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Perhaps of a range as wide as the interesting phenomena displayed by azo aromatic compounds is the variety of molecular systems into which these chromophores can be incorporated. In addition to LC media and amorphous glasses, azobenzenes can be incorporated into self-assembled monolayers and superlattices, sol gel silica glasses, and various biomaterials. The photochromic or photoswitchable nature of azobenzenes can also be used to control the properties of novel small molecules, using an attached aromatic azo group. A review will be presented here of the photochemical and photophysical nature of chromophores in host polymers, the geometric and orientational consequences of this isomerization, and some of the interesting ways in which these phenomena have been expolited recently to exert control over solution and biochemical properties using light. This photoisomerization can be exploited as a photoswitch to orient the chromophore (which induces birefringence), or even to perform all-optical surface topography patterning. These photomotions enable many interesting applications, ranging from optical components and lithography to sensors and smart materials.

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5.5.3 Periodic methods 5.5.4 Coulometry 5.5.5 Electrode materials and surface treatment 5.5.6 Non-electrochemical methods 5.6 Chemical Reactions in Electrode Processes 5.6.1 Classification 5.6.2 Equilibrium of chemical reactions 5.6.3 Chemical volume reactions 5.6.4 Surface reactions 5.7 Adsorption and Electrode Processes 5.7.1 Electrocatalysis 5.7.2 Inhibition of electrode processes 5.8 Deposition and Oxidation of Metals 5.8.1 Deposition of a metal on a foreign substrate 5.8.2 Electrocrystallization on an identical metal substrate 5.8.3 Anodic oxidation of metals 5.8.4 Mixed potentials and corrosion phenomena 5.9 Organic Electrochemistry 5.10 Photoelectrochemistry 5.10.1 Classification of photoelectrochemical phenomena 5.10.2 Electrochemical photoemission 5.10.3 Homogeneous photoredox reactions and photogalvanic effects 5.10.4 Semiconductor photoelectrochemistry and photovoltaic effects 5.10.5 Sensitization of semiconductor electrodes 5.10.6 Photoelectrochemical solar energy conversion

157 157 158

301 303 305 328 344 345 346 347 350 352 352 361 368 369 372 377 381 384 390 390 392 393 397 403 406

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In this text, as in most on the subject, we use azobenzene and azo in a general way: to refer to the class of compounds that exhibit the core azobenzene structure, with different ring substitution patterns (even though, strictly, these compounds should be referred to as diazenes ) There are many properties common to nearly all azobenzene molecules The most obvious is the strong electronic absorption of the conjugated p system The absorption spectrum can be tailored, via the ring substitution pattern, to lie anywhere from the UV to the visible red region It is not surprising that azobenzenes were originally used as dyes and colorants, and up to 70% of the world s commercial dyes are still azobenzene-based (Zollinger, 1987, 1961).

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6 Membrane Electrochemistry and Bioelectrochemistry . . 410 6.1 Basic Concepts and Definitions 410 6.1.1 Classification of membranes 411 6.1.2 Membrane potentials 411 6.2 Ion-exchanger Membranes 415 6.2.1 Classification of porous membranes 415 6.2.2 The potential of ion-exchanger membranes 417 6.2.3 Transport through a fine-pore membrane 419 6.3 Ion-selective Electrodes 425 6.3.1 Liquid-membrane ion-selective electrodes 425 6.3.2 Ion-selective electrodes with fixed ion-exchanger sites . . . . 428 6.3.3 Calibration of ion-selective electrodes 431 6.3.4 Biosensors and other composite systems 431 6.4 Biological Membranes 433 6.4.1 Composition of biological membranes 434 6.4.2 The structure of biological membranes 438 6.4.3 Experimental models of biological membranes 439 6.4.4 Membrane transport 442 6.5 Examples of Biological Membrane Processes 454

The geometrically rigid structure and large aspect ratio of azobenzene molecules make them ideal mesogens: azobenzene small molecules and polymers functionalized with azobenzene can exhibit LC phases (Mohlmann and van der Vorst, 1989; Kwolek et al, 1985) The most startling and intriguing characteristic of the azobenzenes is their highly ef cient and fully reversible photoisomerization Azobenzenes have two stable isomeric states, a thermally stable trans con guration and a metastable cis form Remarkably, the azo chromophore can interconvert between these isomers upon absorption of a photon For most azobenzenes, the molecule can be optically isomerized from trans to cis with light anywhere within the broad absorption band, and the molecule will subsequently thermally relax back to the trans state on a timescale dictated by the substitution pattern This clean photochemistry is central to azobenzene s potential use as a tool for nanopatterning.

6.5.1 6.5.2

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Azobenzenes can be separated into three spectroscopic classes, well described by Rau (1990): azobenzene-type molecules, aminoazobenzene-type molecules, and pseudo-stilbenes (refer to Fig 11 for examples) The particulars of their absorption spectra (shown in Fig 12) give rise to their prominent colors: yellow, orange, and red, respectively Many azos exhibit absorption characteristics similar to the unsubstituted azobenzene archetype These molecules exhibit.

Processes in the cells of excitable tissues Membrane principles of bioenergetics Recalculation Formulae for Concentrations and Activity Coefficients List of Symbols

NO2 (a) (b) (c)

454 464

160 161 163

473 474 477

Figure 1.1. Examples of azomolecules classi ed as (a) azobenzenes, (b) aminoazobenzenes, and (c) pseudo-stilbenes.

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