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Yes - Details unavailable at print time across physical hosts- Sun Cluster and Veritas Cluster Server Yes - across physical hosts

Of the four electrokinetic phenomena, two (electroosmotic flow and the streaming potential) fall into the region of membrane phenomena and will thus be considered in 6. This section will deal with the electrophoresis and sedimentation potentials. If the electric field E is applied to a system of colloidal particles in a closed cuvette where no streaming of the liquid can occur, the particles will move with velocity v. This phenomenon is termed electrophoresis. The force acting on a spherical colloidal particle with radius r in the electric field E is 4^rerE02 (for simplicity, the potential in the diffuse electric layer is identified with the electrokinetic potential). The resistance of the medium is given by the Stokes equation (2.6.2) and equals 6jrr/rv. At a steady state of motion these two forces are equal and, to a first approximation, the electrophoretic mobility v/E is

The ring substitution pattern affects both the trans and the cis absorption spectra, and for certain patterns, the absorption spectra of the two isomers overlap signi cantly (notably for the pseudo-stilbenes) In these cases, a single wavelength of light effectuates both the forward and reverse reaction, leading to a mixed stationary state and continual interconversion of the molecules For some interesting azobenzene photomotions, this rapid and ef cient cycling of chromophores is advantageous, whereas in cases where the azo chromophore is used as a switch, it is clearly undesirable The mechanism of isomerization has undergone considerable debate Isomerization takes place either through a rotation about the N N bond, with rupture of the p bond, or through inversion, with a semilinear and hybrizidized transition state, where the p bond remains intact (refer to Fig 14).

In closer approximations, correction must be made for conductivity effects (relaxation and electrophoretic) and for the real shape of the particles. Thus, the velocity of electrophoretic motion depends on the composition of the

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The thermal backrelaxation is agreed to be via rotation, whereas for the photochemical isomerization, both mechanisms appear viable (Xie et al, 1993) Historically, the rotation mechanism (as necessarily occurs in stilbene) was favored for photoisomerization, with some early hints that inversion may be contributing (Gegiou et al, 1968) More recent experiments, based on matrix or molecular constraints to the azobenzene isomerization, strongly support inversion (Altomare et al, 1997; Liu et al, 1992; Naito et al, 1991; Rau and Lueddecke, 1982) Studies using picosecond Raman and femtosecond uorescence show a double bond (N=N) in the excited state, con rming the inversion mechanism (Fujino et al, 2001; Fujino.

solution, on the properties of the surface of the particles and also on the charge of the particles themselves. If ampholytic particles are involved, then it also depends markedly on the pH, as the particles obtain a charge through dissociation that is dependent on the pH. This fact was utilized by A. Tiselius to develop an electrophoretic method that is especially useful for proteins. At a given pH various proteins are ionized to a different degree and also have different mobilities. The original single sharp boundary between a solution of a protein mixture in a suitable buffer and the pure buffer separates into several boundaries in an electric field, corresponding to differently mobile components. Thus electrophoresis permits analysis of a mixture of proteins without destructive chemical reactions. The experimental methods for determining the boundary position in either classical or free electrophoresis are the same as in the study of diffusion (see Section 2.5.5). In addition, electrophoresis can be carried out by saturating a suitable porous carrier, e.g. filter paper, with a pure buffer and applying the studied solution as spots or bands. The evaluation methods are analogous to those used in paper chromatography. Electrophoresis can be used preparatively to separate the components of a mixture, to concentrate fine suspensions in solution, etc. A further electrokinetic phenomenon is the inverse of the former according to the Le Chatelier-Brown principle: if motion occurs under the influence of an electric field, then an electric field must be formed by motion (in the presence of an electrokinetic potential). During the motion of particles bearing an electrical double layer in an electrolyte solution (e.g. as a result of a gravitational or centrifugal field), a potential difference is formed between the top and the bottom of the solution, called the