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Photocontrolled Transport Phenomenon in Lipid Bilayer Membranes Photocontrolled ion transport across lipid bilayer membranes using photoresponsive compounds such as azobenzene derivatives has been of great interest for potential applications in optoelectronic devices and optical transducers Most research has exploited membrane capacitance change because of the disruption of membrane structures resulting from photoisomerization of azobenzene-containing compounds incorporated into the lipid bilayers Others have used the volumetric change of azobenzene moieties associated with photoisomerization In the 1990s, Yonezawa and coworkers pioneered the studies on the photoresponses of planar black lipid membranes containing an amphiphilic azobenzene derivative, 4-octyl-4u-(5-carbox-pentamethylene-oxy) azobenzene (8A5) (Tanaka and Yonezawa, 1997; Tanaka et al, 1996a,b, 1995; Fujiwara and Yonezawa, 1991) After 8A5 was inserted into the lipid membrane, transient current pulses were generated under alternating irradiation of UV and visible light This method was chosen because of the lipid membrane s capacity change induced by azobenzene trans2cis photoisomerization (Fig.

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Fig. 4.1 Structure of the electric double layer and electric potential distribution at (A) a metal-electrolyte solution interface, (B) a semiconductor-electrolyte solution interface and (C) an interface of two immiscible electrolyte solutions (ITIES) in the absence of specific adsorption. The region between the electrode and the outer Helmholtz plane (OHP, at the distance x2 from the electrode) contains a layer of oriented solvent molecules while in the Verwey and Niessen model of ITIES (C) this layer is absent

1314a) The corresponding cis-8A5 concentration change (Fig 1314b) during alternating light irradiation correlated very well with the current change, demonstrating that the conformational change of the azobenzene ligands controls the K+ ux across the.

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201 change in the charge in the diffuse layer A plane through the centres of the adsorbed ions is termed the inner Helmholtz plane (and quantities connected with this plane are denoted by the subscript 1) In order to be able to derive the basic relationships between quantities characterizing the electrical double layer, the concept of an ideal polarized electrode must be introduced Reversible electrodes, considered in 3, are characterized by a potential that, at equilibrium at a given temperature and pressure, is unambiguously determined by the composition of the solution and electrodes, ie by the appropriate activities If a charge is passed through an ideal reversible electrode, processes occur that immediately restore the original equilibrium; in this sense, such an electrode is an ideal non-polarizable electrode.

Product (Chassis)

10 Ultraviolet ( = 365 nm) 5 [cis-8A5]/[8A5] 30 Current (pA) 1

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In contrast, an ideal polarized electrode can assume an arbitrary potential difference versus a reference electrode by the application of an external voltage source and maintain this potential difference even after the voltage source is disconnected Similarly to the EMF of a reversible galvanic cell, this potential is an equilibrium quantity, as will be demonstrated in Section 42 In contrast to a galvanic cell, the potential of an ideal polarized electrode can be arbitrarily changed through a change in its charge without disturbing the electrode from the equilibrium state Thus this electrode has one degree of freedom more than a non-polarizable electrode whose potential is determined by the composition of the solution An ideal polarized electrode is equivalent to a perfect condenser without leakage The difference between an ideal polarized and ideal non-polarizable electrode is best demonstrated in terms of the original Lippmann definition.

0 Visible ( = 450 nm) 5

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The surface charge density of an ideal polarized electrode o(m) is equal to the charge, Qy that must be supplied to the electrode from a voltage source so that its original potential against a reference electrode is maintained during a reversible increase in its surface area by one area unit Charge a(m) is, of course, a function of the potential of the ideal polarized electrode and can even equal zero For an ideal non-polarizable electrode, no charge need be supplied from an external source during a reversible increase in its surface area Clearly, an electrode whose potential is determined by the given ions or oxidation-reduction system in solution has the properties of a condenser (with leakage), as an electrical double layer with a certain capacity is formed at its surface.

Visible ( = 450 nm)

Nonetheless, for a very slow increase in the surface of an ideal non-polarizable electrode, the half-cell reaction! is a sufficient source of charge for loading the electrical double layer The supply of charge from an external source is then unnecessary for maintenance of a constant electrode potential Real electrodes, at which at least one electrode reaction occurs or can occur with finite velocity (see 5), exhibit behaviour between that of.

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20 10 Time (min) (a)

fThis term is used deliberately, rather than 'electrode reaction' ( 5), as a thermodynamically reversible process is involved.

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