First events in the coil-to-globule transition of PVME in water: An ultrafast temperature jump - time-resolved...

The coil-to-globule transition is an essential phenomenon in protein and polymer solutions. Late stages of such transitions, >1 µs, have been thoroughly studied. Yet, the initial ones are a matter of speculations. Here, we present the first observation of a sub-nanosecond stage of the coil-to-globule transition of poly (vinyl methyl ether), PVME, in water.

The detection of an early stage of the coil-to-globule transition has been possible thanks to a novel experimental approach - time-resolved elastic light scattering study, following an ultrafast temperature jump. We identified a molecular process active in the observed stage of the transition with use of broadband dielectric spectroscopy.

In the experiment's time window, from a few ps to around 600 ps, we observed an increase in the light scattering intensity 300-400 ps after the temperature jump that heated the sample above its lower critical solution temperature (LCST). The observed time coincides with the time of segmental relaxation of PVME, determined by broadband dielectric spectroscopy in the temperature range of the LCST of the PVME/water mixture. This coincidence strongly suggests that the observed herein stage of coil-to-globule transition is the rapid formation of local nuclei along the polymer chain. Those nuclei may grow and aggregate in later stages of the process, which are out of our experimental time window.