Photodegradation of the phenylpyrazole insecticide ethiprole in aquatic environments and a comparison with fipronil.

Ethiprole (ETH) is a phenylpyrazole insecticide that is used worldwide as an alternative to fipronil (FIP). Research on the photodegradation of ETH in aquatic environments has been limited compared with that on FIP. In this study, to clarify the photodegradation of ETH in aquatic systems, the photodegradation pathway and products were investigated using liquid chromatography and liquid chromatography-tandem mass spectrometry. We also determined the photochemical half-lives (t1/2) of ETH and its main degradation products. The primary photodegradation pathway was cyclization/dechlorination and hydroxylation/dechlorination of ETH to form the didechlorinated products (benzimidazole of des-chloro-hydroxy-ETH). Some newly identified photodegradation products and analogs of FIP photodegradation products were also detected as minor products. We compared the photodegradation of ETH with that of FIP under the same conditions. Didechlorinated products of ETH and FIP had the highest photostability. However, although the photochemical t1/2 of EHT was 2.7 times that of FIP, the photochemical t1/2 of the didechlorinated product of ETH was approximately one-third that of the didechlorinated product of FIP. This comparison of the photochemical processes of ETH and FIP provides new insight into the persistence and characteristics of both insecticides in the environment.

Photodegradation of the insecticide fipronil in aquatic environments: photo-dechlorination processes and products.

Fipronil (FIP) is a phenylpyrazole insecticide that, along with neonicotinoid insecticides, is regularly used worldwide. Photodegradation of FIP in aqueous systems is thought mainly to involve the reaction of desulfinylation to give fipronil desulfinyl (FIP-desulfinyl); however, little is known about further degradation reactions. We investigated FIP photodegradation by analyzing photodegradation products by liquid chromatography and liquid chromatography high-resolution tandem mass spectrometry using an Orbitrap instrument. A wide range of products, including dechlorinated compounds, was detected, and the structures were identified. FIP-desulfinyl has previously been found to be an important and persistent FIP photodegradation product; however, we also found that FIP-desulfinyl was photochemically decomposed to a didechlorinated product via a monodechlorinated product. The main photodegradation pathway was probably similar to that of ethiprole, which has a similar skeleton. The photodegradation rate constant was 22.6 times lower for FIP-desulfinyl (0.00372 min-1) than FIP (0.0839 min-1). The photodegradation rate constant was lower for the newly found didechlorinated product (0.001 min-1 or below) than FIP-desulfinyl, suggesting that the product is persistent in aquatic environments and could be an important indicator of long-term FIP contamination.

Proximity Labeling and Proteomics: Get to Know Neighbors.

Protein-protein interactions are essential in biological reactions and fundamental to cell-cell communication (e.g., the binding of secreted proteins, such as hormones, to cell membrane receptors) and the subsequent intracellular signal transduction cascade. Several studies have been extensively carried out on protein-protein interactions because they have the potential to resolve various problems in molecular biology. Biochemical methods, such as chemical cross-linking and immunoprecipitation, have long been used to analyze which proteins interact with each other. However, there are some problems, such as unphysiological states and non-specific binding, that require the development of more useful experimental methods. This chapter discusses the "proximity labeling (Proteomics)" analysis technique, which has been attracting attention in protein-protein interaction analysis in recent years and is used in many biological studies. "Membrane proximity labeling (proteomics)," which analyzes the interaction of cell membrane proteins, and "intracellular proximity labeling (proteomics)" will be explained in-depth.

Migration of terephthalate from scraps of poly(ethylene terephthalate) (PET) in water and artificial seawater.

We report the migration of terephthalate and some low molecular weight organic compounds from poly(ethylene terephthalate) (PET) scraps in Milli-Q water and artificial seawater (ASW). The photochemical processes and the subsequent dark reactions were investigated using PET scraps obtained from postconsumer bottles of commercial non­carbonated mineral water. Concentrations of terephthalate exponentially increased with irradiation time, reaching approximately 6-8 µmol L-1 in ASW after 80 h irradiation. The photochemical migrations of compounds related to terephthalate were also observed. Concentrations of terephthalate and related compounds reached higher concentrations in ASW than in Milli-Q water. After 80 h irradiation, two dark experiments were conducted: one on the solutions after irradiation without PET scraps, and the other on photochemically damaged PET scraps. In ASW in the dark without PET scraps, the terephthalate concentration increased, and concentrations of other compounds related to terephthalate also changed. The results suggested that terephthalate was generated by hydrolytic reaction in dark ASW from the scission products of PET which were generated during the irradiation of PET scraps. Photochemically damaged PET scraps released terephthalate and related compounds in the dark. The half-life of the photo-irradiated PET scraps in the dark is approximately 205 years. Our results show that PET bottles in marine environments can continuously release terephthalate and other low molecular weight organic compounds during the day at the sunny surface, at the dark ocean floor, and during the night.

Production of Agrocinopine A by Ipomoea batatas Agrocinopine Synthase in Transgenic Tobacco and Its Effect on the Rhizosphere Microbial Community.

Agrobacterium tumefaciens is a bacterial pathogen that causes crown gall disease on a wide range of eudicot plants by genetic transformation. Besides T-DNA integrated by natural transformation of plant vegetative tissues by pathogenic Agrobacterium spp., previous reports have indicated that T-DNA sequences originating from an ancestral Agrobacterium sp. are present in the genomes of all cultivated sweet potato (Ipomoea batatas) varieties analyzed. Expression of an Agrobacterium-derived agrocinopine synthase (ACS) gene was detected in leaf and root tissues of sweet potato, suggesting that the plant can produce agrocinopine, a sugar-phosphodiester opine considered to be utilized by some strains of Agrobacterium spp. in crown gall. To validate the product synthesized by Ipomoea batatas ACS (IbACS), we introduced IbACS into tobacco under a constitutive promoter. High-voltage paper electrophoresis followed by alkaline silver nitrate staining detected the production of an agrocinopine-like substance in IbACS1-expressing tobacco, and further mass spectrometry and nuclear magnetic resonance analyses of the product confirmed that IbACS can produce agrocinopine A from natural plant substrates. The partially purified compound was biologically active in an agrocinopine A bioassay. A 16S ribosomal RNA amplicon sequencing and meta-transcriptome analysis revealed that the rhizosphere microbial community of tobacco was affected by the expression of IbACS. A new species of Leifsonia (actinobacteria) was isolated as an enriched bacterium in the rhizosphere of IbACS1-expressing tobacco. This Leifsonia sp. can catabolize agrocinopine A produced in tobacco, indicating that the production of agrocinopine A attracts rhizosphere bacteria that can utilize this sugar-phosphodiester. These results suggest a potential role of IbACS conserved among sweet potato cultivars in manipulating their microbial community.[Formula: see text] Copyright © 2021 The Author(s). This is an open access article distributed under the CC BY-NC-ND 4.0 International license.

Majority-Rules Effect and Allostery in Molecular Recognition of Calix[4]arene-Based Triple-Stranded Metallohelicates.

The triple-stranded metallohelicates 1 a,/1 b-3 a/3 b possessing internal guest binding cavities surrounded by calix[4]arene units were synthesized through coordination-driven self-assembly. UV/Vis titration experiments verified that the metallohelicates encapsulated N-methyl pyridinium cations bearing amino acid groups to form host-guest complexes. The guest chirality was transferred to the helicity of the helicates through the steric contact between the stereogenic center of the amino acid group and the metal cores. The (M) helicity was induced when guests the (R)-4--(R)-6 were accommodated within the cavities. The multiple guest complexation within the self-assembled helicates 2 a and 3 a displayed large positive cooperative effects, indicating that the first guest complexation preorganizes the rest of the cavities to facilitate a subsequent guest binding. This cooperativity results in the majority-rules effect in the chiral guest binding for 2 a and 3 a.

Spontaneous emulsification and self-propulsion of oil droplets induced by the synthesis of amino acid-based surfactants.

It is well known that oil droplets in or on water exhibit spontaneous movement induced by surfactants, and this self-propulsion is regarded as an important factor in droplet-based models for a living cell. We report here an oil-droplet system spontaneously producing amino acid-based surfactants, which are then utilized for the droplets' self-propulsion. Thus this system is an active system capable of producing the fuel for the propulsion by itself, which can be used as a conceptual model for cell metabolism.

Sequence-controlled supramolecular terpolymerization directed by specific molecular recognitions.

Nature precisely manipulates primary monomer sequences in biopolymers. In synthetic polymer sequences, this precision has been limited because of the lack of polymerization techniques for conventional polymer synthesis. Engineering the primary monomer sequence of a polymer main chain represents a considerable challenge in polymer science. Here, we report the development of sequence-controlled supramolecular terpolymerization via a self-sorting behavior among three sets of monomers possessing mismatched host-guest pairs. Complementary biscalix[5]arene-C60, bisporphyrin-trinitrofluorenone (TNF), and Hamilton's bis(acetamidopyridinyl)isophthalamide-barbiturate hydrogen-bonding host-guest complexes are separately incorporated into heteroditopic monomers that then generate an ABC sequence-controlled supramolecular terpolymer. The polymeric nature of the supramolecular terpolymer is confirmed in both solution and solid states. Our synthetic methodology may pave an avenue for constructing polymers with tailored sequences that are associated with advanced functions.Nature can precisely control monomer sequences in biopolymers, but this is somewhat problematic in the formation of synthetic polymers. Here the authors show sequence-controlled supramolecular terpolymerization via self-sorting behavior among three sets of monomers possessing mismatched host-guest pairs.