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moment for the trans isomer than the cis isomer (Simmons et al, 2007), should not be used because of the opposite change in dipole moment upon UV light illumination Another consideration also does not favor the use of azobenzene derivatives with strong electron-donor and electron-acceptor groups This pattern of substitution on azobenzene usually results in overlap of the absorption of transazobenzene (p-p*) with that of cis-azobenzene (n-p*), in the 440 460 nm region Not only does the cis isomer have a fast thermally activated relaxation back to the trans isomer, photons absorbed by trans-azobenzene, inducing the trans cis isomerization, can also be signi cantly absorbed by cis-azobenzene that induces the reverse cis trans isomerization The consequence of the fast thermal relaxation of cisazobenzene and the simultaneous photoisomerization in the two directions is that few azobenzene moieties in the cis form can stay.

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the semiconductor electrode (<p,). Thus, the overall quantum yield of photocurrent (IPCE = incident photon to current efficiency) is a product of all the three quantities: IPCE = <pL cpT <p, (5.10.29)

More information about any of the following OGF standards and activities can be found at http://www.ogf.org.

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Obviously, for light-controllable polymer micelles, a bistable photoswitch is preferred As far as azobenzene is concerned, its derivatives that can undergo a thorough trans cis isomerization upon UV light illumination and have thermally stable cis isomer are mostly interesting From the above analysis, using azobenzene BCPs, a signi cant increase in dipole moment accompanying the trans cis isomerization of the chromophore under UV light can increase the entire polarity of the hydrophobic polymer block and, consequently, shift the hydrophilic hydrophobic balance in the direction thermodynamically unfavorable to the micellar association Although the micellar association is very sensitive to the balance, such a shift may not be necessarily enough to cause the dissociation of BCP micelles; other factors need to be taken into consideration This can be illustrated using a classical small-molecule surfactant as example.

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It actually denotes the number of electrons flowing through the interface per one photon impinging on it, IPCE is usually considered for monochromatic light (radiant power, P, in W/cm2) whose wavelength (A) matches the wavelength of the absorption maximum of the sensitizer, Amax. A more practical equation for IPCE can easily be derived by combining the photocurrent density, ; p h with the radiant power and wavelength: IPCE =jphhc/XPe (5.10.30)

The anionic surfactants of CH3(CH2)nNHCOO has a cmc sensitive to the hydrophilic hydrophobic balance; the cmc is 18 10 4 mol dm 3 for n=13, while it is reduced by an order to 18 10 5 mol dm 3 for n=15 (longer hydrocarbon tail) (Everett DH, 1988) Now, imagine a micellar solution of the surfactant with n=15 exposed to light, if somehow two methylene groups were removed from the hydrocarbon tail, the micelles would be dissociated if the surfactant concentration in solution was below 18 10 4 mol dm 3 (cmc of the surfactant with n=13), while they would remain if the surfactant concentration was above this cmc This simple example points to the fact that an important shift in the hydrophilic hydrophobic balance alone may not be enough to result in the dissociation of the micelles and that other conditions need to be ful lled.

where c is the velocity of light. The light-harvesting efficiency of an electrode covered with an adsorbed sensitizer can be expressed in the form similar to Eq. (5.10.28): <p L =l-10- a d s r > (5.10.31)

Open Grid Services Architecture (OGSA)

As will be discussed later, this indeed is the case for the micelles formed by azobenzenecontaining BCPs In order to achieve an effective dissociation under UV light, a signi cant increase in the dipole moment for azobenzene while converting from the trans to the cis isomer should be conjugated with a hydrophilic block that is weakly hydrophilic, yet enough to induce the formation of BCP micelles in a selective solvent (Tong et al, 2005) The rst BCP micelles exhibiting reversible light-induced control in dissociation and formation were prepared using azobenzene BCPs (Tong et al, 2005; Wang et al, 2004) More important is the fact that inspired by the principles revealed from these studies on azobenzene BCPs using other chromophores, photosensitive BCP micelles with more effective light-induced.

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