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eAfcj) = esc - ec = el - ey (5.10.15)

As expected, the azobenzene molecule did not interact as favorably with the protein host as strongly as the natural retinal Despite this, the azo molecules could be coupled into the protein (in the absence of retinal) and led to signi cant shifts in the physicochemical properties of the complex Moreover, the azo molecule could be used as a probe of the inner protein domain (sensing pH, for instance) A particularly elegant experiment involved using azobenzenes to monitor protein folding (Bredenbeck et al, 2003; Sporlein et al, 2002) Femtosecond two-dimensional infrared (2-D IR) spectroscopy was used as a gauge of the distances between carbonyl groups in the peptide An azobenzene chromophore, incorporated inside the polypeptide chain, acted as the photoswitch, initiating a conformational change, hence initiating protein folding, on.

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where esc and ec are the energies of the lower edge of the conduction band at the surface and in the bulk, respectively, and el and ey are analogous energies of the upper edge of the valence band. The positions of esc and el are determined by the Helmholtz electric layer, hence they remain fixed as long as A|0 is not changed. External changes of the electrode potential, Ey manifest themselves as changes of Afcf), at a certain electrode potential (the flatband potential, E^), the band bending disappears, Af0 = 0. For a more detailed description of the semiconductor/electrolyte interface, it is convenient to define the quasi-Fermi levels of electrons, eFe and holes, eFp,

demand. Simultaneous time-resolved measurements of the azo spectra allowed determination of the folding dynamics. This unique measurement of protein-folding behavior was possible because of the phototriggering nature of the azo unit. Ultrafast laser pulse experiments are used to study a large number of chemical reactions, providing detail not possible before. This technique is, however, obviously limited to systems where the chemical events can be phototriggered. By incorporating azobenzene units into new systems, one can generate a phototriggerable system from an otherwise photoinactive one. This strategy can thus be applied to a wide range of problems in chemical dynamics, with biological systems being obvious targets.

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Stiller B, et al 2004 Optically induced mass transport studied by scanning near eld optical and atomic force microscopy Phys Low Dimens Str 1 2:129 137 Stockermans RJ, Rochon PL 1999 Narrow band resonant grating waveguide lters constructed with azobenzene polymers Appl Opt 38(17):3714 3719 Stracke A, Wendorff JH, Goldmann D, Janietz D, Stiller B 2000 Gain effects in optical storage: thermal induction of a surface relief grating in a smectic liquid crystal Adv Mater 12(4):282 285 Sumaru K, Yamanaka T, Fukuda T, Matsuda H 1999 Photoinduced surface relief gratings on azopolymer lms: analysis by a uid mechanics model Appl Phys Lett 75(13):1878 1880 Tabiryan N, Serak S, Dai XM, Bunning T 2005 Polymer lm with optically controlled form and actuation Opt Express 13(19):7442 7448 Tanchak OM, Barrett CJ 2005 Light induced reversible volume changes in thin lms of azo polymers: the photomechanical effect Macromolecules 38(25):10566 10570.

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= c(x) + kT In [ne(x)/(Nc - ne(x))]