Abstract:The development of molecularly imprinted polymers (MIPs) to target polyphenols present in vegetable extracts was here addressed. Polydatin was selected as a template polyphenol due to its relatively high size and amphiphilic character. Different MIPs were synthesized to explore preferential interactions between the functional monomers and the template molecule. The effect of solvent polarity on the molecular imprinting efficiency, namely owing to hydrophobic interactions, was also assessed. Precipitation and suspension polymerization were examined as a possible way to change MIPs morphology and performance. Solid phase extraction and batch/continuous sorption processes were used to evaluate the polyphenols uptake/release in individual/competitive assays. Among the prepared MIPs, a suspension polymerization synthesized material, with 4-vinylpyridine as the functional monomer and water/methanol as solvent, showed a superior performance. The underlying cause of such a significant outcome is the likely surface imprinting process caused by the amphiphilic properties of polydatin. The uptake and subsequent selective release of polyphenols present in natural extracts was successfully demonstrated, considering a red wine solution as a case study. However, hydrophilic/hydrophobic interactions are inevitable (especially with complex natural extracts) and the tuning of the polarity of the solvents is an important issue for the isolation of the different polyphenols.
Surface molecularly imprinted cellulose‐synthetic hybrid particles are prepared via atom transfer radical polymerization (ATRP). The two‐step process involves the immobilization of α‐bromoisobutyryl bromide in the pristine microcrystalline cellulose, to generate ATRP macroinitiator particles, and then the creation of a crosslinked‐imprinted shell in the particles surface considering ATRP of 4‐vinylpyridine (4VP) and ethylene glycoldimethacrylate (EGDMA) with quercetin as imprinting template. Among the polymerization recipes tested, a system with ethanol as solvent preserves a final size of the hybrid particles suitable for application as adsorbent, while also incorporating the 4VP/EGDMA co‐monomers. Testing of imprinted/non‐imprinted particles for sorption/desorption of standard phenolic compounds shows the modification of the surface of the pristine cellulose and also the achievement of molecular imprinting (imprinting factor ≈2.6). Particles are used for the enrichment of flavonoids in olive leaf extracts and the special features of the developed molecularly imprinted adsorbents are again highlighted with this complex mixture of phenolic compounds. It is shown that production of fractions rich in luteolin‐7‐O‐glucoside, apigenin‐7‐O‐glucoside, or quercetin, among other flavonoids is possible (estimated enrichment factors up to 4). These results point up for the usefulness of natural‐synthetic materials with processes to get high‐added value compounds in the framework of circular bio‐economy.
A simple adsorption process allowing a high retention of polyphenols contained in extracts of onion skin with ethanol/water volume ratio going up to 80/20 is described. We show that the straightforward processing of the extracts is possible, even at low water content, by using quercetin-molecularly imprinted (Q-MIP) adsorbents synthesized with 4-vinylpyridine (4VP) as the functional monomer. The favorable interactions between the pyridyl functional groups of 4VP and the polyphenols, as well as the improved binding site accessibility introduced by molecular imprinting, are at the source for the good performance observed with the Q-MIPs. The usefulness of the Q-MIPs in onion skin polyphenols purification, fractionation and concentration is demonstrated with few sorption/desorption steps and considering sonicated, Soxhlet and supercritical CO 2 extracts. Polyphenol retention of c.a. 88% is possible with Q-MIPs (7% with non-tailored adsorbents) when directly processing ethanol/water 80/20 extracts. Protocatechuic acid and other very hydrophilic molecules (such as simple sugars) were readily removed from the extracts, leaving fractions containing mostly quercetin and quercetin derivatives. Polyphenol recovery higher than 90% (measured with quercetin) and concentration factors up to 34 times were observed with the Q-MIPs.
A kinetic model describing aqueous acrylamide homopolymerization and copolymerization of acrylamide with methylene bisacrylamide, leading to hydrogel formation, is presented and applied in the simulation of these reaction processes. This modeling approach is based on population balances of generating functions and, besides the crosslinking mechanisms inherent to network formation, other specific kinetic steps important in acrylamide polymerization (e.g., branching due to backbiting) are considered in the simulation tool developed. The synthesis of acrylamide polymers and hydrogels was performed at 26 °C and at 40 °C using two different initiation systems. The formation of such materials was monitored using in-line static light scattering (SLS), and the spatial inhomogeneity of the final hydrogels was also measured using this experimental technique. It is shown that the simulations are helpful in describing information provided by SLS in-line monitoring, namely in the early stages of polymerization with the transition from dilute to semi-dilute regime. Indeed, it finds a plausible match between the critical overlap polymer concentration and gelation, this later leading to the observed spatial heterogeneity of the hydrogels. Usefulness of the kinetic model for defining operation conditions (initial composition, semi-batch feed policies, chain transfer, etc.) in making the shift from gelation to the semi-dilute regime is discussed, and the extension of this approach to processes enabling a higher control of gelation (e.g., controlled radical polymerization) is also prospected.
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