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In an effort to make novel materials that accommodate large changes in refractive index, Nishikubo and coworkers prepared a polysilsesquioxane (Mn = 10000, Mw/Mn = 2.89) by hydrolysis and condensation of 4-chloromethylphenyltrimethoxysilane (CPTS) in toluene at 601C for 12 h and modi ed the polysilsesquioxane side chains with 4-tert-butylphenylazophenol or 4-phenylazophenol (Kudo et al., 2006). The resulting polysilsesquioxanes with azobenzene-containing side chains exhibited facile photoisomerization in thin lms. Upon UV light irradiation, the absorption band located at B334 nm (p p* transition) progressively decreased to a photostationary state in ca. 25 s. Two isosbestic points were also observed at B290 and 410 nm, indicating the trans-cis photoisomerization of the azobenzene moieties. The photochemical reaction followed the rst-order kinetics with rate constants of 0.109 s 1 and 0.131 s 1 for 4-tert-butylphenylazophenol and 4-phenylazophenol modi ed polysilsesquioxanes, respectively. The rate constants are several orders of magnitude larger than those of other azobenzene-containing sol gel materials (Sierocki et al., 2006; Liu et al., 2003b), probably owing to the very high power of UV light (500 W) used in the experiments, which is ca. 2-order of magnitude higher than the UV light sources used by others. The refractive indices of the azobenzene-modi ed polysilsesquioxane lms in trans and cis conformations were measured. The differences between the refractive indices (DnD = nD,trans nD,cis) are 0.007 and 0.009 for 4-tert-butylphenylazophenol and 4-phenylazophenol modi ed polysilsesquioxanes, respectively. We can expect that the photocontrolled refractive indices of the azobenzene-modi ed polysilsesquioxanes will have novel applications in optoelectronics, switching devices, optical waveguides, and holographic image records.

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Thus, if no specific ion adsorption occurs, this differential quotient is equal to zero and no surface excess of ions is formed at the electrode This is especially true for ions of the alkali metals and alkaline earths and, of the anions, fluoride at low concentrations and hydroxide Sulphate, nitrate and perchlorate ions are very weakly surface active The remaining ions decrease the surface tension at the maximum on the electrocapillary curve to a greater or lesser degree In the case of a specific ('superequivalent') adsorption we have.

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Photomechanical properties of azobenzene-containing materials were widely studied because of the promising applications in photocontrolled switches and optomechanical actuators Upon UV or visible light irradiation, the azobenzene ligands change conformation and corresponding molecular dimension This molecular level conformational change can be transformed into microscopic and even macroscopic deformation of devices (Kim et al, 2005a,b,c) 13421 Photomechanical Responses of Azobenzene-Containing Materials Ji et al (2004) reported that a self-assembled monolayer (SAM) of azobenzene molecules on a silicon microcantilever created a photon-driven switch Commercial silicon microcantilevers were electron-beam coated on one side with 3 nm of primer layer (chromium), followed by 20 nm of gold An azobenzene derivative with a decanthiol substituent on one ring was used to functionalize the gold surface The thiol (-SH) end attached to the gold surface and the other azobenzene end disposed outward.

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where Fsalt is the surface excess for both components of the electrolyte. One of them may be specifically adsorbed and the second compensates the corresponding excess charge by its excess charge of opposite sign in the diffuse layer. References Frumkin, A. N., Potentials of Zero Charge (in Russian), Nauka, Moscow, 1979. Frumkin, A. N., O. A. Petrii, and B. B. Damaskin, Potential of zero charge, CTE, 1, 221 (1980).

-20 -0.4 -0.8 -1.2 Electrode potential ,V -1.6

Before UV light irradiation, the azobenzene moieties adopted the more stable trans form UV irradiation of the trans-azobenzene-functionalized surface caused the downward de ection of the microcantilever with a maximum bending at B210 nm (Fig 1322) When the UV light was switched off, the position of the microcantilever relaxed back to the level before the UV irradiation This microcantilever deformation under UV irradiation was not observed in control experiments (Fig 1322) for silicon microcantilevers coated with a bare gold surface and a SAM of 1-dodecanethiol on the gold surface This effect was demonstrated to be reversible through numerous cycles (Fig 1322 inset), suggesting potential use in photomechanical devices Ji and coworkers attributed the photoresponses of the azobenzene-functionalized microcantilever to the size change accompanying the trans2cis isomerizations Before UV irradiation, the azobenzene moieties were close-packed as a SAM on the gold surface.

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Fig. 4.3 Surface charge of the mercury electrode a(m) (JUC cm 2) and surface charges due to cations (FrB+) and anions ( F r A ) in 0.1 M KCl and 0.1 M KF at 25 C. (According to D. C. Grahame)

Upon UV irradiation, the azobenzene moieties changed to the cis conformation, which is larger than the trans conformation, leading to the repulsion of molecules in the SAM and, consequently, the downward de ection of the microcantilever Switching off the UV irradiation caused thermal cistrans isomerization of the azobenzene moieties and incurred the complete relaxation of the repulsion force within the SAM, returning the cantilever to its original position Endo and coworkers also investigated the photomechanical behavior of a semi-interpenetrating network (IPN) and a polymer blend that were composed of poly(vinyl ether) containing azobenzene moieties in the side chain and a polycarbonate matrix (Kim et al, 2005a,b,c) Under UV (or UV plus visible) light irradiation, the azobenzene moieties contained in the semi-IPN lm and the polymer blend undergo a trans-cis conformational change that immediately decreases its elasticity and correspondingly increases its strain..

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213 Parsons, R., Thermodynamic methods for the study of interfacial regions in electrochemical systems, CTE, 1, 1 (1980). 4.3 Structure of the Electrical Double Layer

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