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391 reaction which restores the original form of the dye The cycle is terminated by a counterelectrode reaction in the non-illuminated compartment of the cell Both electrode reactions may (but need not) regenerate the reactants consumed at the opposite electrodes The photopotential and photocurrent appear essentially as a result of concentration gradients introduced by an asymmetric illumination of the photoactive electrolyte solution between two inert electrodes Therefore, any photogalvanic cell can, in principle, be considered as a concentration cell The photovoltaic effect is initiated by light absorption in the electrode material This is practically important only with semiconductor electrodes, where the photogenerated, excited electrons or holes may, under certain conditions, react with electrolyte redox systems The photoredox reaction at the illuminated semiconductor thus drives the complementary (dark) reaction at the counterelectrode, which again may (but need not) regenerate the reactant consumed at the photoelectrode.

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The regenerative mode of operation is, according to the IUPAC recommendation, denoted as 'photovoltaic cell' and the second one as 'photoelectrolytic cell' Alternative classification and terms will be discussed below The term 'photovoltaic effect' is further used to denote nonelectrochemical photoprocesses in solid-state metal/semiconductor interfaces (Schottky barrier contacts) and semiconductor/semiconductor {pin) junctions Analogously, the term 'photogalvanic effect' is used more generally to denote any photoexcitation of the dc current in a material (eg in solid ferroelectrics) Although confusion is not usual, electrochemical reactions initiated by light absorption in electrolyte solutions should be termed 'electrochemical photogalvanic effect', and reactions at photoexcited semiconductor electodes 'electrochemical photovoltaic effect' The boundary between effects thus defined is, however, not sharp If, for instance, light is absorbed by a layer of a photoactive adsorbate attached to the semiconductor electrode, it is apparently difficult to identify the light-absorbing medium as a 'solution' or 'electrode material'.

weaker than the energy of transfer of the azobenzene into the nanoparticles In other words, a regime of abrupt saturation of the particles is reached when the distance between azobenzenes in the chain is decreased down to the critical value of loop length The critical transition occurs at Floop=Fbinding The degree of integration of the azobenzene in the polymer de nes the length of the shorter possible loops, and in turn controls the regime of association In the regime of tight multipoint association, the saturation should, however, be reached when either all the binding sites on the particle (eg, number of hydrophobic pockets per protein) are associated or when interloops repulsions damper the energy of association.

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Photoexcited solution molecules may sometimes also react at the photoexcited semiconductor electrode; this process is labelled photogalvanovoltaic effect The electrochemical photovoltaic effect was discovered in 1839 by A E Becquerelt when a silver/silver halide electrode was irradiated in a solution of diluted HNO3 Becquerel also first described the photogalvanic effect in a cell consisting of two Pt electrodes, one immersed in aqueous and the other in ethanolic solution of Fe(ClO4)3 This discovery was made about the same time as the observation of the photovoltaic effect at the Ag/AgX electrodes The term 'Becquerel effect' often appears in the old literature, even for denoting the vacuum photoelectric effect which was discovered almost 50 years later The electrochemical photovoltaic effect was elucidated in 1955 by W H Brattain and G G B Garrett; the theory was further developed.

To estimate the typical number of loops that can be associated on a micelle, we consider that the maximal coverage is almost reached when the loop density brings the bound polymer segments into contact [NloopB4 (1+Rmic/R)2, with R being the radius of a loop and Rmic being the radius of micellar core of the order of 1 nm] At integration levels of the azobenzene signi cantly lower than B5 mol% (constrained by the requirement of small absorbance of solutions), the loops typically contain more than 20 monomers and R would be much higher than 1 nm Accordingly, 4 60 loops could be gathered on a single micelle; a value that matches well with experimental data in Fig 77: 1 g/g bound corresponds here to B40 azobenzene per 100 surfactants, with ca 50% unbound azobenzene.