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Figure 13.14. (a) The current response of the 8A5-doped planar lipid membrane under alternating UV (365 nm) and visible (450 nm) light irradiation. (b) The corresponding cis-8A5 concentration change during alternating light irradiation. (c, d) Concept of a bifunctional vesicle proposed by Hurst et al. (1999). In state c, reduction of internal viologen (V2+) is blocked by membrane polarization; in state d, photoisomerization of the membrane-localized dye increase the permeation and the corresponding transmembrane redox reaction. Source: From Tanaka and Yonezawa, 1997 (parts a and b); and Lei and Hurst, 1999 (parts c and b). Reprinted with permission.

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where no(a) and no((i) are the numbers of nearest neighbours that the particle has in the bulk of phases a and jS, respectively, ns(a) and ns(fi) are the numbers of nearest neighbours from phase a or / that the particle has at the interface, ec(a) and ec(/J) are the bond energies between this particle and its nearest neighbour, r's are the energies required for rearrangement of the particle in the interphase in order to be able to form a bond to a

membrane. In addition to this photoelectric response, photoregulated K+ transport through the lipid membrane and liposome membrane was also reported. As an extension of Yonezawa s work, Hurst and coworkers reported photocontrolled K+ permeation through a dihexadecyl phosphate (DHP) bilayer containing azobenzene amphiphilic molecules (Lei and Hurst, 1999). The concept

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particle in the neighbouring phase, ew(a), ev(j8), and v(s) are the changes in the thermal vibrational energies of the particle at the interface as a result of formation of the free surface and contact between the phases, N(a) and N(p) are the numbers of particles per unit surface area for the free surface of phases a and /3, c(s) is the bond energy between the particles of phases a and jS in the interphase and N(s) is the number of such bonds per unit surface area at the interphase. If we assume that N(a) = N((3) = N(s)9 that species at the surface have only one free bond (n0-ns=l) and that ec er, v, then (s) (4.2.3)

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(Fig 1314c,d) was to build a vesicle containing two functional elements, a photoisomerizable molecule (dye) to control the ion permeation and an electrogenic transmembrane redox system to control the membrane polarization The conformational change of the dye molecule disrupts the side-chain packing of the membrane surfactants, and, hence, changes the permeation rates In the ideal circumstance, the dye molecule functions as an ion gate with an on/off switch and the membrane is on (ion permeable) in one conformation but off (ion impermeable) in the other Photoisomerizable azobenzene derivatives are good candidates for the ion gates Hurst and coworkers synthesized an amphiphilic azobenzene derivative, 4-dodecy-4u-(3-phosphate-trimethyleneoxy)azobenzene (DPMA) and incorporated it into DHP vesicles K+ ions were entrapped in the vesicles during the vesicle formation.

This expression can be roughly interpreted as the difference between the Gibbs energy of adhesion of the two phases and the sum of the Gibbs energies of cohesion for the two phases. These considerations can also be used to derive the Dupre equation, where AG(s) is the Gibbs energy of adsorption of the solvent per unit area of the metal surface: AG(s) = y m / a + y 1 / a - y (4.2.4)

Photocontrolled release of K+ ions across the vesicle membrane was conducted by monitoring the K+ ion concentration released into the solution under UV and visible light irradiation conditions UV/visible spectroscopic studies con rmed that DPMA molecules were dispersed into the vesicle membrane without aggregation and isomerized reversibly in the vesicle membrane under UV and visible light irradiation Diffusion of entrapped K+ from DHP vesicles was extremely slow but photocontrollable The transmembrane K+ diffusion rate at room temperature was only slightly enhanced by the trans-cis photoisomerization of the azobenzene ligands At higher temperatures (close to the phase transition temperature), the release rate of K+ from DHP vesicles was increased several fold (up to vefold) The reversible switching of azobenzene between trans and cis conformations leads to alternately increasing and decreasing K+ diffusion rates under alternating UV and visible light irradiation.

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