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Above their cloud point, aqueous solutions of the thermoresponsive polymer poly( N -isopropylacrylamide) (PNIPAM) form large mesoglobules. We have carried out very small-angle neutron scattering (VSANS with q = 0.21-2.3 × 10 -3 Å -1 ) and Raman spectroscopy experiments on a 3 wt % PNIPAM solution in D 2 O at atmospheric and elevated pressures (up to 113 MPa). Raman spectroscopy reveals that, at high pressure, the polymer is less dehydrated upon crossing the cloud point. VSANS shows that the mesoglobules are significantly larger and contain more D 2 O than at atmospheric pressure. We conclude that the size of the mesoglobules and thus their growth process are closely related to the hydration state of PNIPAM.

The rate of molecular exchange in diblock copolymer micelles is strongly dependent on the chain length of the core-forming insoluble block. Less is known about the influence of the soluble block forming the micellar corona. In this study we present a time-resolved small angle neutron scattering (TR-SANS) study exploring systematically the effect of corona chain length on the dynamics of chain exchange. As a model system we have taken amphiphilic AB diblock copolymers of the type C 27 H 55 -poly(ethylene oxide) x (C 27 -PEO x ) with varying x between 4 and 36 kg/mol in aqueous solution in which well-defined spherical micelles with partially crystalline cores are formed. The TR-SANS results show that the chain exchange slows down considerably upon increasing PEO molecular weight, while the characteristic "attempt time" constant, τ 0 , was found to increase with a power law dependence τ 0 ∼ M PEO 9/5 . The results are in excellent agreement with the Halperin and Alexander model1 and can be attributed to a reduced diffusion rate through the micellar corona. Our results clearly demonstrate that the rate for molecular exchange is not directly coupled to the solubility of the amphiphile and the critical micellar concentration, as has previously been indicated.

Here we systematically study the equilibrium molecular exchange kinetics of a series of amphiphilic n -alkyl-poly(ethylene oxide) (C n -PEO) micelles containing partly crystallized cores. Using differential scanning calorimetry (DSC), we determined the melting transition and extracted the enthalpy of fusion, Δ H fus , of the n -alkyl chains inside the micellar core. Molecular exchange kinetics was measured below the melting point using a time-resolved small-angle neutron scattering technique (TR-SANS) based on mixing deuterated and proteated but otherwise identical micelles. Comparing both kinetic and thermodynamic data, we find that crystallinity within the micellar cores leads to significant enthalpic and the entropic contributions to the activation barrier for molecular exchange. While the former leads to an enhanced stability, the positive entropic gain favors the process. Interestingly, the entropic term contains an excess term beyond what is expected from the measured entropy of fusion. Based on calculations using the Rotational Isomeric State (RIS) model, we suggest that the excess entropy is due to the gain in conformational entropy upon releasing the chain from the confined state in the core. The study thus provides deep insight into the fundamental processes of micellar kinetics and which might be relevant also to other semicrystalline soft matter and biological systems including lipid membranes.