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A series of well-defined hydrophilic and hydrophobic polyelectrolytes of various chain lengths and effective charge fractions have been adsorbed onto oppositely charged solid surfaces immersed in aqueous solutions. \emph{In situ} high energy X-ray reflectivity has provided the thickness , the electron density and the roughness of the adsorbed layer in its aqueous environment. In the case of hydrophobic polyelectrolytes, we have found , in agreement with a pearl-necklace conformation for the chains induced by a Rayleigh-like instability.

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