基于方差分析的质谱性能影响因素量化研究

Quantitative Research of Mass Spectrometry Performance Factors Based on Analysis of Variance

  • 摘要: 基于质谱的现场、实时、准确、快速检测技术研究大多集中于电离技术和分析检测方法,而关于质谱技术实际应用中影响灵敏度、重复性和一致性等性能指标的因素量化分析研究较少。通过气相色谱-电子轰击电离-质谱法对化学毒剂模拟剂甲基膦酸二甲酯(DMMP)进行240组条件实验,采用方差分析法量化色谱进样口温度、色谱-质谱接口传输线温度和离子源温度等因素的影响程度。单因素方差分析结果表明,进样口温度影响最显著、离子源温度次之、传输线温度影响较弱;多因素方差分析结果表明,进样口温度和离子源温度交互效应对信号强度影响显著。基于量化分析结果优化相关影响因素参数,对6个不同浓度的DMMP进行线性定量和检测重复性实验,优化参数后的信号强度提高近10倍,线性定量范围可覆盖1~50 mg/L,在20~50 mg/L浓度范围内的相对标准偏差(RSD)低于5%。因此,影响因素的方差分析量化研究可为提高质谱仪检测性能提供数据支持。

     

    Abstract: The in-situ, real time, accurate and rapid detection based on mass spectrometry mostly focus on ionization technology and analytical method. However, the quantitative research of mass spectrometry performance factors that affect sensitivity, repeatability and constancy in the application is rather little. 240 groups of condition experiments for dimethyl methylphosphonate (DMMP) were conducted with gas chromatography-electron ionization-mass spectrometry (GC-EI-MS), and the analysis of variance (ANOVA) method was used to quantitative the influence extent of the inlet temperature of gas chromatography, the transmission line temperature between GC and MS, and the ion source temperature. The results of single factor ANOVA showed that the average F-ratio and p-value were 59.56 and 3.2×10-4, 23.94 and 0.027, 68.12 and 0.022 (F0.05(3,8)=4.07, F0.05(4,10)=3.48 and the threshold of p-value is 0.05) for inlet temperature, transmission line temperature and ion source temperature, respectively. So through comparing the F-ratio and p-value, it could be included that inlet temperature was the most significant factor that affect the performance of MS, and ion source temperature was less, and transmission line temperature was least. The results of multi-factor ANOVA showed that F-ratio and p-value were 854.25 and 0, 112.79 and 0, 71.26 and 0 (F0.05(3,160)=2.60, F0.05(9,160)=1.88 and the threshold of p-value is 0.05) for inlet temperature, ion source temperature, the interaction between inlet and ion source temperature, respectively. So it could be further testified that the inlet temperature and ion source temperature were the significant factors. Experiments of linear quantify and repeatability based on the optimized factors was conducted with six different concentrations of DMMP. The results showed that linear quantify of GC-MS could cover 1.50 mg/L using the optimized factors, comparing with 10.50 mg/L of linear quantify without optimization. The average relative standard deviation (RSD) for DMMP with six different concentrations was about 20%, yet, RSD better than 5% could be achieved with 20.50 mg/L when using optimized factors. However, RSD without optimization was about 27%. The quantitative analysis of factors can provide data support for the enhancement of performance of mass spectrometry, especially for the sensitivity, linear quantify and repeatability.

     

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