Enantioselective and Synergistic Herbicidal Activities of Common Amino Acids Against Amaranthus tricolor and Echinochloa crus-galli

Amino acids have a wide range of biological activities, which usually rely on the stereoisomer presented. In this study, glycine and 21 common α-amino acids were investigated for their herbicidal property against Chinese amaranth (Amaranthus tricolor L.) and barnyard grass (Echinochloa crus-galli (L.) Beauv.). Both d- and l-isomers, as well as a racemic mixture, were tested and found that most compounds barely inhibited germination but moderately suppressed seedling growth. Various ratios of d:l-mixture were studied and synergy between enantiomers was found. For Chinese amaranth, the most toxic d:l-mixtures were at 3:7 (for glutamine), 8:2 (for methionine), and 5:5 (for tryptophan). For barnyard grass, rac-glutamine was more toxic than the pure forms; however, d-tryptophan exhibited greater activity than racemate and l-isomer, indicating the sign of enantioselective toxicity. The mode of action was unclear, but d-tryptophan caused bleaching of leaves, indicating pigment synthesis of the grass was inhibited. The results highlighted the enantioselective and synergistic toxicity of some amino acids, which relied upon plant species, chemical structures, and concentrations. Overall, our finding clarifies the effect of stereoisomers, and provides a chemical clue of amino acid herbicides, which may be useful in the development of herbicides from natural substances.

Deep eutectic solvent-based emulsification liquid–liquid microextraction for the analysis of phenoxy acid herbicides in paddy field water samples

An emulsification liquid–liquid microextraction (ELLME) method was successfully developed using phenolic-based deep eutectic solvent (DES) as an extraction solvent for the determination of phenoxy acid herbicides, 3,6-dichloro-2-methoxybenzoic acid (dicamba) and 2-methyl-4-chlorophenoxyacetic acid (MCPA) in environmental water samples. Five different phenolics-based DESs were successfully synthesized by using phenol (DES 1), 2-chlorophenol (DES 2), 3-chlorophenol (DES 3), 4-chlorophenol (DES 4) and 3,4-dichlorophenol (DES 6) as the hydrogen-bond donor (HBD) and choline chloride as the hydrogen-bond acceptor (HBA). The DESs were mixed at 1 : 2 ratio. A homogeneous solution (clear solution) was observed upon the completion of successful synthesis. The synthesized DESs were characterized by using Fourier transform infrared and nuclear magnetic resonance (NMR). Under optimum ELLME conditions (50 µl of DES 2 as extraction solvent; 100 µl of THF as emulsifier solvent; pH 2; extraction time 5 min), enrichment factor obtained for dicamba and MCPA were 43.1 and 59.7, respectively. The limit of detection and limit of quantification obtained for dicamba were 1.66 and 5.03 µg l −1 , respectively, meanwhile for MCPA were 1.69 and 5.12 µg l −1 , respectively. The developed ELLME-DES method was applied on paddy field water samples, with extraction recoveries in the range of 79–91% for dicamba and 82–96% for MCPA.

The Influence of Hard Water on 2,4-D Formulations for the Control of Dandelion

The herbicide 2,4-D is used in a variety of cropping systems, especially in grasses since it is a selective postemergence broadleaf herbicide. However, the most common formulation (2,4-D dimethylamine) is antagonized when mixed in hard water. The objective of this research was to determine which formulations of 2,4-D or premixes of various formulations of synthetic auxin herbicides are subject to hard water antagonism. Formulations surveyed for hard water antagonism in the first experiment included 2,4-D dimethylamine, 2,4-D diethanolamine, 2,4-D monomethylamine, 2,4-D isopropylamine salt, 2,4-D choline salt, 2,4-D isooctyl ester, and 2,4-D ethylhexyl ester. Synthetic auxin formulation types in the second experiment included water-soluble, emulsifiable concentrates and emulsion-in-water. All formulations were mixed with both soft and hard water (600 mg CaCO3 L-1) and applied to dandelions to determine if antagonism occurred in hard water. Water-soluble (amine and choline) 2,4-D formulations were antagonized by hard water, but water-insoluble (ester) 2,4-D formulations were not antagonized. Similar results were found by formulation type with water-soluble synthetic auxin premixes antagonized but emulsifiable concentrates not antagonized. Further, water-soluble salt formulations were not antagonized when formulated in premixes with other synthetic auxin herbicides as an emulsion-in-water. This research demonstrates that all 2,4-D water-soluble formulations and water-soluble premixes with phenoxycarboxylic acid herbicides are subject to hard water antagonism. Formulations of 2,4-D containing emulsifying agents protect against antagonism by the water-insoluble nature of ingredients in their formulation.