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The presence of surface states results in a certain compression of the space charge region and leads to a decrease in the band bending The situation of the electric double layer at a semiconductor/electrolyte solution interface affected by light radiation will be dealt with in Section 510 452 Interfaces between two electrolytes The electrical double layer has also been investigated at the interface between two immiscible electrolyte solutions and at the solid electrolyteelectrolyte solution interface Under certain conditions, the interface between two immiscible electrolyte solutions (ITIES) has the properties of an ideally polarized interphase.

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The dissolved electrolyte must have the following properties: (a) The electrolyte in the aqueous phase, BXAX (assumed to dissociate completely to form cation B ^ and anion A ^ ) , is strongly hydrophilic, while the electrolyte in the organic phase, B2A2 (completely dissociated to cation B 2 + and anion A2~), is strongly hydrophobic These properties can be expressed quantitatively by the conditions for the distribution coefficients between water and the organic phase k^ Ax and k^ Al: <oAl l, ^ A 2 1 (b) The equilibria of the exchange reactions Bi+(w) + B2+(o) ^ Bj+(o) + B2+(w) Ar(w) + A 2 -(o) Ar(o) + A2~(w) (4516).

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2b), but does not change the qualitative properties of high solubility (respectively swelling of a gel or of isolated chains) at low temperature and low solubility (respectively gel shrinkage or collapse of the chain) at temperature beyond the modi ed LCST The generality of this effect is re ected by the diverse chemical structures of macromolecules found in literature, including derivatives of poly(N-isopropylacrylamide) (Liu et al, 2001; Irie, 1993; Mamada et al, 1990), copolymers of isopropylacrylamide and hydroxyalkylacrylamide (Menzel et al, 1995), methyl and hydroxypropyl cellulose derivatives (Zheng et al, 2004), elastinlike polypeptides (Alonso et al, 2001), collagenlike systems (Kusebauch et al, 2006; Strzegowski et al, 1994) The LCST of a modi ed chain decreases typically in proportion to the fraction of azobenzene hydrophobes (Alonso et al, 2001; Menzel et al, 1995) (Eq 71) Fig 7.

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2b schematizes the azo-induced shifts under UV exposure and in the dark, respectively, with published magnitudes illustrated in Table 71 Because of the polarity of the cis isomer of azobenzene, the dark-adapted form of polymers has most typically a lower LCST than the UV-exposed ones, predominantly in its cis forms TLCST T0 a %azo with 0oacis oatrans 7:1.

241 are shifted to the left In other words, the standard potential difference between water and the organic phase for the transfer of the cation of the aqueous phase and the anion of the organic phase must be as positive as possible and the corresponding potential difference for the cation of the organic phase and the anion of the aqueous phase must be as negative as possible In addition, there must be a sufficiently large difference between the less positive value of A 0 for the first pair and the less negative value for the second pair (cf Section 328) Under these conditions, the potential difference between the two phases AQ0 can be changed by charge injection from an external electric current source The appropriate experimental arrangement is shown in Fig 518 E J W Verwey and K F.

It is clear from Fig. 7.2 and Table 7.1, that the samples are made lightresponsive in the temperature range comprised between the LCSTs of the cis and trans forms, respectively. This range might be optimized by proper choice of chemical structures (nature of substituents on azobenzene, nature and length of spacer between the azo and polymer backbone), but except for hydroxypropyl, methyl-cellulose (HPMC), the present data re ect a contribution of azo side groups essentially of the same order of magnitude. A typical value of aUV atrans is, up to now, of 21C711C/mol% azo (except for the HMPC data that reach 6 71C/ mol%). Recalling the constraint of using chains with less than a few mol% azo (cf. introduction), this simple estimate shows that a degree of integration of 1 mol% in chains would impart the system with a typical phototriggered LCST-shift of 21C, only compatible with applications in highly controlled temperature conditions.

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