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219 decreasing to as little as 6 at potentials more distant from Epzc (for the mercury-water interface; these values vary with the electrode metal) It can be seen from Fig 45 that a maximum (or 'hump') appears at potentials somewhat more positive than the potential of the electrocapillary maximum on the differential capacity-potential curve This capacity maximum can be explained by postulating that, in the corresponding potential range, the orientation of the water molecules is minimal, ie the permittivity is maximal; at more positive potentials, the water dipoles are oriented so that their negative ends (ie the oxygen atoms) are directed towards the electrode surface while at more negative potentials this orientation is reversed The disagreement between the potential of the 'hump' and the potential of the electrocapillary maximum is apparently a result of weak chemical interaction between the water molecules and the surface of the electrode.

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Asano T, Okada T. 1984. Thermal 2 E isomerization of azobenzenes. The pressure, solvent, and substituent effects. J Org Chem 49:4387 4391. Besson E, Mehdi A, Lerner DA, Reye C, Corriu RJP. 2005. Photoresponsive ordered hybrid materials containing a bridged azobenzene group. J Mater Chem 15:803 809. Bohm N, Materny A, Kiefer W, Steins H, Muller MM, Schottner G. 1996. Spectroscopic investigation of the thermal cis trans isomerization of disperse red 1 in hybrid polymers. Macromolecule. 29:2599 2604. Brinker CJ, Lu Y, Sellinger A, Fan H. 1999. Evaporation induced self assembly: Nanos tructures made easy. Adv Mater 11:579 585. Chia S, Cao J, Stoddart JF, Zink JI. 2001. Working supramolecular machines trapped in glass and mounted on a lm surface Angew Chem Int Ed 40:2447 2451. Clark T, Ruiz JD, Fan H, Brinker CJ, Swanson BJ, Parikh AN. 2000. A new application of uv ozone treatment in the preparation of substrate supported, mesoporous thin lms. Chem Mater 12:3879 3884. Dillow AK, Brown JS, Liotta CL, Eckert CA. 1998. Supercritical uid tuning of reactions rates: the cis trans isomerization of 4 4u disubstituted azobenzenes. J Phys Chem A 102:7609 7617. Fu Q, Rao GVR, Ista LK, Wu Y, Andrzejewski BP, Aklar LA, Ward TL, Lopez GP. 2003. Control of molecular transport through stimuli responsive ordered mesoporous materi als. Adv Mater 15:1262 1266. Fujiwara H, Yonezawa Y. 1991. Photoelectric response of a black lipid membrane containing an amphiphilic azobenzene derivative. Nature 351:724 726. Hernandez R, Tseng HR, Wong JW, Stoddart JF, Zink JI. 2004. An operational supramolecular nanovalve. J Am Chem Soc 126:3370 3371.

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It should be noted that the dependence of the differential capacity for some mercury-solvent interfaces is simpler than that for water (eg for methanol or formic acid) and for others is more complicated (propylene carbonate, dimethylsulphoxide, sulpholane, etc) In water, the hump disappears at higher temperatures The picture of the compact double layer is further complicated by the fact that the assumption that the electrons in the metal are present in a constant concentration which discontinuously decreases to zero at the interface in the direction towards the solution is too gross a simplification.

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Hugel T, Holland NB, Cattani A, Moroder L, Seitz M, Gaub HE 2002 Single molecule optomechanical cycle Science 296:1103 1106 Ji HF, Feng Y, Xu X, Purushotham V, Thundat T, Brown GM 2004 Photon driven nanomechanical cyclic motion Chem Commun 22:2532 2533 Jin T 2007 Calixarene based photoresponsive ion carrier for the control of Na+ ux across a lipid bilayer membrane by visible light Mater Lett 61:805 808 Jin T, Kinjo K, Koyama T, Kobayashi Y, Hirata H 1996 Selective Na+ transport through phospholipid bilayer membrane by a synthetic calix[4]arene carrier Langmuir 12: 2684 Jin T, Kinjo M, Kobayashi Y, Hirata H 1998 Ion transport activity of calix[n]arene (n 4, 5, 6, 7, 8) esters toward alkali metal cations in a phospholipid bilayer membrane J Chem Soc Faraday Trans 94:3135 Kim HK, Wang XS, Fujita Y, Sudo A, Nishida H, Fujii M, Endo T 2005a.

Indeed, Kornyshev, Schmickler, and Vorotyntsev have pointed out that it is necessary to assume that the electron distribution in the metal and its surroundings can be represented by what is called a 'jellium': the positive metal ions represent a fixed layer of positive charges, while the electron plasma spills over the interface into the compact layer, giving rise to a surface dipole This surface dipole, together with the dipoles of the solvent molecules, produces the total capacity value of the compact double layer Specific adsorption occurs, ie ions enter the compact layer, in a considerable majority of cases The most obvious result of specific adsorption is a decrease and shift in the maximum of the electrocapillary curve to negative values because of adsorption of anions (see Fig 42) and to positive values for the adsorption of cations.

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