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where ym/a is the interfacial tension of the metal-air interface, y1/a is the interfacial tension of the solution-air interface and y is the interfacial tension of the metal-solution interface. Now the relationship between the interfacial tension and the composition of the two phases in contact will be analysed thermodynamically by using the approach of J. W. Gibbs. The interphase can be considered as a particular phase s of thickness h. This phase differs from the homogeneous phases only in that the effect of pressure is accompanied by the effect of the interfacial tension y. Consider a rectangle with sides h (perpendicular to the interphase) and / (parallel with the interphase) located perpendicular to the interphase. The force acting on the rectangle is not equal to the product phi (as for an area in the bulk of the solution) but phi yl. If the volume of the interphase V(s) is increased by dV(s) by increasing the thickness of the interphase by dh, then area A = V(s)/h increases by cL4. The overall work, Wy connected with this process consists of volume work accompanying the increase in the thickness of the interphase and volume and surface work connected with an increase of the surface area: W(s) = -pA dh + {-ph + y) cL4 = -p dV(s) + y dA (4.2.5)

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Permeability coef cients at 411C were estimated to be 4 1012 cm s 1 and 2 1011 cm s 1 for vesicles containing the trans and cis forms of azobenzene, respectively As a comparison, the K+ release rate from DHP vesicles containing predominantly cis-stilbene, which has a similar molecular structure to that of azobenzene, was only enhanced to ca twofold of that from the trans-stilbene Hurst and coworkers attempted to use viologens for constructing an arti cial ion-gated electron transport system because electrogenic transmembrane redox pathways can be selected by appropriate structural con rmations (Lymar and Hurst, 1994, 1992; Patterson and Hurst, 1993) However, the system was not very successful because the reducing potential of the viologen radical cations is suf ciently high to reduce the azobenzene species doped in the DHP vesicle membrane Thus, the vesicles lost the capacity to photoregulate ionic ux across the membrane.

Because of this formation, a different definition of the enthalpy must be introduced for the interphase, differing from the usual expression for a homogeneous phase: H(s) = U(s) + pV(s) - yA (4.2.6)

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where U(s) is the internal energy of the interphase. For the differential Gibbs energy of the interphase we have dG(s) = d[//(s) - TS(s)] = dU(s) + p dV(s) - V(s) dp - y dA - A dy - T dS(s) - 5(s) dT + 2 ft d^i(s) (4-2.7) /=o where nf-(s) is the amount of the ith component of the system in phase s and n is the total number of components. As dU(s) + p dV(s) -ydA-T it follows that dG(s) = ~S(s) dT + V(s) dp - A dy + J) pg dnt(s)

Further investigation is needed to develop electrogenic transmembrane pathways, using less reducing electron carriers and strong oxidizing electron acceptors within the inner vesicle core Recently Jin (2007) synthesized an azobenzene-modi ed calix[4]arene, which acts as a photoresponsive ion carrier for the control of Na+ ux across lipid bilayer membranes The photoresponsive carrier was synthesized in two steps: rst reacting hydrazine with calix[4]arene to form monohydrozide calix[4]arene and.

dS(s) = 0

then grafting 4-dimethylaminoazobenzene to the hydrazide group through a reaction between the hydrazide and the sulfonyl chloride groups. (Fig. 13.15a) The azobenzene-modi ed calix[4]arene has two kinds of functionalities: the ether derivative of calix[4]arene acts as the Na+ carrier (Jin et al., 1998, 1996) and the azobenzene provides photoresponses. Upon combination of these two functionalities, the azobenzene-modi ed calix[4]arene can regulate the Na+ ux across the lipid bilayer membrane after it is incorporated into the membrane. The azobenzene-modi ed calix[4]arene is one of the photochromic compounds that undergoes trans-cis isomerization upon visible light irradiation (p p* transition at 440 nm). It can be easily incorporated into planar soybean phospholipid membranes by using the folding method (Montal and Mueller, 1972). An ampli er was used to record the trans-membrane currents and to control the voltages across the bilayer membrane. In the experiments, the ionic ux current was measured using a voltage-clamping method. It was found that the trans-membrane

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(4.2.8)

THF3/CH2CH3)3

(4.2.9)

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Figure 13.15. (a) Synthetic scheme of the azobenzene-modi ed calix[4]arene. (b) Photoresponses of the membrane currents at 50 mV in the presence of azobenzene-modi ed calix[4]arene. Source: From Jin, 2007. Reprinted with permission.

The NH2 radical rapidly reacts with excess oxalic acid required to form the oxalate complexes of titanium. Partial regeneration of the product of the electrode reaction by a disproportionation reaction is characteristic for the reduction of the uranyl ion in acid medium, which, according to D. H. M. Kern and E. F. Orleman and J. Koutecky and J. Koryta, occurs according to the scheme (5.6.21)

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