-529
Figure 10.25. Absorption and CD spectra of NK-529 added in E44/R811 (95/5wt%) (1), E44/S811 (95/5wt%) (2), and E44/azo-1 (95/5wt%) (3).
(curves 1 and 2). The laser emission properties were studied by excitation with the second harmonic light at 532 nm from a Q-switched Nd:YAG laser beam (pulse repetition frequency: 10 Hz, the pulse width: 15 ns). The laser beam was focused on the glass cell by using a convex lens. The Ch sample was irradiated with a laser beam at an incident angle of 451 from the surface normal. By excitation with the second harmonic light of Nd-YAG laser at lower light intensity, a sharp band at 532 nm as well as a broad band at B565 nm were