The internal structure of nanometric microgels in water has been studied as a function of temperature, crosslinker content, and level of deuteration. Small-angle neutron scattering from poly(N-isopropylmethacrylamide) (pNIPMAM, volume phase transition ≈ 44 °C) microgel particles of radius well below 100 nm in D2O has been measured. The intensities have been analyzed with a combination of polymer chain scattering and form-free radial monomer volume fraction profiles defined over spherical shells, taking polydispersity in size of the particles determined by AFM into account. A reverse Monte Carlo optimization using a limited number of parameters was developed to obtain smoothly decaying profiles in agreement with the experimentally scattered intensities. Result are compared to the swelling curve of microgel particles in the temperature range from 15 to 55 °C obtained from photon correlation spectroscopy (PCS). In addition to hydrodynamic radii measured by PCS, our analysis provides direct information about internal water content and gradients, the strongly varying steepness of the density profile at the particle-water interface, the total spatial extension of the particles, and the visibility of chains. The model has also been applied to a variation of the crosslinker content, N,N′-methylenebisacrylamide (BIS), from 5 to 15 mol%, providing insight in the impact of chain architecture and crosslinking on water uptake and on the definition of the polymer-water interface. The model can easily be generalized to arbitrary monomer contents and types, in particular mixtures of hydrogenated and deuterated species, paving the way to detailed studies of monomer distributions inside more complex microgels, in particular core-shell particles.
Colloidal aqueous microgels have attracted notable attention due to their possible applications in both polymer chemistry and the (bio)material sector. Due to their soft internal network structure and their response to different external stimuli, they are suitable as carrier systems for different kinds of molecules (e.g. nanoparticles, drugs, diagnostic agents, and enzymes), as optically active materials or even as model systems for fundamental research on soft condensed matter. Within the class of microgels, a variety of molecular structures is possible. The aim of this manuscript is to review recent progress in the domain of copolymer microgels with different architectures. Although most of the work is based on microgels with poly(N-isopropyl acrylamide) (NIPAM) as one component, non-NIPAM based copolymer systems are also presented and discussed.
Abstract:In this work, we compare the properties of smart homopolymer microgels based on N-n-propylacrylamide (NNPAM), N-isopropylacrylamide (NIPAM) and N-isopropylmethacrylamide (NIPMAM) synthesized under identical conditions. The particles are studied with respect to size, morphology, and swelling behavior using scanning electron and scanning force microscopy. In addition, light scattering techniques and fluorescent probes are employed to follow the swelling/de-swelling of the particles. Significant differences are found and discussed. Poly(N-n-propylacrylamide) (PNNPAM) microgels stand out due to their very sharp volume phase transition, whereas Poly(N-isopropylmethacrylamide) (PNIPMAM) particles are found to exhibit a more homogeneous network structure compared to the other two systems.
Stimuli responsive surface structures attract increasing attention due to a large variety of envisioned applications. The controlled organization of poly(N-isopropyl acrylamid), PNIPAM microgel particles at solid surfaces inspired numerous research activities. In this review article, we briefly discuss the swelling/deswelling properties of adsorbed microgel particles in comparison to the behavior in the bulk phase. The presence of the solid interface highly influences and changes their behavior with respect to the properties in solution. Furthermore, the confinement on a solid substrate allows the direct and in-situ investigation of the mechanical properties of the microgel particles. Additionally, we briefly review the research on microgel particles at liquid interfaces. At these interfaces new interesting effects occur. Moreover, we discuss some interesting work on potential applications. In this context, microgel particles are often used as an active component for responsive coatings of various functionality envisioning applications, e.g. in medicine, biotechnology, and nanooptics.Zusammenfassung: Responsive Oberflächenmaterialien finden aufgrund der damit verbundenen potentiellen technischen Anwendungsmöglichkeiten große Beachtung in der aktuellen Forschung. Die Möglichkeit, kolloidale Gelpartikel aus poly(N-Isopropylacrylamid), PNIPAM an festen Oberflächen kontrolliert anzuordnen, inspirierte vielfältige Forschungsakivitäten. In diesem Übersichtsartikel diskutieren wir das Quellverhalten adsorbierter Mikrogelpartikel im Vergleich zu
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