Coil-to-globule transition and dynamics of inhomogeneities in aqueous solutions of graft copolymers of NIPAM with different content of oligolactide groups were studied using spin probe continuous wave EPR spectroscopy. The technique of the suppressing of TEMPO as spin probe by spin exchange with Cu2+ ions was applied. This approach allowed us to detect individual EPR spectra of the probe in collapsed globules and estimate its magnetic and dynamic parameters reliably. The formation of inhomogeneities at temperatures lower than the volume phase transition temperature measured via transmission, and differential scanning calorimetry was fixed. An increase in oligolactide content in copolymers leads to the formation of looser globules, allowing for the exchange of the probe molecules between the globules and the external solution.
Keywords: coil-to-globule; electron paramagnetic resonance; inhomogeneities; nitroxides; spin probe; thermoresponsive polymers.