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丙溴磷对映异构体在柑橘中的残留分析及选择性降解

董超 李晶 杨秦 张耀海 赵其阳 焦必宁

董超, 李晶, 杨秦, 张耀海, 赵其阳, 焦必宁. 丙溴磷对映异构体在柑橘中的残留分析及选择性降解[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0063
引用本文: 董超, 李晶, 杨秦, 张耀海, 赵其阳, 焦必宁. 丙溴磷对映异构体在柑橘中的残留分析及选择性降解[J]. 农药学学报. doi: 10.16801/j.issn.1008-7303.2021.0063
Chao DONG, Jing LI, Qing YANG, Yaohai ZHANG, Qiyang ZHAO, Bining JIAO. Residual analysis and selective degradation of profenofos enantiomers in citrus[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0063
Citation: Chao DONG, Jing LI, Qing YANG, Yaohai ZHANG, Qiyang ZHAO, Bining JIAO. Residual analysis and selective degradation of profenofos enantiomers in citrus[J]. Chinese Journal of Pesticide Science. doi: 10.16801/j.issn.1008-7303.2021.0063

丙溴磷对映异构体在柑橘中的残留分析及选择性降解

doi: 10.16801/j.issn.1008-7303.2021.0063
基金项目: 柑橘类水果质量安全保障技术应用及示范 (2019YFC1605604);农业农村部现代农业 (柑橘) 产业技术体系建设专项 (CARS-26);国家柑橘及热带作物产品质量安全风险评估专项 (GJFP2018004)
详细信息
    作者简介:

    董超,男,硕士,E­mail:DC027689@163.com

    通讯作者:

    焦必宁,通信作者 (Author for correspondence),男,研究员,研究方向为果蔬质量安全与检测技术,E-mail:Bining_Jiao@163.com

  • 中图分类号: O657.63;TQ450.26

Residual analysis and selective degradation of profenofos enantiomers in citrus

  • 摘要: 基于手性固定相/高效液相色谱- 串联质谱结合QuEChERS前处理技术建立了柑橘中丙溴磷对映体残留的分析方法,并通过田间试验研究了丙溴磷对映异构体在柑橘中的选择性降解行为。柑橘样品经乙腈快速提取,多壁碳纳米管净化。丙溴磷对映体采用ND(2)-RH手性色谱柱分离,正离子多反应监测模式 (MRM) 检测,基质匹配标准曲线法定量。方法验证结果表明,丙溴磷对映体在2.5~250 μg/L质量浓度范围内线性关系良好 (r ≥ 0.999 6),方法定量限 (LOQ) 为5 μg/kg。在3个添加水平(5、100、500 μg/kg)下,丙溴磷对映体的平均回收率为76%~83%,相对标准偏差 (RSD) 为2.6%~6.0%。田间试验结果表明,丙溴磷对映体在柑橘中的降解规律符合一级反应动力学方程,(+)-丙溴磷和 (−)-丙溴磷的降解半衰期分别为12.53 d和14.14 d;在施药后30 d,丙溴磷2个对映体的对映体分数值达到0.43,表明其在柑橘中的降解存在明显的对映体选择性差异。
  • 1  丙溴磷结构式

    1.  The structural formula of profenofos

    图  1  丙溴磷在ND(2)-RH柱上的拆分结果

    流动相为V(甲醇) : V(水) = 70 : 30,流速0.2 mL/min,柱温35 ℃。

    Figure  1.  Resolution of profenofos on ND(2)-RH columns

    Mobile phase was consist of V(methanol) : V(water) = 70 : 30, flow rate was 0.2 mL/min and column temperature was 35 ℃.

    图  2  丙溴磷对映体在ND(2)-RH柱上流出顺序

    Figure  2.  Elution order of the enantiomers of profenofos on ND(2)-RH column

    图  3  九种不同组合净化剂的比较

    A~D为10 mg多壁碳纳米管 (内径分别为8~10 nm,10~20 nm,20~30 nm,30~50 nm);E为50 mg PSA;F为100 mg PSA;G为50 mg GCB;H为100 mg GCB;I为50 mg GCB+50 mg PSA。

    Figure  3.  Comparison of 9 different cleanup sorbent combinations

    A-D represents multi-walled carbon nanotubes with different inner diameters of 8-10 nm, 10-20 nm, 20-30 nm and 30-50 nm, respectively; E, F, G, H and I represents 50 mg PSA, 100 mg PSA, 50 mg GCB, 100 mg GCB and 50 mg GCB+50 mg PSA, respectively.

    图  4  丙溴磷对映体在柑橘中的降解曲线及对映体分数 (EF值) 变化曲线

    A. (+)-丙溴磷的降解动态;B. (−)-丙溴磷的降解动态;C. 对映体分数。

    Figure  4.  Degradation curve and curve of EF value of profenofos enantiomers in citrus

    A. Degradation dynamic of (+)-profenofos; B. Degradation dynamic of (−)-profenofos; C. Enantiomeric fraction.

    表  1  七种商品化的多糖类手性固定相色谱柱

    Table  1.   Seven different kinds of chiral column of polysaccharide-based chiral stationary phases

    商品名
    Trade name
    手性固定相
    Chiral stationary phase
    粒径
    Particle size/μm
    规格
    Size
    Lux Amylose-2 直链淀粉-三 (5-氯-2-甲基苯基氨基甲酸酯) Amylose-tris (5-chloro-2-methylphenyl carbamate) 3 150 mm × 2.0 mm
    Lux Cellulose-1 纤维素-三 (3,5-二甲基苯基氨基甲酸酯) Cellulose-tris (3,5-dimethylphenyl carbamate) 3 150 mm × 2.0 mm
    Lux Cellulose-4 纤维素-三 (4-氯-3-甲基苯基氨基甲酸酯) Cellulose-tris (4-chloro-3-methylphenyl carbamate) 3 150 mm × 2.0 mm
    Lux Cellulose-3 纤维素-三 (4-甲基苯甲酸酯) Cellulose-tris (4-methylbenzoate) 3 150 mm × 2.0 mm
    ND(2)-RH 直链淀粉-三 (3,5-二甲基苯基氨基甲酸酯) Amylose-tris (3,5-dimethylphenyl carbamate) 3 150 mm × 2.1 mm
    NS(2)-RH 直链淀粉-三 ((S)-α-甲基戊基氨基甲酸酯) Amylose-tris ((S)-α-methylpentyl carbamate) 3 150 mm × 2.1 mm
    NZ(2)-RH 直链淀粉-三 (3-氯-4-甲基苯基氨基甲酸酯) Amylose-tris (3-chloro-4-methylphenyl carbamate) 3 150 mm × 2.1 mm
    下载: 导出CSV

    表  2  丙溴磷检测的质谱参数

    Table  2.   Mass spectrometry parameters of profenofos determination

    母离子
    Precursor ion, m/z
    子离子
    Product ion, m/z
    锥孔电压
    Declustering potential/V
    碰撞能
    Collision energy/eV
    入口电压
    Entrance potential/V
    出口电压
    Collision cell exit potential/V
    374.9304.9120251010.5
    347.2171010.5
    下载: 导出CSV

    表  3  流动相中甲醇所占体积比和柱温对ND(2)-RH柱上丙溴磷对映体分离的影响

    Table  3.   Effects of volume proportion of methanol in mobile phase and column temperatures on the enantiomeric separation of profenofos on ND(2)-RH column

    参数
    Parameters
    k1k2αRs
    流动相中甲醇所占体积比
    Volume proportion of methanol in mobile phase
    85%3.151
    80%4.811
    75%7.017.551.080.65
    70%10.7412.251.141.51
    65%18.5321.141.141.83
    柱温 Temperature20 ℃21.8924.401.111.31
    26 ℃16.1718.091.121.38
    30 ℃13.3315.021.131.43
    35 ℃10.7412.251.141.51
    40 ℃8.9410.201.141.57
    下载: 导出CSV

    表  4  丙溴磷对映体的线性范围

    Table  4.   The linear range of the enantiomers of profenofos

    分析物
    Analyte
    基质
    Matrix
    线性范围
    Linear range/(μg/L)
    标准校正曲线
    Standard calibration curve
    基质效应
    Matrix effect/%
    斜率
    Slope
    截距
    Intercept
    相关系数
    r
    (+)-丙溴磷
    (+)-profenofos
    乙腈 Acetonitrile 2.5~250 174982 65243 0.9996
    全果 Whole fruit 2.5~250 164390 24990 0.9998 −6.1
    果肉 Pulp 2.5~250 193604 63619 0.9999 +10.6
    (−)-丙溴磷
    (−)-profenofos
    乙腈 Acetonitrile 2.5~250 175308 45683 0.9996
    全果 Whole fruit 2.5~250 174735 25699 0.9999 −0.3
    果肉 Pulp 2.5~250 192350 76951 0.9998 +9.7
    下载: 导出CSV

    表  5  丙溴磷对映体的添加回收率及相对标准偏差

    Table  5.   Recoveries and RSD of profenofos enantiomers

    分析物
    Analyte
    添加水平
    Spiked
    level/
    (μg/kg)
    果肉
    Pulp
    全果
    Whole fruit
    平均
    回收率
    Average
    recovery/%
    相对标准
    偏差
    RSD/%
    平均
    回收率
    Average
    recovery/%
    相对标准
    偏差
    RSD/%
    (+)-丙溴磷
    (+)-profenofos
    5 81 4.2 76 5.4
    100 81 3.0 82 3.2
    500 81 2.6 82 3.4
    (−)-丙溴磷
    (−)-profenofos
    5 82 3.9 78 6.0
    100 80 3.7 82 3.9
    500 81 3.0 83 5.6
    下载: 导出CSV

    表  6  柑橘全果中丙溴磷对映体的降解方程

    Table  6.   Dissipation equations of profenofos enantiomers in the whole fruit of citrus

    对映体
    Enantiomers
    降解方程
    Dissipation equations
    R2t1/2/daPb
    (+)-丙溴磷
    (+)-profenofos
    ct=0.339e−0.054t0.8112.53 ± 0.130.001
    (−)-丙溴磷
    (−)-profenofos
    ct=0.367e−0.049t0.7914.14 ± 0.29
    注: a半衰期以平均值 ± 标准偏差表示 (n = 3)。bP值通过单因素方差分析检验 (95%置信区间) 对比两个对映异构体t1/2计算。Note: aThe values of half-lives were expressed as the mean ± standard deviation (n = 3). bP value was calculated by One-way analysis of variance test (95% confidence interval) to compare the t1/2 of 2 enantiomers.
    下载: 导出CSV
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  • 收稿日期:  2020-09-02
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