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The main goal of this chapter is to describe the theories used to analyze the data from such electrophoretic sieving experiments . However, there arc other ways , at least in principle, to achieve separation. For instance, one can modify the friction coefficient of the DNA without changing its total charge (or vice-versa) such that the ratio force/friction in Eq. 32 2 Electrophoresis Theories (13 ) becomes mole cular s ize dependen t even in free solution. Such schemes have been sug gested [44 -4 8] but publi shed result s appea r to be rather modest at this time (for late st developments, see Ch apter 13).

In situations where a gel or a polymer solution is used to sieve the analytes, the concentration of this matrix may fluctuate along the migration path d~e to the preparation steps or local temperature gradients (indeed, one may wonder if the polymer concentration remains uniform if the capillary is bent or coiled). Wall coatings may be inhomogeneous and the DNA molecules may thus interact with certain wall defects. These, as well as other inhomogeneities, have been studied both experimentally and theoretically.

Recently, our group has started the development of a new siev ing model for hard particles [56-59]. We have shown that the Ogston model is actually a mean field model that replaces the matrix by an effective, structureless matrix; the reduced mobility is then indeed related to the fractional available volume [57]. Our new model allows for exact zero-field mobilities to be calculated for a variety of gel structures. An important conclusion of this work is that Eq . (17) must be replaced by the polynomial expansion 11* == 1 + I, PJR.

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