Helix–coil transition for poly(L‐glutamic acid) in water–ethanol solutions

Potentiometric 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.

[1]  H. Scheraga,et al.  The helix-coil transition of poly-L-lysine in methanol-water solvent mixtures. , 1968, Biopolymers.

[2]  A. Holtzer,et al.  The stability of the polyglutamic acid alpha helix. , 1968, Journal of the American Chemical Society.

[3]  D. Puett,et al.  Potentiometric titrations and the helix–coil transition of poly(L‐glutamic acid) and poly‐L‐lysine in aqueous salt solutions , 1968, Biopolymers.

[4]  D. Puett,et al.  Pseudo-phase diagrams of poly-L-lysine and poly(L-glutamic acid) in aqueous salt solutions. , 1968, Biopolymers.

[5]  S. N. Timasheff,et al.  Preferential binding of solvent components to proteins in mixed water--organic solvent systems. , 1968, Biochemistry.

[6]  J. T. Yang,et al.  Helix-coil transition of poly-L-ornithine in solution. , 1968, Biochemistry.

[7]  S. N. Timasheff,et al.  The interaction of beta-lactoglobulin with solvent components in mixed water-organic solvent systems. , 1968, Journal of the American Chemical Society.

[8]  C. Tanford,et al.  Intrinsic dissociation constants of aspartyl and glutamyl carboxyl groups. , 1967, The Journal of biological chemistry.

[9]  J. Hermans,et al.  Effect of binding on melting transitions in polymer–diluent systems , 1967 .

[10]  J. Hermans The Effect of Protein Denaturants on the Stability of the α Helix1 , 1966 .

[11]  J. Hermans Experimental free energy and enthalpy of formation of the alpha-helix. , 1966, The Journal of physical chemistry.

[12]  J. Cassim,et al.  The effects of solvent environment on the optical rotatory dispersion parameters of polypeptides. II. Studies on poly-L-glutamic acid. , 1965, Biophysical journal.

[13]  A. Holtzer,et al.  The Helix-Coil Transition in Solutions of Polyglutamic Acid , 1964 .

[14]  S. Rice,et al.  The helix-coil transition in charged macromolecules , 1960 .

[15]  W. Moffitt,et al.  THE OPTICAL ROTATORY DISPERSION OF SIMPLE POLYPEPTIDES. I. , 1956, Proceedings of the National Academy of Sciences of the United States of America.

[16]  G. Fasman [126] Optical rotatory dispersion , 1963 .

[17]  P. Doty,et al.  Optical rotation and the conformation of polypeptides and proteins. , 1961, Advances in protein chemistry.