Adhesion Peptide-Functionalized Biobased Microgels for Controlled Delivery of Pesticides.

Widespread use of plant protection agents in agriculture is a major cause of pollution. Apart from active ingredients, the environmental impact of auxiliary synthetic polymers should be minimized if they are highly persistent. An alternative to synthetic polymers is the use of natural polysaccharides, which are abundant and biodegradable. In this study, we explore pectin microgels functionalized with anchor peptides (P-MAPs) to be used as an alternative biobased pesticide delivery system. Using copper as the active ingredient, P-MAPs effectively prevented infection of grapevine plants with downy mildew under semi-field conditions on par with commercial copper pesticides. By using anchor peptides, the microgels tightly bind to the leaf surface, exhibiting excellent rain fastness and prolonged fungicidal activity. Finally, P-MAPs are shown to be easily degradable by enzymes found in nature, demonstrating their negligible long-term impact on the environment.

Influence of Architecture on the Interfacial Properties of Polymers: Linear Chains, Stars, and Microgels.

Surface-active polymers have important applications as effective and responsive emulsifiers, foaming agents, and coatings. In this contribution, we explore the impact of the polymer architecture on the behavior at oil-water interfaces by comparing different poly(N-isopropylacrylamide) (pNIPAM)-based systems, namely, monolayers of linear and star-shaped macromolecules, ultralow cross-linked, regular cross-linked, and hollow microgels. Compression isotherms were determined experimentally as well as by computer simulations. The latter provides information about the conformational changes of the individual macromolecules as well as the interfacial properties of the monolayer, including the surface structure and the density distribution of an ensemble of interacting macromolecules near an interface. Surprisingly, the isotherms of the linear polymer, of the star polymer, and of the ultralow cross-linked microgel have an identical shape that differs from the isotherms of regular and hollow microgels. We introduced the mass fraction of adsorbed polymer, which gives a measure of the polymer segments contributing to the isotherm in relation to the most flexible architecture, i.e., the linear polymer, and allows a comparison of polymers with different architectures. The data demonstrate that increasing the number of cross-links leads to a significantly lower amount of polymer in the proximity of the interface as the increase in cross-linker reduces the deformability or softness of the polymers at the interface. The volume fraction profiles along the normal to the interface are essentially different in the microgel monolayers as compared to those in the linear and star polymer. The profiles through the microgel contact line and their growth upon initial compression are similar to those of the linear chains. Herewith, the profiles through the center of mass practically do not change upon compression. Therefore, the initial growth in the microgel surface pressure reveals the polymer-like behavior and is related to the deformation of the peripheral part of the microgel. Further compression of the microgel monolayer leads to 3D interactions of the microgels within the aqueous side of the interface and soft colloid-like behavior.

A plea for the integration of Green Toxicology in sustainable bioeconomy strategies - Biosurfactants and microgel-based pesticide release systems as examples.

A key aspect of the transformation of the economic sector towards a sustainable bioeconomy is the development of environmentally friendly alternatives for hitherto used chemicals, which have negative impacts on environmental health. However, the implementation of an ecotoxicological hazard assessment at early steps of product development to elaborate the most promising candidates of lowest harm is scarce in industry practice. The present article introduces the interdisciplinary proof-of-concept project GreenToxiConomy, which shows the successful application of a Green Toxicology strategy for biosurfactants and a novel microgel-based pesticide release system. Both groups are promising candidates for industrial and agricultural applications and the ecotoxicological characterization is yet missing important information. An iterative substance- and application-oriented bioassay battery for acute and mechanism-specific toxicity within aquatic and terrestrial model species is introduced for both potentially hazardous materials getting into contact with humans and ending up in the environment. By applying in silico QSAR-based models on genotoxicity, endocrine disruption, skin sensitization and acute toxicity to algae, daphnids and fish, individual biosurfactants resulted in deviating toxicity, suggesting a pre-ranking of the compounds. Experimental toxicity assessment will further complement the predicted toxicity to elaborate the most promising candidates in an efficient pre-screening of new substances.