Reduction-responsive molecularly imprinted nanogels for drug delivery applications.

Degradable molecularly imprinted polymers (MIPs) with affinity for S-propranolol were prepared by the copolymerization of methacrylic acid as functional monomer and a disulfide-containing cross-linker, bis(2-methacryloyloxyethyl)disulfide (DSDMA), using bulk polymerization or high dilution polymerization for nanogels synthesis. The specificity and the selectivity of DSDMA-based molecularly imprinted polymers toward S-propranolol were studied in batch binding experiments, and their binding properties were compared to a traditional ethylene glycol dimethacrylate (EDMA)-based MIP. Nanosized MIPs prepared with DSDMA as crosslinker could be degraded into lower molecular weight linear polymers by cleaving the disulfide bonds and thus reversing cross-linking using different reducing agents (NaBH4, DTT, GSH). Turbidity, viscosity, polymer size and IR-spectra were measured to study the polymer degradation. The loss of specific recognition and binding capacity of S-propranolol was also observed after MIP degradation. This phenomenon was applied to modulate the release properties of the MIP. In presence of GSH at its intracellular concentration, the S-propranolol release was higher, showing that these materials could potentially be applied as intracellular controlled drug delivery system.

Valorisation of grape pomace by the extraction of phenolic antioxidants: Application of high voltage electrical discharges.

The aim of this study was to optimise the electrically assisted extraction in order to obtain grape pomace extracts with high polyphenols content, which would be potentially interesting for applications as natural antioxidants. High voltage electrical discharges (HVED) were applied for intensification of the extraction. The effects of the energy input, the electrodes distance gap and the liquid-to-solid ratio were studied. Diffusion was then carried out in different mixtures of water and ethanol for one hour at 20, 30, 40 and 60°C. The most efficient extraction was (i) an HVED pre-treatment at 80kJ/kg with an electrodes distance of 5mm in a liquid-to-solid ratio of 5 followed by (ii) a diffusion with 30% ethanol in water at 60°C for 30min. The highest total polyphenols content reached 2.8±0.4gGAE/100gDM with a corresponding antioxidant activity of 66.8±3.1gTEAC/kgDM. The polyphenols extraction rate increased with temperature in accordance to an Arrhenius type of relationship: activation energy of 21.5±1.1kJ/mol for HVED treated systems against 0.5±0.2kJ/mol for untreated ones.