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1) is then valid, where Q(m) is the charge corresponding to the surface area A of the interface on the electrode side and Q(s) is the charge in that part of the double layer in the solution According to the oldest hypothesis, put forward by H L F Helmholtz, the electrical double layer has the character of a plate condenser, whose plates are represented by homogeneously distributed charge in the metal and ions of the opposite charge lying in a parallel plane in the solution at a minimal distance from the surface of the metal According to modern conceptions, the electron cloud in the metal extends to a certain degree into the region of the layer of solvent molecules in the immediate vicinity of the metal surface In this layer, the dipoles of the solvent molecules are oriented to various degrees towards the metal surface.

However, for BSPA TEOS co-gel thin lm samples without P123 template and pure BSPA gel lms, the azobenzene moieties showed no change in the UV/visible spectra under UV light irradiation, indicating hindered photoisomerization This observation is consistent with Brinker and coworkers ndings on the hybrid silica materials prepared using azobenzene-bridged organosilane (BSUA) In Brinker s case (Liu et al, 2002), the hydrogen-bonding interaction between the urea groups not only self-assembles BSUA into highly ordered lamellar structures but also locks in the structures and hinders the photoisomerization of the azobenzene ligands Only after dilution of BSUA with TEOS and.

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Ions can gather in the solution portion of the interphase as a result of the electrostatic field of the electrode ('electrostatic adsorption') They can also, however, be adsorbed specifically on the electrode through van der Waals, hydrophobic and chemical forces If they are less polar than the solvent molecules, uncharged molecules from the solution can also be adsorbed and replace solvent molecules that were originally in direct contact with the electrode In the electrode-solution interphase, the adsorption of these substances is also affected by the influence of the electric field in the double layer on their dipoles Substances that collect in the interphase as a result of forces other than electrostatic are termed surface-active substances or surfactants.

HMDS to prevent the close packing of the BSUA molecules did the azobenzene ligands exhibit reversible photoisomerization. In Corriu s case, the BSPA/TEOS co-gel lms and the pure BSPA gel lms did not exhibit photoisomerization because of the lack of suf cient space for isomerization or the close packing of azobenzene ligands in the lm. The P123-templated nanoporous lms prepared using BSPA and TEOS precursors exhibited similar photoisomerization to those in solution because the removal of the surfactant molecules provided large free volume for the isomerization of the azobenzene ligands positioned on the pore surfaces.

In the simple case of electrostatic attraction alone, electrolyte ions can approach to a distance given by their primary solvation sheaths, where a monomolecular solvent layer remains between the electrode and the solvated ions The plane through the centres of the ions at maximum approach under the influence of electrostatic forces is called the outer Helmholtz plane and the solution region between the outer Helmholtz plane and the electrode surface is called the Helmholtz or compact layer Quantities related to the outer Helmholtz plane are mostly denoted by symbols with the subscript 2 However, electrostatic forces cannot retain ions at a minimal distance from the electrode, as thermal motion continually disperses ions to a greater.

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Nanovalves are devices that can regulate mass transport at the nanoscale by means of light, pH, heat, or other external stimuli Mesoporous materials provide an excellent platform for constructing the nanovalves because of their sizecontrollable nanoscale pores and versatile surface chemistries In an effort to make such devices, Mal et al (2003a,b) synthesized coumarin-modi ed MCM-41 mesoporous silica powders that showed reversible control of release of guest molecules (cholestane) using UV light (l = 250 nm) A team led by Stoddart and Zink built nanovalves that can regulate the controlled-release of guest molecules from nanoporous silica particles using redox-controllable bistable[2]rotaxane molecules (Nguyen et al, 2005; Hernandez et al, 2004) or pH-controllable supermolecules (Leung et al, 2006; Nguyen et al, 2006) to switch the opening and closing of nanopores Azobenzene derivatives have also been used to control mass transport through lipid bilayer membranes 13331.

200 distance from the phase boundary. In this way the Gouy or diffuse layer is formed, i.e. the region between the outer Helmholtz plane and the bulk of the solution. When only electrostatic forces act on the ions, the entire charge is concentrated in this diffuse layer (see Fig. 4.1). The charge accumulated by specific adsorption is partly compensated by a