The effect of deuteration on the volume phase transition (VPT) temperature of poly (N-isopropylmethacrylamide) (pNIPMAM) microgels in aqueous suspension is determined via IR spectroscopy and size measurements by photon correlation spectroscopy (PCS). We study the effect of a hydrogenated and a deuterated solvent (H2O/D2O), and of the hydrogenated and (partially) deuterated monomer. Deuteration of the monomer or copolymerization with deuterated monomers shifts the volume phase transition temperature (VPTT) by up to 8.4 K to higher temperatures, in good agreement with known results for pNIPAM microgels. Moreover, the shape of the swelling curve is found to depend on deuteration, with the highest deuteration leading to the sharpest VPT. Finally, the quantitative agreement between FTIR spectroscopy and PCS evidences the spatial homogeneity of the microgel particles. Our results are rationalized in terms of the effect of deuteration on hydrogen bonding. They shall be of primary importance for any experimental measurements close to the VPT involving isotopic substitution, and in particular contrast variation small angle neutron scattering.
26 December 2023 in Physical Chemistry Chemical Physics
The formation and properties of smart (stimuli-responsive) membranes are reviewed, with a special focus on temperature and pH triggering of gating to water, ions, polymers, nanoparticles, or other molecules of interest. The review is organized in two parts, starting with all-smart membranes based on intrinsically smart materials, in particular of the poly(N-isopropylacrylamide) family and similar polymers. The key steps of membrane fabrication are discussed, namely the deposition into thin films, functionalization of pores, and the secondary crosslinking of pre-existing microgel particles into membranes. The latter may be free-standing and do not necessitate the presence of a porous support layer. The temperature-dependent swelling properties of polymers provide a means of controlling the size of pores, and thus size-sensitive gating. Throughout the review, we highlight “positive” (gates open) or “negative” (closed) gating effects with respect to increasing temperature. In the second part, the functionalization of porous organic or inorganic membranes of various origins by either microgel particles or linear polymer brushes is discussed. In this case, the key steps are the adsorption or grafting mechanisms. Finally, whenever provided by the authors, the suitability of smart gating membranes for specific applications is highlighted.
11 January 2011 in The Journal of Physical Chemistry B