High performance anion exchange-integral pulse method for detection of free glucosamine in amino-oligosaccharins pesticides
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摘要: 建立了采用高效阴离子交换-积分脉冲法检测氨基寡糖素母药及水剂中游离氨基葡萄糖含量的方法。以DionexAminoTrap Column (氨基捕获柱)和DionexCarboPac PA100阴离子交换柱为分离柱，用17 mmol/L的氢氧化钠溶液洗脱目标物游离氨基葡萄糖，200 mmol/L的氢氧化钠溶液冲洗氨基寡糖素，流速为1.0 mL/min，总分析时间为30 min。在最优分离条件下，可消除氨基寡糖素对氨基葡萄糖的干扰，氨基葡萄糖的检出限可达到0.01 mg/L (S/N=3)，标准线性范围为0.02~10 mg/L，相关系数为0.9999。对市售的氨基寡糖素母药及水剂进行检测，3次平行样品相对标准偏差小于1.9%，添加回收率在90%~99%之间，检测结果准确可靠。该方法可用于氨基寡糖素母药及水剂中游离氨基葡萄糖的检测，对氨基寡糖素农药质量判断具有一定指导意义。
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关键词:
- 阴离子交换-积分脉冲 /
- 氨基寡糖素 /
- 氨基葡萄糖 /
- 离子色谱 /
- 壳寡糖
Abstract: A high performance anion exchange-integral pulse method was established to determine the content of free glucosamine in amino-oligosaccharin technical concentrates and aqueous solution. Using the DionexAminoTrap Column and DionexCarboPac PA100 anion exchange column as the separation column, the target free glucosamine was eluted with 17 mmol/L sodium hydroxide, and the chitosan oligosaccharide was flushed by 200 mmol/L sodium hydroxide. The flow rate was 1.0 mL/min, and the total analysis time was 30 min. Under the optimal separation conditions, the interference of chitosan oligosaccharides on glucosamine could be eliminated. The detection limits of glucosamine reached 0.01 mg/L (S/N=3), the calibration curve ranged from 0.02 to 10 mg/L, and the correlation coefficients was 0.999 9. For the analysis of commercially available amino-oligosaccharin technical concentrates and aqueous solution at 3 replicates, the relative standard deviation was less than 1.9%, and the spiked recoveries were between 90%-99%, which indicated that the established method was accurate and reliable. Therefore, this method could be used for the detection of free glucosamine in amino-oligosaccharin technical concentrates and aqueous solution, and could provide method for the quality evaluation of the amino-oligosaccharin pesticides. -
图 1 分析系统中增加氨基捕获柱前(A)后(B)对比图
Figure 1. The comparison diagram before(A) and after(B) adding an amino trap column in the analysis system
图 2 不同柱温下氨基葡萄糖与杂质离子分离图谱
Figure 2. Separation spectrum of glucosamine and impurity ions at different column temperatures
图 3 不同淋洗液(氢氧化钠溶液)浓度下氨基葡萄糖与杂质分离图谱
Figure 3. The separation of glucosamine and impurities with different eluent (sodium hydroxide solution) concentrations
表 1 淋洗液梯度程序
Table 1. Eluent gradient program
时间Time/
min流速Flow rate/
(mL/min)淋洗液 Eluent A：水A: Water
(18.25 MΩ.cm)/%氢氧化钠溶液
Sodium hydroxide solution/%B: 100 mmol/L C: 200 mmol/L 0.0 1.0 83 17 0 18.0 1.0 83 17 0 18.1 1.0 0 0 100 25.0 1.0 0 0 100 25.1 1.0 83 17 0 30.0 1.0 83 17 0 
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表 2 氨基寡糖素母药及水剂样品分析结果
Table 2. Analysis results of the amino-oligosaccharin technical concentrates and aqueous solution samples
氨基寡糖素
Amino-oligosaccharin稀释倍数
Dilution factor检测结果Test results/
(mg/kg)样品结果Sample results/
(mg/kg)平均结果Average results/
(mg/kg)相对标准偏差
RSD/%母药
Technical concentratesSample1#-1 1000 1.4566 1456.6 1457.1 0.50 Sample1#-2 1.4501 1450.1 Sample1#-3 1.4647 1464.7 水剂
Aqueous solutionSample1#-1 200 0.1829 36.6 36.7 1.8 Sample1#-2 0.1802 36.0 Sample1#-3 0.1869 37.4
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表 3 氨基寡糖素母药及水剂样品添加回收结果
Table 3. The spiked recoveries for amino-oligosaccharin technical concentrates and aqueous solution
氨基寡糖素(含量)amino-oligosaccharin
(content)/(mg/kg)添加水平Spiked level/
(mg/kg)添加回收结果Spiked test results/
(mg/kg)回收率
Recovery/%相对标准偏差
RSD/%母药 (1457.1 mg/kg)
Technical concentrates (1457.1 mg/kg)200 1642.8 93 1.9 1500 2903.4 96 0.93 3000 4423.5 99 0.75 水剂 (36.7 mg/kg)
Aqueous solution (36.7 mg/kg)5 41.2 90 1.9 30 65.8 97 0.98 70 105.2 98 0.92
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