Li-Xia Zhao,Jian-Feng Peng,Feng-Yi Liu,Yue-Li Zou,Shuang Gao,Ying Fu,Fei Ye
Protoporphyrinogen oxidase (PPO, EC 1.3.3.4) is an important target for discovering novel herbicides, and it causes bleaching symptoms by inhibiting the synthesis of chlorophyll and heme. In this study, the active fragments of several commercial herbicides were joined by substructure splicing and bioisosterism, and a series of novel diphenyl ether derivatives containing five-membered heterocycles were synthesized. The greenhouse herbicidal activity and the PPO inhibitory activity in vitro were discussed in detail. The results showed that most compounds had good PPO inhibitory activity, and target compounds containing trifluoromethyl groups tended to have higher activity. Among them, compound G4 showed the best inhibitory activity, with a half-maximal inhibitory concentration (IC50) of 0.0468 μmol/L, which was approximately 3 times better than that of oxyfluorfen (IC50 = 0.150 μmol/L). In addition, molecular docking indicated that compound G4 formed obvious π–π stacking interactions and hydrogen bond interactions with PHE-392 and ARG-98, respectively. Remarkably, compound G4 had good safety for corn, wheat, rice, and soybean, and the cumulative concentration in crops was lower than that of oxyfluorfen. Therefore, compound G4 can be used to develop potential lead compounds for novel PPO inhibitors.
The widespread occurrence of sulfonamides (SAs) in natural waters, wastewater, soil and sediment has raised increasing concerns about their potential risks to human health and ecological systems. Sulfate radical (SO 4 − )-based advanced oxidation processes (SR-AOPs) have become promising technologies to remove such contaminants in the environment. The present study systematically investigated the degradation of four selected SAs with different five-membered heterocyclic rings, namely, sulfamethoxazole (SMX), sulfisoxazole (SIX), sulfathiazole (STZ), and sulfamethizole (SMT), by thermo-activated persulfate (PS) process, and the role of heterocyclic rings was assessed particularly. The results revealed that all the selected SAs could be degraded efficiently by thermo-activated PS process and their decay rates were appreciably increased with increasing temperature. For instance, degradation rates of STZ increased from 0.3 × 10 −3 to 19.5 × 10 −3 min −1 as the temperature was increased from 30 to 60 °C. Under the same experimental conditions, the degradation rates of SAs followed the order of SIX > SMX ≈ STZ > SMT, which was in accordance with decay rates of their R-NH 2 moieties. Kinetic results indicated that five-membered heterocyclic rings could serve as reactive moieties toward SO 4 − attack, which were confirmed by frontier electron density (FED) calculations. Based on the transformation products identified by high-resolution mass spectrometry (HR-MS), five different oxidation pathways, including hydroxylation, aniline moiety oxidation, dimerization , sulfonamide bond cleavage, and heterocyclic ring oxidation/cleavage were proposed. Moreover, the degradation efficiency in real surface water (RSW) was found to be slightly slower than that in artificial surface water (ASW), suggesting that SR-AOPs could be an efficient approach for remediation of soil and water contaminated by these SAs.
危险品化学品经营许可证（带存储）