0000000000236464
AUTHOR
Adrien Lerbret
Experimental design approach in the synthesis of molecularly imprinted polymers specific for iprodione fungicide
International audience; An experimental design (ED) approach was applied to study the weight of three factors in the synthesis of a molecularly imprinted polymer (MIP) specific for iprodione fungicide. The objective was to obtain a high specific polymer with the best performance of iprodione binding. Thirteen iprodione-imprinted polymers and 13 non-imprinted polymers (NIP) were synthesized according to ED having 3 influencing factors: the polymerization method, the crosslinker nature and the functional monomer type. For each factor, two levels were studied: bulk and precipitation polymerization for the first factor, trimethylolpropane trimethacrylate (TRIM) and ethylene glycol dimethacrylat…
Controlled loading and release of beta-lactoglobulin in calcium-polygalacturonate hydrogels
International audience; We show here how the structure of polygalacturonate (polyGalA) hydrogels cross-linked by Ca2+ cations via external gelation controls the loading and the release rate of betalactoglobulin (BLG), a globular protein. Hydrogels prepared from a polyGalA/BLG solution are found similar to those obtained from a polyGalA solution in our previous study (Maire du Poset, et al. Biomacromolecules 2019, 20(7), 2864-2872): they exhibit similar transparencies and gradients of mechanical properties and polyGalA concentration. The nominal BLG/polyGalA ratio of the mixtures is almost recovered within the whole mixed hydrogel despite such strong concentration gradients, except in the pa…
Tuning the Structure of Galacturonate Hydrogels: External Gelation by Ca, Zn, or Fe Cationic Cross-Linkers
International audience; We show here how the nature of various divalent cations M2+ (Ca2+, Zn2+, or Fe2+) influences the structure and mechanical properties of ionotropic polygalacturonate (polyGal) hydrogels designed by the diffusion of cations along one direction (external gelation). All hydrogels exhibit strong gradients of polyGal and cation concentrations, which are similar for all studied cations with a constant ratio R = [M2+]/[Gal] equal to 0.25, showing that every M2+ cation interacts with four galacturonate (Gal) units all along the gels. The regions of the hydrogels formed in the early stages of the gelation process are also similar for all cations and are homogeneous, with the s…
Structural behaviour differences in low methoxy pectin solutions in the presence of divalent cations (Ca 2+ and Zn 2+ ): a process driven by the binding mechanism of the cation with the galacturonate unit
International audience; In this paper, we compare the interactions between low methoxy pectin (LMP) and either Ca2+ or Zn2+ in semi-dilute solutions. Intrinsic viscosity and turbidity measurements reveal that pectin-calcium solutions are more viscous, but yet less turbid, than pectin-zinc ones. To get a molecular understanding on the origin of this rather unexpected behavior, we further performed isothermal titration calorimetry, small angle neutron scattering experiments, as well as molecular dynamics simulations. Our results suggest that calcium cations induce the formation of a more homogeneous network of pectin than zinc cations do. The molecular dynamics simulations indicate that this …
Binding characteristics of molecularly imprinted polymers based on fungicides in hydroalcoholic media
An iprodione-imprinted polymer was prepared by copolymerization of methacrylamide and ethylene glycol dimethacrylate using a noncovalent imprinting approach. Methacrylamide was chosen using molecular dynamics simulations. To concentrate iprodione from hydro-alcoholic solutions, batch sorption of iprodione on the imprinted polymer were conducted. The equilibrium time for iprodione sorption is 20 min, and the corresponding kinetic mechanism follows the pseudo-second order indicating a strong interaction between iprodione and the imprinted polymer. Langmuir, Freundlich, and Dubinin-Radushkevich models were used to fit the isotherm of iprodione sorption. The imprinted polymer was found to be mo…
How Accurate Is the Egg-Box Model in Describing the Binding of Calcium to Polygalacturonate? A Molecular Dynamics Simulation Study
We performed molecular dynamics (MD) simulations of octameric galacturonate, GalA8, chains in the presence of Ca2+ in a ratio of R = [Ca2+]/[GalA] = 0.25 in order to determine to which extent the popular "egg-box model" (EBM) is able to describe the association between Ca2+ cations and polygalacturonate (polyGalA) chains. To this aim, we slig h t l y revised the empirical parameters for the interaction between Ca2+ and the carboxylate oxygen atoms of GalA units so as to reproduce the experimental Ca2+-GalA association constant. We also defined an ad hoc order parameter, referred to as the egg-box score (EBS), that quantifies any deviation of the local coordination geometry of calcium cation…