Design, synthesis and insecticidal activities of 4-propargyloxybenzene sulfonamide derivatives substituted with amino acids.

Sixty-nine 4-propargyloxybenzene sulfonamide derivatives with different amino acids as amino substituent were synthesized and evaluated for their insecticidal activity against third-instar Mythimna separate. The bioassay results revealed that some derivatives bearing amino acid ester group performed good insecticidal activity against third-instar M.separata, such as the LC50 values of D18 and D19 were 4.28 and 2.96 mg/ml after 48 h, in particular, the LC50 of D16 was 2.38 mg/ml and the activity was improved by 14 times compared to celangulin V (34.48 mg/ml). The above results provided theoretical and experimental basis for the discovery of novel insecticidal active compounds.

Knockin of the G275E mutation of the nicotinic acetylcholine receptor (nAChR) α6 confers high levels of resistance to spinosyns in Spodoptera exigua.

Spinosyns, including spinosad and spinetoram, act on the insect central nervous system, gradually paralyzing or destroying the target insect. Spinosad resistance is associated with loss-of-function mutations in the nicotinic acetylcholine receptor (nAChR) α6 subunit in a number of agricultural pests. Using gene editing, nAChR α6 has been verified as a target for spinosyns in five insect species. Recently, a point mutation (G275E) in exon 9 of nAChR α6 was identified in spinosad-resistant strains of Thrips palmi and Tuta absoluta. To date, no in vivo functional evidence has been obtained to support that this mutation is involved in spinosyn resistance in lepidopteran pests. In this study, the G275E mutation was introduced into the nAChR of Spodoptera exigua using clustered regularly interspaced short palindromic repeats (CRISPR) / CRISPR-associated protein 9 (Cas9) gene-editing technology. Reverse transcriptase-polymerase chain reaction and sequencing confirmed that this mutation was present in exon 9 of the nAChR transcripts in the edited 275E strain. The results of bioassays showed that the 275E strain was highly resistant to spinosad (230-fold) and spinetoram (792-fold) compared to the unedited background strain, directly confirming that the G275E mutation of the nAChR α6 subunit confers high levels of spinosyn resistance in S. exigua. Inheritance analysis showed that the resistance trait is autosomal and incompletely recessive. This study employs a reverse genetics approach to validate the functional role played by the G275E mutation in nAChR α6 of S. exigua in spinosyns resistance and provides another example of the use of CRISPR/Cas9 gene-editing technology to confirm the role played by candidate target site mutations in insecticide resistance.

Synthesis and larvicidal activity against Culex pipiens pallens of new triazole derivatives of phrymarolin from Phryma leptostachya L.

Twelve new triazole derivatives of Phrymarolin were prepared from Phrymarolin I and the structures of all the derivatives were fully characterized by (1)H-NMR, (13)C-NMR and MS spectral data analyses. Larvicidal activities against 4rd instar larvae of Culex pipiens pallens of these Phrymarolin analogues were assayed. Although the triazole derivatives of Phrymarolin showed certain larvicidal activity, they showed lower activity than Phrymarolin I. The typical non-natural groups triazole substituents reduced the larvicidal activity of Phrymarolin derivatives.

Larvicidal activity of lignans from Phryma leptostachya L. against Culex pipiens pallens.

The larvicidal activity of crude petroleum ether, ethyl acetate, and methanol extracts of the whole plants of Phryma leptostachya L. was assayed for its toxicity against the early fourth instar larvae of Culex pipiens pallens. The larval mortality was observed after 24 h of exposure. Among three solvent extracts from Phyrma leptostachya L., the petroleum ether extract exhibited the best larvicidal activity. The corresponding LC50 values of petroleum ether, ethyl acetate, and methanol extracts were 3.23, 5.23, and 61.86 ppm against the early fourth instar larvae of Culex pipiens pallens. The petroleum ether extract was successively subjected to column chromatography and preparative high performance liquid chromatography, and yielded the three lignans, phrymarolin-I, haedoxane A, and haedoxane E, which were isolated and identified as new mosquito larvicidal compounds. Phrymarolin-I, haedoxane A, and haedoxane E showed high larvicidal activity, for which the lethal doses LC50 were estimated at 1.21, 0.025, and 0.15 ppm against the early fourth instar larvae of Culex pipiens pallens, respectively. The structures were elucidated by analyses of IR, UV, MS, and NMR spectral data. This is the first report on the mosquito larvicidal activity of the three compounds, phrymarolin-I, haedoxane A, and haedoxane E from Phyrma leptostachya L.