Abstract

AbstractPotentiometric titrations and some complementary optical rotation data are presented for solutions of poly(L‐ glutamic acid) (PGA) in several H2O–ethanol mixtures. The data allow the determination of the intrinsic pK (pK0), slope of the apparent. pK (pKapp), versus degree of ionization curves and of the enthalpy of ionization as a function of ethanol concentration. The variation of the degree of ionization at which the helix–coil transformation occurs with ethanol and temperature is also determined. Finally free energy, enthalpy, and intropy changes associated with the helix–coil transformation for the uncharged conformers are determined from the titration curves. The effect of the ethanol is to increase the stability of the helical conformation of PGA for both the charged and the uncharged forms of the polymer. The stabilization of the uncharged helix is essentially an entropic effect.

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