A series of fully renewable triphenols (TPs) with various number of methoxy group substituents (n = 0–6) were synthesized using lignin-derived phenols (guaiacol and 2,6-dimethoxyphenol) and aldehydes (4-hydroxybenzaldehyde, vanillin, and syringaldehyde). The structural evolution from TPs to epoxy thermosets was followed by nuclear magnetic resonance (NMR) and Fourier transform infrared (FTIR) spectroscopy. Thermomechanical properties of the resulting epoxy thermosets were investigated by dynamic mechanical analysis (DMA), tensile analysis (TA), and thermogravimetric analysis (TGA). Increasing the content of methoxy groups decreased the glass transition temperature (132–118 °C) and glassy modulus (2.7–2.2 GPa). Thermal stability of high-methoxy-content thermosets was reduced due to electron-donating effects and higher oxygen content. Conversions and isolated yields of TPs significantly decreased as the number of methoxy substituents increased, which markedly determined the feasibility of TPs as precursors for polymers. This work widens the synthesis route of fully lignin-derived polyphenols, yielding polymers with thermomechanical properties comparable to bisphenol A (BPA) based materials. Evaluation of methoxy substitution provides insight for the selection of lignin-derived monomers.
Knowledge of dissolution, aggregation, and stability of nanoagrochemicals in root exudates (RE) and soil leachate will contribute to improving delivery mechanisms, transport in plants, and bioavailability. We characterized aggregation, stability, and dissolution of four nanoparticles (NPs) in soybean RE and soil leachate: nano-CeO 2 , nano-Mn 3 O 4 , nano-Cu(OH) 2 , and nano-MoO 3 . Aggregation differed considerably in different media. In RE, nano-Cu(OH) 2 , and nano-MoO 3 increased their aggregate size for 5 days; their mean sizes increased from 518 ± 43 nm to 938 ± 32 nm, and from 372 ± 14 nm to 690 ± 65 nm, respectively. Conversely, nano-CeO 2 and nano-Mn 3 O 4 disaggregated in RE with time, decreasing from 289 ± 5 nm to 129 ± 10 nm, and from 761 ± 58 nm to 143 ± 18 nm, respectively. Organic acids in RE and soil leachate can be adsorbed onto particle surfaces, influencing aggregation. Charge of the four NPs was negative in contact with RE and soil leachate, due to organic matter present in RE and soil leachate. Dissolution in RE after 6 days was 38%, 1.2%, 0.5%, and <0.1% of the elemental content of MoO 3 , Cu(OH) 2 , Mn 3 O 4 , and CeO 2 NPs. Thus, the bioavailability and efficiency of delivery of the NPs or their active ingredients will be substantially modified soon after they are in contact with RE or soil leachate.
A series of liquid and curable lignin-containing epoxy prepolymers were prepared for making renewable epoxy thermosets. First, lignin was modified to phenolated lignin (PL) in a solvent-free reaction. PL was subsequently co-oligomerized with salicyl alcohol (SA) in water without the use of formaldehyde to obtain fully bio-based polyphenols (PL-SA). Glycidylation of lignin-based polyphenols yielded exclusively liquid epoxy prepolymers without production of solid co-products. The liquid epoxy prepolymers (with lignin content up to 21 wt %) were curable with amine hardener (diethylenetriamine) to generate homogeneous thermosets, which required no epoxy co-prepolymer. The structural evolution from starting monomers to epoxy thermosets was followed by nuclear magnetic resonance and Fourier transform infrared spectroscopy. Compared to common syntheses in which lignin is glycidylated prior to being blended with epoxy co-prepolymers, the herein reported methodology conferred networks with increased α-relaxation temperature (106–114 vs 96 °C), storage modulus (1843–2151 vs 1828 MPa), cross-link density (8.2–16.0 vs 5.4 mmol/cm3) and tensile properties (stress of 66.9–68.1 vs 28.7 MPa, and strain of 3.3–3.7 vs 1.4%). Moreover, bio-based thermosets exhibited comparable or superior thermomechanical properties to conventional bisphenol A (BPA)-based counterpart. By producing liquid-phase lignin-containing epoxy prepolymers, this study provides a formaldehyde-free method for incorporating lignin into epoxy thermosets without the need for additional co-prepolymers.
Metabolomics is an emerging tool to understand the potential implications of nanotechnology, particularly for agriculture. Although molybdenum (Mo) is a known plant micronutrient, little is known of its metabolic perturbations. Here, corn and wheat seedlings were exposed to MoO 3 nanoparticles (NPs) and the corresponding bioavailable Mo 6+ ion at moderate and excessive levels through root exposures. Physiologically, corn was more sensitive to Mo, which accumulated up to 3.63 times more Mo than wheat. In contrast, metabolomics indicated 21 dysregulated metabolites in corn leaves and 53 in wheat leaves. Five more metabolomic pathways were perturbed in wheat leaves compared to corn leaves. In addition to the overall metabolomics analysis, we also analyzed individual metabolite classes (e.g., amino acids, organic acids, etc.), yielding additional dysregulated metabolites in plant tissues: 7 for corn and 7 for wheat. Most of these were amino acids as well as some sugars. Additional significantly dysregulated metabolites (e.g., asparagine, fructose, reduced glutathione, mannose) were identified in both corn and wheat, due to Mo NP exposure, by employing individual metabolite group analysis. Targeted metabolite analysis of individual groups is thus important for finding additional significant metabolites. We demonstrate the value of metabolomics to study early stage plant responses to NP exposure.
Surfactants are commonly used in foliar applications to enhance interactions of active ingredients with plant leaves. We employed metabolomics to understand the effects of TritonTM X-100 surfactant (SA) and nanomaterials (NMs) on wheat (Triticum aestivum) at the molecular level. Leaves of three-week-old wheat seedlings were exposed to deionized water (DI), surfactant solution (SA), NMs-surfactant suspensions (Cu(OH)2 NMs and MoO3 NMs), and ionic-surfactant solutions (Cu IONs and Mo IONs). Wheat leaves and roots were evaluated via physiological, nutrient distribution, and targeted metabolomics analyses. SA had no impact on plant physiological parameters, however, 30+ dysregulated metabolites and 15+ perturbed metabolomic pathways were identified in wheat leaves and roots. Cu(OH)2 NMs resulted in an accumulation of 649.8 μg/g Cu in leaves; even with minimal Cu translocation, levels of 27 metabolites were significantly changed in roots. Due to the low dissolution of Cu(OH)2 NMs in SA, the low concentration of Cu IONs induced minimal plant response. In contrast, given the substantial dissolution of MoO3 NMs (35.8%), the corresponding high levels of Mo IONs resulted in significant metabolite reprogramming (30+ metabolites dysregulated). Aspartic acid, proline, chlorogenic acid, adenosine, ascorbic acid, phenylalanine, and lysine were significantly upregulated for MoO3 NMs, yet downregulated under Mo IONs condition. Surprisingly, Cu(OH)2 NMs stimulated wheat plant tissues more than MoO3 NMs. The glyoxylate/dicarboxylate metabolism (in leaves) and valine/leucine/isoleucine biosynthesis (in roots) uniquely responded to Cu(OH)2 NMs. Findings from this study provide novel insights on the use of surfactants to enhance the foliar application of nanoagrochemicals.
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