From green chemistry and nature-like technologies towards ecoadaptive chemistry and technology

Abstract Nature-like technologies can be considered as a logical development of green chemistry principles implemented to design novel materials and processes aimed at mimicking and reproducing natural life-sustaining mechanisms on molecular level. Humic substances which penetrate throughout the entire environment and represent from 50 to 90% of organic matter in soil and water ecosystems, play multiple life-sustaining functions on Earth. To name a few, HS regulate transport and availability of biogenic elements to plants, immobilize and mitigate toxicity of hazardous elements in the contaminated ecosystems, protect plants from non-specific abiotic stresses, play key role for fertility of soils determining water-retention and structure. Here we represent a novel platform for nature-inspired synthesis of soft and hybrid (nano)materials aimed at their use for soil and water clean up, carbon sequestration, soil fertility restoration. It is based on a smart use of natural hyperbranched polyelectrolytes – humic substances, which possess multiple functional groups including carboxyl, hydroxyl, amide, and others. Multiple functional groups of HS make them amenable both for classical chemical modification as well as for producing interpolyelectrolyte complexes. In this work, we present both approaches for manufacturing silicon-containing humic derivatives and supramolecular complexes with acquired new property – self-adhesion to both inorganic and bio-surfaces. The synthesis is conducted using humic materials from different sources and functional organosilanes. Self-assembly of the supramolecular silicon-humic systems occurs with formation of humic-silsesquioxane networks capable to adhere to mineral surfaces. This process is similar to immobilization of organic coatings to mineral surfaces. We have shown how this process can be realized in the ground waters for the purposes of the environmental clean up. We have also proposed to use the silicon-humic complexes for improving humus content of soils and for reconstructing soil restoration processes both in the lab and in the field. Another field of our research is synthesis of iron-containing humics-stabilized nanoparticles (NPs), which can be used as a source for plants nutrition instead of synthetic iron chelates. The idea is based on the natural phenomenon that in soils, water-stable sols of iron-containing NPs are formed due to complexing with HS, which can bind large amounts of poorly ordered iron (hydr)oxides providing for stabilization of colloidal iron in the form of NPs. It has been numerously shown that the presence of HS improves iron acquisition by plants in soils, but there was no systematic study so far with respect to a relationship between size and crystallinity of humics-stabilized iron-containing NPs and their availability to plants. We have conducted such a study and could establish conditions when humics-stabilized NPs could be taken up by plants with similar efficiency as FeEDTA. The presented data demonstrate good prospects for a use of green humics-based materials in nature-like technologies. We also hope that these studies will give rise to new branch of chemistry and technology which can be called ecoadaptive chemistry and technology.