Quantitative Structure-Activity Relationship of Humic-Like Biostimulants Derived From Agro-Industrial Byproducts and Energy Crops

Abstract

Humic-like substances (HLSs) isolated by alkaline oxidative hydrolysis from lignin-rich agro-industrial residues have been shown to exert biostimulant activity toward maize (Zea mays L.) germination and early growth. The definition of a quantitative structure-activity relationship (QSAR) between HLS and their bioactivity could be useful to predict their biological properties and tailor plant biostimulants for specific agronomic and industrial uses. Here, we created several projection on latent structure (PLS) regression by using published analytical data on the molecular composition of lignin-derived HLS obtained by both ¹³C-CPMAS-NMR spectra directly on samples and ³¹P-NMR spectra after derivatization of hydroxyl functions with a P-containing reagent (2-chloro-4,4,5,5-tetramethyl-1,3,2-dioxaphospholane). These spectral data were used to model the effect of HLS on the elongation of primary root, lateral seminal roots, total root apparatus, and coleoptile of maize. The ¹³C-CPMAS-NMR data suggested that methoxyl and aromatic moieties positively affected plant growth, while the carboxyl/esterified functions showed a negative impact on the overall seedling development. Alkyl C seems to promote Col elongation while concomitantly reducing that of the root system. Additionally, ³¹P-NMR-derived spectra revealed that the elongation of roots and Col were enhanced by the occurrence of aliphatic hydroxyl groups, and guaiacyl and p-Hydroxyphenyl lignin monomers. The PLS models based on raw dataset from ¹³C-CPMAS-NMR spectra explained more than 74% of the variance for the length of lateral seminal roots, total root system and coleoptile, while other parameters derived from ¹³C-CPMAS-NMR spectra, namely the Hydrophobicity and Hydrophilicity of materials were necessary to explain 83% of the variance of the primary root length. The results from ³¹P-NMR spectra explained the observed biological variance by 90, 96, 96, and 93% for the length of primary root, lateral seminal roots, total root system and coleoptile, respectively. This work shows that different NMR spectroscopy techniques can be used to build up PLS models which can predict the bioactivity of lignin-derived HLS toward early growth of maize plants. The established QSAR may also be exploited to enhance by chemical techniques the bioactive properties of HLS and enhance their plant stimulation capacity.

Keywords: -dioxaphospholane; 2; 2-chloro-4; 3; 4; 5; 5-tetramethyl-1; biorefinery and agro-industrial byproducts; biostimulants; humic-like substance; liquid-state 31P-NMR spectroscopy; partial least square regression; projection on latent structure regression; solid-state 13C-CPMAS NMR spectroscopy.