Laccases are oxidases that only require O 2 as a terminal oxidant. Thus, they provide an attractive green alternative to established alcohol oxidation protocols. However, laccases typically require catalytic amounts of mediator molecules to serve as electron shuttles between the enzyme and desired substrate. Consequently, laccase-mediator systems are defined by a multitude of parameters such as, e. g., the choice of laccase and mediator, the respective concentrations, pH, and the oxygen source. This complexity and a perceived lack of comparable data through-out literature represent an entry burden into this field. To provide a solid starting point, particularly for organic chemists, we herein provide a time-resolved, quantitative laccase and mediator screening based on the oxidation of anis alcohol as model reaction. We measured the redox potentials of mediators under the reaction conditions to relate them to their performance. Lastly, for particularly efficient laccase-mediator pairs, we screened important reaction parameters, resulting in an optimized setup for mediator-assisted laccase catalyzed oxidations.

The processing of polysaccharide-based polymer compounds represents a major challenge because these materials behave considerably different compared to their petro-based counterparts. Especially in the manufacture of thermoplastic starch (TPS)-polyester films by means of blown film extrusion, an increase in the natural material proportion generally leads to processing difficulties. In addition, higher TPS contents adversely affect mechanical material characteristics. The present study focuses on the effect of malic acid (MA) on processing parameters and on the quality of TPS/poly(butylene adipate-co-terephthalate) films. The MA enantiomers D(1) and L(-) as well as the racemate were applied at various concentrations (0.2, 0.4, and 0.8 wt %). Results indicate that the addition of racemic MA at concentrations of 0.2% and 0.4% significantly improved the processibility of TPS. Simultaneously, positive effects such as improved ductility and water sorption characteristics were found.

This article describes the effect of processing on the properties and morphology of thermoplastic starch (TPS) and poly(butylene adipate‐co‐terephthalate) (PBAT) blends and films with high starch content. Different process parameters were modified during compounding of blends and extrusion of blown films. Morphology was examined through scanning electron microscopy. Mechanical and optical characterization of films was carried out as well. Decreasing specific throughput during compounding led to an increase in strain at break of the blends from 66 to 497%. The tensile strength increased from 6 to 22 MPa as well. The highest elastic modulus and tear resistance were achieved at intermediate specific throughputs, whereas the maximum TPS particle size and the lowest color difference were obtained at high specific throughputs. A decrease of color difference from 6.4 to 2.2 was observed by reducing the temperature profile in 5 °C. In the case of blown film extrusion, increasing the temperature profile resulted in a reduction of color difference of the films from 7.9 to 4.2. In addition, tensile strength and strain at break slightly increased. Color difference decreased with decreasing screw speed as well. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019, 136, 47990.

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A novel strategy for improving wet resistance and bonding properties of starch-based adhesives using enzymatically polymerized lignosulfonates and carboxylic acids as additives was developed. Therefore, lignosulfonates were polymerized by laccase to a molecular weight of 750 kDa. Incorporation of low concentrations (up to 1% of the starch weight) of 1,2,3,4-butanetetracarboxylic acid (BTCA) led to further improvement on the properties of the adhesives, while addition of greater amounts of BTCA led to a decrease in the properties measured due to large viscosity increases. Great improvements in wet-resistance from 22 to 60 min and bonding times (from 30 to 20 s) were observed for an adhesive containing 8% enzymatically polymerized lignin and 1% BTCA. On the other hand, the addition of citric acid (CA) deteriorated the properties of the adhesives, especially when lignosulfonate was present. In conclusion, this study shows that the addition of the appropriate amount of enzymatically polymerized lignosulfonates together with carboxylic acids (namely BTCA) to starch-based adhesives is a robust strategy for improving their wet resistance and bonding times.