pH-dependent helix folding dynamics of poly-glutamic acid

Poly-L-glutamic acid (PGA) is an ideal model system for investigating the transition between α-helical and random coil peptide conformations, since its secondary structure is highly sensitive not only to temperature, but also to pH. Laser pulse-induced temperature jumps were used to observe pH-dependent PGA helix-coil relaxation dynamics on the microsecond time scale. The relaxation was found to be non-exponential, particularly if only short helical segments are present before the temperature jump, indicating the multi-step nature of the process which involves helix nucleation and propagation. Helix-coil relaxation is slowest near the mid-point of the pH-induced helix-coil transition, in agreement with theoretical predictions.

Graphical abstractDownload full-size imageHighlights► The helical stability of poly-glutamic acid is sensitive to temperature and pH. ► Helix-coil dynamics were studied using nanosecond temperature jumps and IR detection. ► Dynamics are non-exponential, indicating the multi-step nature of the process. ► Dynamics are slowest near the mid-point of the pH-induced helix-coil transition. ► This agrees with theoretical predictions for cooperative transitions in polymers.