Irina Zgura

One-Pot Enzymatic Production of Lignin-Composites

A novel and efficient one-pot system for green production of artificial lignin bio-composites has been developed. Monolignols such as sinapyl (SA) and coniferyl (CA) alcohols were linked together with caffeic acid (CafAc) affording a polymeric network similar with natural lignin. The interaction of the dissolved SA/CA with CafAc already bound on a solid support (SC2/SC6-CafAc) allowed the attachment of the polymeric product direct on the support surface (SC2/SC6-CafAc-L1 and SC2/SC6-CafAc-L2, from CA and SA, respectively). Accordingly, this procedure offers the advantage of a simultaneous polymer production and deposition. Chemically, oxi-copolymerization of phenolic derivatives (SA/CA and CAfAc) was performed with H2O2 as oxidation reagent using peroxidase enzyme (2-1B mutant of versatile peroxidase from Pleurotus eryngii) as catalyst. The system performance reached a maximum of conversion for SA and CA of 71.1 and 49.8%, respectively. The conversion is affected by the system polarity as resulted from the addition of a co-solvent (e.g., MeOH, EtOH, or THF). The chemical structure, morphology, and properties of the bio-composites surface were investigated using different techniques, e.g., FTIR, TPD-NH3, TGA, contact angle, and SEM. Thus, it was demonstrated that the SA monolignol favored bio-composites with a dense polymeric surface, high acidity, and low hydrophobicity, while CA allowed the production of thinner polymeric layers with high hydrophobicity.

Layered materials of LDH-type containing Zn ions: Dielectric measurements show rotational fluctuations of water molecules

Layered double hydroxide (LDH) materials containing Zn ions were studied by broadband dielectric spectroscopy to follow up rotational molecular dynamics of confined water. One main relaxation process was observed in the experimental window; it was assigned to fluctuations of water molecules forming a strongly adsorbed thin layer upon the oxide surface. The temperature dependence of the relaxation rates has an unusual shape characterized by the presence of a maximum. Despite the characteristic parameters, this non-monotonous dependence is shown to be a rather general feature for water confined to LDHs.