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Can someone explain the concept of entropic traps, or provide good sources to look up? The term is not present in any chemistry books I own, and I cannot find online sources explaining it.

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  • $\begingroup$ Can you give some context of where you came across the term? $\endgroup$ – jerepierre Jan 27 '16 at 20:59
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I think this should address your query:

The separation of macromolecules such as polymers and DNA by means of electrophoresis, gel permeation chromatography or filtration exploits size-dependent differences in the time it takes for the molecules to migrate through a random porous network. Transport through the gel matrices, which usually consist of full swollen crosslinked polymers depends on the relative size of the macromolecule compared with the pore radius. Sufficiently small molecules are thought to adopt an approximately spherical conformation when diffusing through the gel matrix, whereas larger ones are forced to migrate in a snake-like fashion. Molecules of intermediate size, however, can get temporarily trapped in the largest pores of the matrix, where the molecule can extend and thus maximize its conformational entropy. This 'entropic trapping' is thought to increase the dependence of diffusion rate on molecular size. Here we report the direct experimental verification of this phenomenon. Bragg diffraction from a hydrogel containing a periodic array of monodisperse water voids confirms that polymers of different weights partition between the hydrogel matrix and the water voids according to the predictions of the entropic trapping theory. Our approach might also lead to the design of improved separation media based on entropic trapping. – Source

I don't know if you needed a textbook definition, but thought you'll get a more elaborate view from this.

This is a schematics of an entropic trap device(ref: Anal. Chem. 2002, 74, 394-401)

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  • $\begingroup$ So basically the energy of a molecule is lowered because the conformational entropy is maximized? In the case above, macromolecules are allowed to "extend" (i.e. stretch out, occupy a larger volume) in suitable pores, which then becomes a favoured state for the molecule ("trapped" in a local minima on its potential energy surface). But why is it trapped? Is the minima deep? Can it not easily escape? Could you explain how the entropic trapping works for chemiluminescence of 1,2-dioxetane? (see pubs.acs.org/doi/abs/10.1021/jp074063g) $\endgroup$ – Yoda Jan 27 '16 at 16:26

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