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In order to better understand the collapse of polyions in poor solventconditions the effective charge and the solvent quality of the hypotheticallyuncharged polymer backbone need to be known. In the present work this isachieved by utilizing poly-2-vinylpyridine quaternized to 4.3% withethylbromide. Conductivity and light scattering measurements were utilized tostudy the polyion collapse in isorefractive solvent/non-solvent mixturesconsisting of 1-propanol and 2-pentanone, respectively, at nearly constantdielectric constant. The solvent quality of the uncharged polyion could bequantified which, for the first time, allowed the experimental investigation ofthe effect of the electrostatic interaction prior and during polyion collapse,by comparing to a newly developed theory. Although the Manning parameter forthe investigated system is as low as $l_B/l = 0.6$ ($l_B$ the Bjerrum lengthand $l$ the mean contour distance between two charges), i.e. no counterionbinding should occur, a qualitative interpretation of the conductivity datarevealed that the polyion chain already collects its counter ions when thedimensions start to shrink below the good solvent limit but are still wellabove the $\theta$-dimension.

The collapse of linear polyelectrolyte chains in a poor solvent: When does a collapsing polyelectrolyte collect its counter ions?