Herein, we provide a brief overview of the synthesis and applications of trifluoromethylpyridine (TFMP) and its derivatives in the agrochemical and pharmaceutical industries. Currently, the major use of TFMP derivatives is in the protection of crops from pests. Fluazifop-butyl was the first TFMP derivative introduced to the agrochemical market, and since then, more than 20 new TFMP-containing agrochemicals have acquired ISO common names. Several TFMP derivatives are also used in the pharmaceutical and veterinary industries; five pharmaceutical and two veterinary products containing the TFMP moiety have been granted market approval, and many candidates are currently undergoing clinical trials. The biological activities of TFMP derivatives are thought to be due to the combination of the unique physicochemical properties of the fluorine atom and the unique characteristics of the pyridine moiety. It is expected that many novel applications of TFMP will be discovered in the future.

The OECD 301F ready biodegradability test has been approved for use under the Japanese Chemical Substances Control Law since 2018. This test uses activated sludge obtained from a sewage treatment plant instead of the standard activated sludge used for the 301C test. In addition, the test is allowed to add an inert support or emulsifying agent, and/or to change the volume of the test medium. In this study, we first confirmed that the standard sludge had lower biodegradation activities than the sludge taken from a sewage treatment plant. Second, we showed that biodegradation percentages were increased by adding suitable amounts of silica gel or Tween 80. Third, we found that the biodegradations were accelerated by only increasing the medium volume under the conditions that concentrations of chemical, silica gel, and sludge were held constant. These findings are expected to contribute to the appropriate evaluation of chemical fate in a realistic environment.

Tolpyralate, a new selective postemergence herbicide developed for the weed control in corn, possesses a unique chemical structure with a 1-alkoxyethyl methyl carbonate group on the N-ethyl pyrazole moiety. This compound shows high herbicidal activity against many weed species, including glyphosate-resistant Amaranthus tuberculatus. Tolpyralate targets 4-hydroxyphenylpyruvate dioxygenase (4-HPPD), which is involved in the tyrosine degradation pathway. Inhibition of the enzyme destroys the chlorophyll, thereby killing the susceptible weeds. Details of tolpyralate discovery, structure optimization, and biological activities are described.

Specimens should be examined as much as possible to obtain a precise estimate of the proportion of resistance alleles in agricultural fields. Monitoring traps that use semiochemicals on sticky sheets are helpful in this regard. However, insects captured by such traps are ordinarily left in the field until collection. Owing to DNA degradation, the amount of DNA greatly varies among insects, causing serious problems in obtaining maximum likelihood estimates and confidence intervals of the proportion of the resistance alleles. We propose a statistical procedure that can circumvent this degradation issue. R scripts for the calculation are provided for readers. We also propose the utilization of a Sanger sequencer. We demonstrate these procedures using field samples of diamide-resistant strains of the diamondback moth, Plutella xylostella (Lepidoptera: Plutellidae). The validity of the assumptions used in the statistical analysis is examined using the same data.

Synthetic insecticides are widely used to control pests in various crop fields. Especially in soybean [Glycine max (L.) Merr.] fields, the insecticide etofenprox, which is a pyrethroid derivative, has been used to manage hemiptera pests. To date, soybean phytotoxicity response has not been reported to etofenprox derivatives, two Korean cultivars, Danbaek and Kwangan, were first identified to show leaf shape shrinkage damage after etofenprox application. We confirmed that the causal substance for phytotoxicity is etofenprox and that it had dosage effects. Through genetic analysis using three F₂ populations, sensitivity to etofenprox is confirmed to be managed by a single dominant gene, and that gene is the same in Danbaek and Kwangan. Although further genetic research is required to identify the gene responsible for sensitivity to etofenprox, the results of this study will help to elucidate the interaction between plants and chemicals when breeding new cultivars or developing pesticides.

In five regions of Korea, a total of 963 hot pepper powder samples were analyzed for 113 pesticides and one synergist using gas chromatography-mass spectrometry. For three years, sampling was performed every producing day in production plants according to ISO 24153 : 2009 methods. The limit of detection and limit of quantification ranges were 0.17–1.46 and 0.52–4.44 µg kg⁻¹, respectively. The recovery ranges were 62.8–128.6% when spiked with 10 and 100 µg kg⁻¹ of pesticides. Certified reference materials, such as chlorfenapyr and indoxacarb, were used for the validation of the analytical method. In total, 21 pesticides and one synergist were detected. Six pesticides, chlorfenapyr, indoxacarb, chlorantraniliprole, cypermethrin, difenoconazole, and pendimethalin, were detected at more than 50%, and nine pesticides, cyhalothrin, fenvalerate, picoxystrobin, deltamethrin, pyridalyl, propiconazole, iprodione, prochloraz, and bifenthrin, were detected at more than 10%. All monitoring results were under the Korean maximum residue limit.

The method for evaluating soybean (Glycine max) antixenosis against the common cutworm (Spodoptera litura) was developed based on a dual-choice assay aided by a statistical analysis model. This model was constructed from the results of a dual-choice assay in which Enrei, a soybean cultivar susceptible to S. litura, was used as both a standard and a test leaf disc for 2nd–5th instar larvae. The statistical criterion created by this model enabled the evaluation of the presence of antixenosis. This method was applied to four soybean varieties, including Tamahomare (susceptible), Himeshirazu (resistant), IAC100 (resistant), and Peking (unknown), as well as Enrei. Subsequently, the degrees of antixenosis were also compared by F-test, followed by maximum likelihood estimation (MLE). According to the results, the antixenosis of Tamahomare, Himeshirazu, and IAC100 was statistically reevaluated and Peking exhibited a novel antixenosis, which was stronger for 3rd–5th instar larvae than for 2nd instar.

We synthesized 33 new phenylpiperazine derivatives and assessed their acaricidal activity. These derivatives were synthesized through sequential reactions consisting of the sulfonylation of 2-substituted 4-methylaniline with chlorosulfonic acid, reduction with red phosphorus and iodine, alkylation by alkyl halide, cyclization with bis(2-chloroethyl)amine hydrochloride, and N-substitution reaction of phenylpiperazines with various reagents. All phenylpiperazines synthesized were evaluated for acaricidal activity and their structure–activity relationships discussed, it was found that 4-substituted 1-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenyl]piperazine derivatives exhibited good acaricidal activity. Among them, 1-[2-fluoro-4-methyl-5-(2,2,2-trifluoroethylsulfanyl)phenyl]-4-(trifluoromethylsulfonyl) piperazine showed the highest level of activity against Tetranychus urticae and provided a high level of activity against Tetranychus kanzawai and Panonychus citri. In addition, studies on the effect at various stages of T. urticae exhibited that this compound showed good activity against both adults and eggs.

Aminopyrifen is a novel 2-aminonicotinate fungicide with unique chemistry and a novel mode of action. The fungicide showed high antifungal activity mainly against Ascomycetes and its related anamorphic fungi under in vitro and pot conditions (EC₅₀ values: 0.0039–0.23 mg/L and 1.2–12 mg/L, respectively). The active ingredient strongly inhibited germ-tube elongation of Botrytis cinerea below 0.1 mg/L and invasion into a plant. The compound exhibited no cross-resistance to commercial fungicides in B. cinerea. The antifungal agent showed high preventive efficacy and translaminar action. In the field, aminopyrifen controlled gray mold and powdery mildew at 150 mg/L. Our findings suggest that aminopyrifen is useful for protecting crops from various plant pathogens.

Flutianil, a fungicide effective only on powdery mildew, was previously reported to affect the host cell's haustorial formation and nutrient absorption. Studies were conducted to investigate flutianil's primary site of action on Blumeria graminis morphology using transmission electron microscope (TEM) observation and RNA sequencing (RAN-seq) techniques. TEM observation revealed that flutianil caused the extra-haustorial matrix and fungal cell wall to be obscured, without remarkable changes of other fungal organelles. RNA-seq analysis indicated that, unlike other powdery-mildew fungicides, flutianil did not significantly affect the constantly expressed genes for the survival of B. graminis. Genes whose expression is up- or downregulated by flutianil were found; these are the three sugar transporter genes and various effector genes, mainly expressed in haustoria. These findings indicate that the primary site of action of flutianil might be in the haustoria.

Atrazine is the most extensively used herbicide in the agricultural and forestry sectors. Nevertheless, along with the increasing usage amount of Atrazine, its harm exposed gradually, the main problem is its residues in the environment. Microbial adsorption may effectively reduce the pollution caused by atrazine residue in the environment. In this study, a strain of fungi with the function of adsorbing atrazine was selected using microbial screening technology. According to its phenotypic characteristics and 18S rDNA gene sequencing, this strain was of the species genus Aspergillus and was named ECUST-TXZC2018. By studying the dynamic adsorption effect of this strain on atrazine, we found that this strain adsorbed atrazine after 36 hr at pH=5–7, and 20–30°C with more than 70% adsorption. These results demonstrated that ECUST-TXZC2018 had potential application ability to control atrazine residue pollution through the biosorption function.

This study aimed to characterize nanoparticles loaded with clove (Syzygium aromaticum) essential oil-based polyethylene glycol (PEG) and to know their insecticidal activity against red flour beetle (Tribolium castaneum). The nanoparticles have irregular shapes in good dispersion. The nanoformulation could not enhance clove oil contact toxicity to T. castaneum, but could protect the oil from degradation and evaporation while simultaneously allowing sustained release, as indicated by the continued high toxicity for 16 weeks of storage.

To investigate the effects of bioisosteric replacement of the phenyl group with the thienyl group, N-phenylcarboxamide and three regioisomers of N-(substituted-thienyl)carboxamide were synthesized. The inhibitory activity on the succinate dehydrogenase prepared from the gray mold Botrytis cinerea as well as the fungicidal activity against B. cinerea were evaluated. Two isomers, N-(2-substituted-3-thienyl)carboxamide and N-(4-substituted-3-thienyl)carboxamide exhibited the same level of activity as the phenyl derivative, whereas N-(3-substituted-2-thienyl)carboxamide exhibited lower activity than the phenyl derivative, suggesting that the 2-substituted-3-thienyl and 4-substituted-3-thienyl groups functioned as bioisosteres of the phenyl group in N-phenylcarboxamide, but the other did not.

The reactions of a 3-amidothiophene derivative, which is a partial structure of penthiopyrad, with various carbonyl compounds were investigated. Depending on the carbonyl compound that was used as a reactant, different products (alkenes and bis-products) were obtained from the attack of the carbon at the 2-position of the 3-amidothiophene on the carbonyl compounds. Density functional theory (DFT) calculations revealed that dehydration conditions were important for the first carbonyl addition to shift the reaction toward the product, as the products are more unstable than reactants other than aldehyde. The DFT calculations also suggested that the relative stability of the alkenyl state determined whether the second bis-product formation would proceed; i.e., the relatively unstable disubstituted alkene led to bis-products, and the stable trisubstituted or conjugated alkene yielded alkenyl products.

Damage caused by Orobanchaceae root parasitic weeds is a substantial agricultural problem for global food security. Many studies have been conducted to establish practical methods of control, but efforts are still required for successful management. Seed germination of root parasitic weeds requires host-derived germination stimulants including strigolactones (SLs). Studies on SLs have revealed that a butenolide ring is the essential moiety for SL activity as a germination stimulant. Interestingly, recent studies have revealed that butenolide hormones regulate the biosynthesis of secondary metabolites and mediate communication in actinomycete bacteria. Because of the structural similarity between SLs and the bacterial butenolides, we evaluated the germination stimulatory activity of butenolides isolated from Streptomyces albus J1074 on root parasitic weeds. These butenolides were found to specifically induce seed germination of Orobanche minor. Our findings contribute to understanding the molecular mechanisms of germination stimulant perception and to the development of a method for their biological control.