Scientia Agricultura Sinica ›› 2022, Vol. 55 ›› Issue (9): 1790-1799.doi: 10.3864/j.issn.0578-1752.2022.09.008

• PLANT PROTECTION • Previous Articles     Next Articles

Synthesis and Bioactivity of Sex Pheromone Analogues of Protoschinia scutosa

LI Hui1(),YIN ShiCai2,GUO ZongXiang2,MA HaoYun1,REN ZiQi1,3,SHE DongMei1,MEI XiangDong1,*(),NING Jun1,*()   

  1. 1State Key Laboratory for Biology of Plant Diseases and Insect Pests, Institute of Plant Protection, Chinese Academy of Agricultural Sciences, Beijing 100193
    2Gaomi Municipal Bureau of Agriculture and Rural Affairs, Gaomi 261500, Shandong
    3College of Life Science, Northeast Forestry University, Harbin 150040
  • Received:2021-11-09 Revised:2021-12-02 Online:2022-05-01 Published:2022-05-19
  • Contact: XiangDong MEI,Jun NING E-mail:13470007293@163.com;xdmei@ippcaas.cn;jning@ippcaas.cn

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Abstract:

【Background】In recent years, with the significant increase in the area planted with the newly introduced crop quinoa, Protoschinia scutosa, which prefers quinoa, has gradually increased and become a major pest of quinoa, posing a potential threat to the production of agriculture in China.【Objective】The objective of this study is to synthesize two different types of analogues modified with the polar group of the sex pheromone (Z)-hexadec-11-en-1-yl acetate (Z11-16:Ac), as the parent structure, and determine the biological activity, providing a theoretical basis for using sex pheromones and analogues for the green control of P. scutosa.【Method】The sex pheromone precursor (Z)-hexadec-11-en-1-ol (Z11-16:OH) was used as the raw material, and triethylamine was used as the acid-binding agent (4-dimethylaminopyridine was added as the catalyst for the reaction with the anhydride), and the esterification reactions with 2-bromopropionyl chloride, 2-chloroacetyl chloride, difluoroacetic anhydride, trifluoroacetic anhydride, methacryloyl chloride, and 2-butenoyl chloride were carried out respectively, the halogen atom modified analogues (K1-K4) and carbon chain end double bond modified analogues (K5-K6) were synthesized, separated and purified by column chromatography. Different concentrations (0.001, 0.01, 0.1, 1, 10, 100 μg·μL-1) of sex pheromone analogues (K1-K6) were prepared by gradient dilution. The EAG response values of analogues K1-K6 were measured by direct stimulation on the male tentacles of P. scutosa using different concentrations of analogues. Sex pheromone analogue trap lures were prepared by adding different doses of analogues to the sex pheromone. The field trapping trials were conducted in the summer of 2021 in Yanqing, Beijing, and the analogue activity was analyzed by counting the male moth in the traps.【Result】As the stimulation concentration increased from 0.001 to 100 μg·μL-1, the electrophysiological response values of male tentacles to analogues K1 to K5 showed a gradual increase trend. Male tentacles responded most strongly to the compound (Z)-hexadec-11-en-1-yl 2-bromopropanoate (K1), with a response value of 1.34 mV at 100 μg·μL-1. The EAG activities of analogues K5 and K6 were relatively poor, with EAG response values of 0.67 and 0.57 mV at 100 μg·μL-1, respectively. All the six analogues synthesized showed good biological activity in field trapping experiments. K5 had the highest average trapped number of 35.00 heads at an additive level of 100 μg, which was significantly higher than the sex pheromone control. The average number of trapped adults of analogue K1 was 32.33 heads at an additive level of 10 μg during the whole period (15 d) of field trapping tests, which was significantly higher than the sex pheromone control.【Conclusion】The analogues K1 and K5 showed potentiation activity and can be used as potentiators of sex pheromones as verified by EAG and field trials. The addition of different doses of analogues K2, K3, K4 and K6 exhibited comparable activity to sex pheromones. This study provides a scientific and theoretical basis for the green control of P. scutosa.

Key words: Protoschinia scutosa, sex pheromone analogue, chemical synthesis, bioactivity, chemical control of insect behavior

Fig. 1

Synthetic route of the analogue (Z) hexadec-11-en-1-yl 2-bromopropanoate (K1)"

Fig. 2

Synthetic route of the analogue (Z)-hexadec-11-en-1-yl (E)-but-2-enoate (K5)"

Table 1

Number of different doses of sex pheromone analogues"

性信息素类似物
Sex pheromone analogue		 剂量Dose (μg)
0.1 1 10 100 1000
K1 A1 A2 A3 A4 A5
K2 B1 B2 B3 B4 B5
K3 C1 C2 C3 C4 C5
K4 D1 D2 D3 D4 D5
K5 E1 E2 E3 E4 E5
K6 F1 F2 F3 F4 F5

Fig. 3

The structures of sex pheromone analogues K1 to K6"

Table 2

The EAG relative response value of direct stimulation to P. scutosa at different concentrations of analogues K1 to K6"

性信息素类似物
Sex pheromone analogue		 直接刺激EAG相对响应值EAG relative response value of direct stimulation (m<BOLD>V</BOLD><BOLD>)</BOLD>
0.001 μg·μL-1 0.01 μg·μL-1 0.1 μg·μL-1 1 μg·μL-1 10 μg·μL-1 100 μg·μL-1
K1 0.07±0.02c 0.13±0.003c 0.14±0.03c 0.29±0.04bc 0.44±0.07b 1.34±0.09a
K2 0.04±0.05d 0.16±0.07cd 0.20±0.02cd 0.31±0.07bc 0.51±0.07ab 0.72±0.04a
K3 0.05±0.01c 0.11±0.09bc 0.15±0.06bc 0.27±0.06bc 0.42±0.09ab 0.75±0.08a
K4 0.04±0.03d 0.11±0.05d 0.24±0.05cd 0.34±0.02bc 0.56±0.06ab 0.75±0.06a
K5 0.06±0.01d 0.18±0.01cd 0.23±0.02c 0.29±0.02b 0.38±0.03a 0.67±0.05a
K6 0.08±0.11ab 0.08±0.04ab -0.04±0.17b -0.12±0.17b 0.34±0.16ab 0.57±0.07a

Fig. 4

Population dynamics of P. scutosa was monitored by sex pheromone"

Table 3

Field trapping effect of sex pheromone and analogues of P. scutosa"

性信息素类似物
Sex pheromone analogue		 平均诱捕数量/诱捕器/15 d Average number of trapped adults/trap/15 d
性信息素SP 0.1 μg 1 μg 10 μg 100 μg 1000 μg
K1 14.00±2.00bc 8.00±2.08c 11.67±1.45bc 32.33±0.67a 18.67±1.45b 12.00±2.08bc
K2 10.00±2.31a 7.33±3.53a 14.33±3.84a 14.67±7.51a 13.33±3.71a 8.67±3.33a
K3 3.00±1.00a 11.33±2.73a 8.67±3.53a 4.67±2.73a 3.67±2.03a 1.67±0.33a
K4 9.00±3.21a 15.67±4.81a 8.67±0.33a 6.33±1.76a 6.00±0.58a 4.67±2.33a
K5 16.00±3.21bc 8.67±0.88c 11.67±1.45bc 16.67±1.20bc 35.00±4.62a 22.33±1.76b
K6 7.67±2.03a 20.00±4.16a 16.67±2.67a 7.33±3.53a 13.33±3.71a 9.33±2.67a

Fig. 5

Trapping effect of sex pheromone SP and added analogues treatment A3 and E4 in the field trial"

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