Temperature Controlled Loading and Release of the Anti-Inflammatory Drug Cannabidiol by Smart Microgels.

CBD is a promising candidate for treatment of many diseases and plays a major role in the growing trend to produce high-end drugs from natural, renewable resources. In the present work, we demonstrate a way to incorporate the anti-inflammatory drug CBD into smart microgel particles. The copolymer microgels that we chose as carrier systems exhibit a volume phase transition temperature of 39 ∘C, which is just above normal body temperature and makes them ideal candidates for hyperthermia treatment. While a simple loading route of CBD was not successful due to the enormous hydrophobicity of CBD, an alternative route was developed by immersing the microgels in ethanol. Despite the expected loss of thermoresponsive behaviour of the microgel matrix due to the solvent exchange, a temperature-dependent release of CBD was detected by the material, creating an interesting question of interactions between CBD and the microgel particles in ethanol. Furthermore, the method developed for loading of the microgel particles with CBD in ethanol was further improved by a subsequent transfer of the loaded particles into water, which proves to be an even more promising approach due to the successful temperature-dependent release of the drug above the collapse temperature of the microgels.

UV cross-linked smart microgel membranes as free-standing diffusion barriers and nanoparticle bearing catalytic films.

In this study we use poly(N-isopropylacrylamide) (PNIPAM) based copolymer microgels to create free-standing, transferable, thermoresponsive membranes. The microgels are synthesized by copolymerization of NIPAM with 2-hydroxy-4-(methacryloyloxy)-benzophenone (HMABP) and spin-coated on Si wafers. After subsequent cross-linking by UV-irradiation, the formed layers easily detach from the supporting material. We obtain free standing microgel membranes with lateral extensions of several millimetres and an average layer thickness of a few hundred nanometres. They can be transferred to other substrates. As one example for potential applications we investigate the temperature dependent ion transport through the membranes via resistance measurements revealing a sharp reversible increase in resistance when the lower critical solution temperature of the copolymer microgels is reached. In addition, prior to cross-linking, the microgels can be decorated with silver nanoparticles and cross-linked afterwards. Such free-standing nanoparticle hybrid membranes are then used as catalytic systems for the reduction of 4-nitrophenol, which is monitored by UV/Vis spectroscopy.

Tuning the Swelling Properties of Smart Multiresponsive Core-Shell Microgels by Copolymerization.

The present study focuses on the development of multiresponsive core-shell microgels and the manipulation of their swelling properties by copolymerization of different acrylamides-especially N-isopropylacrylamide (NIPAM), N-isopropylmethacrylamide (NIPMAM), and NNPAM-and acrylic acid. We use atomic force microscopy for the dry-state characterization of the microgel particles and photon correlation spectroscopy to investigate the swelling behavior at neutral (pH 7) and acidic (pH 4) conditions. A transition between an interpenetrating network structure for microgels with a pure poly-N,-n-propylacrylamide (PNNPAM) shell and a distinct core-shell morphology for microgels with a pure poly-N-isopropylmethacrylamide (PNIPMAM) shell is observable. The PNIPMAM molfraction of the shell also has an important influence on the particle rigidity because of the decreasing degree of interpenetration. Furthermore, the swelling behavior of the microgels is tunable by adjustment of the pH-value between a single-step volume phase transition and a linear swelling region at temperatures corresponding to the copolymer ratios of the shell. This flexibility makes the multiresponsive copolymer microgels interesting candidates for many applications, e.g., as membrane material with tunable permeability.

Improved Smart Microgel Carriers for Catalytic Silver Nanoparticles.

Acrylamide-based, thermoresponsive core-shell microgels with a linear phase transition region are used as improved carriers for catalytically active silver nanoparticles in the present study. In this context, we investigated the swelling behavior of the carriers and the stability of the silver nanoparticles inside the polymer network with photon correlation spectroscopy, transmission electron microscopy, and by following the surface plasmon resonance of the nanoparticles. Depending on the cross-linker content of the microgel core, we observed very good stability of the nanoparticles inside the microgel network, with nearly no bleeding or aggregation of the nanoparticles over several weeks for core cross-linker contents of 5 and 10 mol %. The architecture of the hybrid particles in the swollen state was investigated with cryogenic transmission electron microscopy. The particles exhibit a core-shell structure, with the silver nanoparticles located mainly at the interface between the core and shell. This architecture was not used before and seems to grant advanced stability to the nanoparticles inside the network in combination with good switchability of the catalytic activity. This was measured by following the reduction of 4-nitrophenole, which is a well-studied model reaction. The obtained Arrhenius plots show that similar to previous works, the swelling of the core and shell can influence the catalytic activity of the silver nanoparticles. As mentioned before, the cross-linker content of the core seems to be a very important parameter for the switchability of the catalytic activity. A higher cross-linker content of the core seems to be connected to a stronger influence of the carrier swelling degree on the catalytic activity of the silver nanoparticles.

Synthesis of smart dual-responsive microgels: correlation between applied surfactants and obtained particle morphology.

Thermo- and pH-responsive copolymer microgels were obtained by surfactant-assisted precipitation polymerization of N-isopropylacrylamide (NIPAM) and acrylic acid (AAc). The surfactants used were sodium dodecylsulfate (SDS), dodecyltrimethylammonium bromide (DTAB) and the nonionic n-octyl-ß-d-glucopyranoside (C8G1). We investigate the influence of the surfactants on the acrylic acid incorporation rate, the particle size, particle morphology, and the swelling behaviour at pH 4 and pH 7, at which AAc is neutral or charged, respectively. It is shown that each surfactant has a specific influence, which is connected to its role in the polymerization mechanism and its charge. A combined FTIR and PCS study reveals that the particles undergo a temperature-induced change in microstructure, even if the particle hydrodynamic radius does not change significantly.

Role of Anionic Surfactants in the Synthesis of Smart Microgels Based on Different Acrylamides.

We investigated the influence of two anionic surfactants, namely, sodium dodecyl sulfate and sodium decyl sulfate, on acrylamide-based microgels consisting of N-n-propylacrylamide. In this context, the main focus was on the influence of surfactant addition on the size of the microgels. The surfactant was added to the reaction mixture before or during the polymerization at different points in time. Microgels were characterized via photon correlation spectroscopy and atomic force microscopy. All results were compared to those for other more common acrylamide-based microgels consisting of N-isopropylacrylamide and N-isopropylmethacrylamide. A significant difference between the three microgels and a strong dependence on the surface activity of the surfactant was found.