In order to find a novel type of fluorescent phloem-mobile insecticides, a facile one-pot solvothermal strategy via fipronil addition-elimination substitution reaction with the corresponding acyl chloride derivatives has been employed to construct series of phenylpyrazole amide derivatives ( PAs ) fused olefin moieties in high yields. The investigation for insecticidal bioactivities of PAs against 3rd instar larvae of Plutella xylostella exhibited better activities than that of fipronil , which can be elucidated by enhanced phloem mobility and calcium ions' coordination with amide N-C=O, C C double bonds and chloride ions, extended conjugate moieties and decreasing steric hindrance of the stereoscopic structure. The introduction of amide units conferred phloem mobility to PAs , which was evaluated by the hydrophobic parameters determined with reversed-phase HPLC through the chromatographic capacity factor. By introducing conjugate moieties and organic chromophore into phenylpyrazole parent structure to increase their conjugation degree and light absorption abilities, PAs exhibited good photodegradation properties. The relationships between extended conjugate moieties of parent structure, electronegativity of substituted groups and photodegradation properties have been discussed. The olefin units connected to PAs caused electronic absorption and fluorescent wavelengths bathochromic shifted. Under simulated solar irradiation, PAs can be reconverted into fipronil parent fragments by photodegradation, thereby enhancing their insecticidal activity. The fluorescent quantum yields of PAs were almost 4 times that of fipronil, which also laid a foundation for the natural degradation and fluorescence detection of insecticide residues.
Abstract Current methods for measurement of unsymmetrical dimethylhydrazine (UDMH) in wastewater suffer from a small detection range and complex pretreatment. In this study, ion chromatography (IC) with conductivity detection was used to directly analyze UDMH in wastewater, without any derivatization pretreatment, and the measurement range was as wide as 0.5–1000 μg·mL −1 . The effects of column temperature and sample pH on the detection were investigated. Furthermore, the chromatography conditions were optimized by combining the effects of different combinations of nitric acid, 2,6-pyridinedicarboxylic acid (PDCA), and methanesulfonic acid (MSA) on the analysis of mixed samples of UDMH and alkali metal ions. The linearity of the detected peak height ( H ) and peak area ( A ) versus UDMH concentration was studied at low, medium, and high concentrations. A good linear relationship was observed in the range of 0.5–1000 μg·mL −1 , especially for A , the relative standard deviation (RSD) and correlation coefficient ( R 2 ) of which were 0.077–1.653% and 0.9998–1.0000, respectively. In addition, the method showed good sensitivity with a limit of detection (LOD) of 0.05 μg·mL −1 and a limit of quantitation (LOQ) of 0.16 μg mL −1 . The precision and accuracy (expressed by recovery) were verified, where the RSD were less than 1.49% and 3.17%. Interference between hydrazines and alkali metal ions was discussed. Finally, actual UDMH samples were determined, confirming the applicability of the developed method for analyzing UDMH in wastewater during the degradation process. Graphic Abstract
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