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A different methodology is to immobilize the protein of interest inside a photoisomerizable copolymer matrix, which was used to control a-chymotrypsin (Willner and Rubin, 1993; Willner et al, 1991b, 1993) The azobenzene need not be directly incorporated into an enzyme of interest In one case, the activity of tyrosinase could be modi ed by isomerization of small-molecule azo inhibitors (Komori et al, 2004) The photoselective binding of short peptide fragments into enzymes can be used to inhibit, thus control, activity (Harvey and Abell, 2000, 2001) Similarly, the binding of an azopeptide with a monoclonal antibody was found to be photoreversible (Harada et al, 1991) The photoresponse of azobenzene can thus be used to control the availability of key biomolecules In one case, NAD+ was modi ed with an azobenzene group, and introduced into a mixture with an antibody that binds to the trans form (Hohsaka et al.

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(5.9.1)

, 1994) This binding makes NAD+ unavailable, whereas irradiation of the solution with UV light induces the trans to cis isomerization, and thereby liberates NAD+ Bioengineering has more recently been broadened by expanding the natural protein alphabet with arti cial amino acids This enables novel and nonnatural protein sequences to be created, while still exploiting the highly ef cient natural synthesis machinery Chiral azobenzene amino acids have been synthesized and incorporated into protein sequences (Wang and Schultz, 2004) The introduction of arti cial photoactive residues opens the possibility of.

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The first step is so fast that it can hardly be measured experimentally, while the second step is much slower (probably as a result of the repulsion of negatively charged species, R" and R2", in the negatively charged diffuse electric layer). The reduction of an isolated benzene ring is very difficult and can occur only indirectly with solvated electrons formed by emission from the electrode into solvents such as some amines (see Section 1.2.3). This is a completely different mechanism than the usual interaction of electrons from the electrode with an electroactive substance. In the presence of a proton donor, such as water, radical anions accept a proton and the reaction scheme assumes the form R

(in amorphous materials), the rigidity of the matrix prevents the relaxation required for crystallization, and thus photoexpansion is frozen in place. However above a crossover temperature, mobility is suf cient for azo groups to reorganize and crystallize into higher density states. It may thus be that liquid crystal materials exhibit photocontraction simply because they are above their characteristic crossover temperature under normal measurement conditions. These results imply that mass transport can be explained within the framework of photomechanical effects.

+H RH (5.9.2)

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In the oxidation of aromatic substances at the anode, radical cations or dications are formed as intermediates and subsequently react with the solvent or with anions of the base electrolyte. For example, depending on the conditions, 1,4-dimethoxybenzene is cyanized after the substitution of one methoxy group, methoxylated after addition of two methoxy groups or acetoxylated after substitution of one hydrogen on the aromatic ring, as shown in Fig. 5.55, where the solvent is indicated over the arrow and the base electrolyte and electrode under the arrow for each reaction; HAc denotes acetic acid. J. Heyrovsky and K. Holleck and B. Kastening pointed out that the reduction of aromatic nitrocompounds is characterized by a fast oneelectron step, e.g. NO2 (5.9.3) This reduction step can be readily observed at a mercury electrode in an aprotic solvent or even in aqueous medium at an electrode covered with a suitable surfactant. However, in the absence of a surface-active substance, nitrobenzene is reduced in aqueous media in a four-electron wave, as the first step (Eq. 5.9.3) is followed by fast electrochemical and chemical reactions yielding phenylhydroxylamine. At even more negative potentials phenylhydroxylamine is further reduced to aniline. The same process occurs at lead and zinc electrodes, where phenylhydroxylamine can even be oxidized to yield nitrobenzene again. At electrodes such as platinum, nickel or iron, where chemisorption bonds can be formed with the products of the

The formation of an SRG is typically monitored via the diffraction of a probe laser beam. One must be careful in analyzing this diffraction ef ciency, however, because a number of simultaneous gratings will be generated in an azo sample during illumination with a light pattern (Fig. 4.6a d). A light intensity pattern will lead to a chemical grating, since illuminated regions will be more cis rich than dark regions. The resultant spatial variation of absorbance and refractive index will lead to various optical effects, including diffraction. This grating is temporary,

96.1 30.4 9.61 3.04 0.96 0.30

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