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To improve the bioavailability of plant protection compounds we used an approach based on the non-covalent binding of natural water-soluble polysaccharides and oligosaccharides as delivery systems. This approach is widely used in the pharmaceutical industry to develop new drugs with increased solubility and bioavailability. The complexation of various plant protection compounds (antidotes to herbicides: naphthalic anhydride and floroksam; pesticides: tebuconazole, imidacloprid, imazalil and prochloraz) with natural poly- and oligosaccharides (arabinogalactan, glycyrrhizic acid, sodium salt of carboxymethyl cellulose) have been studied by NMR relaxation technique. It was demonstrated the solubility enchancement of plant protection compounds in the complexes under study. The influence of delivery systems on penetration efficacy of plant protection products into wheat, barley, rapeseed and corn seeds was also investigated by NMR methods. A significant improvement in the penetration of the active components in the presence of complexants (0.1-1%) was found. Such effect was also observed when arabinogalactan and glycyrrhizic acid were added in standard patented composition for grains treatment. To understand the mechanism of this effect at molecular level, the influence of polysaccharides and oligosaccharides on artificial lipid membrane was studied by NMR relaxation method. It was concluded that the effect of polysaccharides and oligosaccharides on the penetration efficacy of plant protection products might be associated with the detected solubility enhancement and the affinity of delivery systems to the surface of cell membranes.