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College Park, Maryland      June 6 - 10 , 2004

M4-D1 (3:45 PM): Counterion undressing from flexible polyelectrolytes (Invited)

V. M. Prabhu , E.J. Amis (NIST Polymer Division), D. Bossev, N. Rosov (NIST Center for Neutron Research)

At low ionic strength, organic counterions dress a flexible charged polymer as measured directly by small-angle neutron scattering (SANS) and neutron spin-echo (NSE) spectroscopy. This dressed state, quantified by the concentration dependence of the static correlation length, illustrates the polymer-counterion coupled nature on the nanometer length scale. The counterions, made visible by selective hydrogen and deuterium labeling, undress from the polymeric template by addition of sodium chloride. The addition of this electrolyte leads to two effects; increased Debye electrostatic screening and decoupled counterion–polymer correlations. Neutron spin echo spectroscopy measures a slowing–down of the effective diffusion coefficient of the labeled counterions at the length scale of 8 nm, the static correlation length, indicating the nanosecond counterion dynamics mimics the polymer. These experiments, performed with semidilute solutions of tetramethylammonium poly(styrene sulfonate) [(h–TMA+) d–PSS], apply to relevant biopolymers including single and double stranded DNA and unfolded proteins, which undergo orchestrated dynamics of counterions and chain segments to fold, unfold and assemble.

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