Enantioselectivity of chiral compounds is receiving growing concern. Lactofen, a chiral herbicide widely used in field crops and vegetables to control broadleaf weeds, is still sold as racemate. In this work, the herbicidal activity and metabolism behavior of lactofen were investigated on an enantiomeric level. Two common broadleaf weeds (Eclipta prostrata L. and Portulaca oleracea L.) were used to evaluate the herbicidal activity of rac-/R- and S-lactofen, and their metabolism behavior in loach and rat liver microsomes was explored. Higher herbicidal activity of S-lactofen was observed, with the 20d-EC₅₀ values being 1.9–3.4 times lower than R-lactofen. Both loach and rat liver microsomes had ability to metabolize rac-lactofen, with half-lives of 1.93 and 1.28 h, respectively. Enantioselective metabolism behaviors were observed in loach and rat liver microsomes and the direction of enantioselectivity were different. R-lactofen was preferentially metabolized in loach liver microsome, while S-lactofen was preferentially metabolized in rat liver microsome. No interconversion of R- and S-lactofen was found. Besides, the main metabolic pathways of R- and S-lactofen were found to be significantly different. R-lactofen was metabolized to R-desethyl lactofen in both loach and rat liver microsomes without further metabolism. However, S-lactofen was metabolized to both S-desethyl lactofen and acifluorfene in rat liver microsome, which was mainly metabolized to acifluorfene in loach liver microsome. This study indicated enantioselectivity and metabolites should be taken into consideration when overall evaluating the environmental behavior of lactofen.

This work describes efforts to encapsulate savory (Satureja hortensis L.) essential oil (EO) with different natural polymers (i.e., Arabic gum/gelatin (AGG), apple pectin (AP), gelatin (G)) and, as a separate set of experiments, with bio cross-linkers (i.e., citric acid and transglutaminase enzyme). The phytotoxic activity of encapsulated savory EO on tomato (Lycopersicon esculentum Mill.) and amaranth weed (Amaranthus retroflexus L.) was investigated. The micro-capsules were evaluated in terms of size, polydispersity, stability, encapsulation efficiency, morphology, and release properties. The Korsmeyer–Peppas model operated when EO was being released from the micro-capsules. Carvacrol (52.5%) and γ-terpinene (30.2%) comprised the main constituents of the savory EO. Based on the results, encapsulating the EO with cross-linked biopolymers increased the stability and herbicidal activity of EO, as compared to simple EO emulsions. Maximum toxicity injuries (MTI) were caused by encapsulations of apple pectin, cross-linked with APe enzyme (15 ml/L) on both plant species. MTI were observed 2 days after using the micro-encapsulated herbicides (MCHs). However, the injury caused by MCHs on tomato was not significant. The lowest values of fresh weight (2.80 g), chlorophyll a (0.194 mg/g Fw), and total chlorophyll content (0.219 mg/g Fw) of amaranth occurred in response to APe (15 ml/L). Moreover, using AP(e) (10 ml/L) caused the lowest values of starch (0.444 mg/g Fw) and flavonoid contents (4.18 mg Cat/g Fw) in amaranth which measured as 59% and 90% reductions, respectively, in comparison with the control. The highest values of MDA (0.0109 nmol/g Fw) and H₂O₂ (0.0432 μmol/g Fw) were observed in amaranth plants treated with AP(e) (10 ml/L). In summary, cross-linked apple pectin can perform well in slow release delivery systems of agrochemicals. It can be recommended for use in the production of commercial, EO-based natural herbicides.

Polycaprolactone nanocapsules (PCL) containing pretilachlor were prepared, and Fourier transform infrared spectroscopy, atomic force microscopy, and transmission electron microscopy were used for their structural and morphological investigations. The results revealed that the nanocapsules had irregular shape and their particles size was in the range of 70–200 nm. The encapsulation efficiency of pretilachlor was measured as 99.5 ± 1.3% using high-performance liquid chromatography analysis. The physicochemical stability studies over 60 days showed that the nanocapsules were stable in the suspension without any aggregation. The herbicide activity was examined in a pre-emergence manner using barnyard grass as a target plant and rice as a non-target plant. The nanoformulation had no negative effect on rice plant. However, its effect on barnyard grass was significant. The cytotoxicity analysis indicated that the nanocapsulated herbicide is less toxic rather than the commercial formulation. Therefore, encapsulation of pretilachlor in PCL nanocapsules can be used effectively to construct environmentally friendly PCL-herbicide systems in agriculture.

Some tetrahydroisoindoline-1,3-dione derivatives (TDDs) possess potent herbicidal activity. To assess possible impacts of TDDs on humans, the interactions between TDDs and human serum albumin (HSA) were evaluated with steady-state and time-resolved fluorescence spectroscopy, synchronous fluorescence spectroscopy, Fourier transform-infrared spectroscopy, and circular dichroism spectroscopy. The thermodynamic data obtained at temperatures of 298, 307, and 316 K indicate that TDDs spontaneously bind to HSA and thus form a TDD-HSA complex. The conformation and secondary structure of HSA are changed, and the intrinsic fluorescence of HSA is statically quenched by TDDs. Moreover, the TDD-HSA complex is formed primarily through electrostatic interactions and has only one binding site on HSA. A competitive ligand-binding assay revealed that site II (subdomain IIIA) displays the greatest affinity for TDDs. In addition, an acute toxicity bioassay showed no zebrafish mortality upon exposure to 4000 μg L⁻¹ of TDDs. This work is helpful for understanding interactions between TDDs and HSA.

Slow-release formulations of the herbicide metribuzin (MET) embedded in the polymer matrix of degradable poly-3-hydroxybutyrate [P(3HB)] in the form of microparticles, films, microgranules, and pellets were developed and tested. The kinetics of polymer degradation, MET release, and accumulation in soil were studied in laboratory soil microecosystems with higher plants. The study shows that MET release can be controlled by using different techniques of constructing formulations and by varying MET loading. MET accumulation in soil occurs gradually, as the polymer is degraded. The average P(3HB) degradation rates were determined by the geometry of the formulation, reaching 0.17, 0.12, 0.04, and 0.05 mg/day after 60 days for microparticles, films, microgranules, and pellets, respectively. The herbicidal activities of P(3HB)/MET formulations and commercial formulation Sencor Ultra were tested on the Agrostis stolonifera and Setaria macrocheata plants. The parameters used to evaluate the herbicidal activity were plant density and the weight of fresh green biomass measured at days 10, 20, and 30 after sowing. All P(3HB)/MET formulations had pronounced herbicidal activity, which varied depending on MET loading and the stage of the experiment. In the early phases of the experiment, the herbicidal effect of P(3HB)/MET formulations with the lowest MET loading (10 %) was comparable with that of the commercial formulation. The herbicidal effect of P(3HB)/MET formulations with higher MET loadings (25 and 50 %) at later stages of the experiment were stronger than the effect of Sencor Ultra.