\r汪 日燕1，刘海培1，孙传强1，韩文念2，贾明正2，蒋学慧1

AuthorsHTML:\r汪 日燕1，刘海培1，孙传强1，韩文念2，贾明正2，蒋学慧1

AuthorsListE:\rWang Yan¹，Liu Haipei¹，Sun Chuanqiang ¹，Han Wennian ²，Jia Mingzheng ²，Jiang Xuehui¹

AuthorsHTMLE:\rWang Yan¹，Liu Haipei¹，Sun Chuanqiang ¹，Han Wennian ²，Jia Mingzheng ²，Jiang Xuehui¹

Unit:\r1. 天津大学精密仪器与光电子工程学院，天津 300072；
2. 天津国科医工科技发展有限公司，天津 300399


Unit_EngLish:\r1. School of Precision Instrument and Optoelectronics Engineering，Tianjin University，Tianjin 300072，China；
2. Tianjin Guoke Medical Engineering and Technology Development Company Limited，Tianjin 300399，China

Abstract_Chinese:\r基于自主研制的三重四极杆质谱仪，设计开发整套谱图信息提取分析方法，包括原始数据去噪、色谱解析与识别、谱峰匹配、曲线拟合等算法．设计一种依赖曲线信号与噪声自身数据特点的算法对原始谱图噪声进行自动去除，采用平滑Z-score法与多段斜率法相结合的算法对目标化合物质量色谱峰进行解析，实现对复杂基质样品中拖尾峰、肩峰和低浓度峰的准确识别，对待测谱峰进行保留时间校正，并对曲线拟合权重进行讨论，最终建立标准曲线进行定量分析．以人体血清中25-羟基维生素D检测实验为例，采用自开发算法，完成了一套液相色谱-三重四极杆质谱多反应监测(MRM)扫描模式下的配套定量分析算法包．计算结果表明，选取1/X²权重进行线性拟合，维生素D₂和维生素D₃的检出限分别为1.1mg/L、1.5mg/L，定量下限分别为3.7mg/L、5.1mg/L，线性相关系数达0.998以上．连续6d对高低两个浓度的维生素D₂和维生素D₃质控品测量其变异系数(CV值)在7% 以内，满足日间精密度要求，实验结果验证了该分析算法的准确性．对人体血清中脂溶性维生素A和维生素E以及血浆中甲氧基肾上腺素(MN)和甲氧基去甲肾上腺素(NMN)两个临床应用的数据结果进行定量分析，进一步验证算法的可行性及普适性．本算法具有自适应性，减少了优化时间，提高了谱图数据处理自动化水平，可为临床相关疾病检测诊断提供工具．

Abstract_English:\rOn the basis of a self-developed triple quadrupole mass spectrometer，a complete set of spectral information extraction and analysis method is designed and developed. This method includes original data denoising，chromatographic analysis and identification，spectral peak matching，curve fitting，and other algorithms. A kind of algorithm which depends on data signals itself and noise characteristic is designed to automatically remove the noise from original mass spectrometry．Smooth Z-score method is used with the multistage slope algorithm of target compounds，chromatographic peak of quality analysis，implementation of complex matrix samples，shoulder peak and low concentration peak，and tailing peak of accurate identification．Then，spectrum peak retention time correction is performed，and the measurement and weights of curve fitting are discussed. Finally，a standard curve for quantitative analysis is established．Taking 25-hydroxy vitamin D in human serum as an example，a set of matching quantitative analysis algorithm package under the MRM scanning mode of liquid chromatography-triple quadrupole mass spectrometry was completed by using the self-developed algorithm．Calculation results show that when 1/X² weighted linear fitting was selected，the limits of detection for vitamin D₂ and vitamin D₃ were 1.1mg/L and 1.5mg/L，respectively，while the limits of quantitation were 3.7 mg/L and 5.1 mg/L，respectively，and their correlation coefficient was above 0.998．For six consecutive days，the coefficient of variation for vitamin D₂ and vitamin D₃ quality control products with high and low concentrations was within 7%，which met the requirements of intra-day precision．Experimental results verified the accuracy of the analysis algorithm．The results of two clinical applications of human serum fat-soluble vitamins A and E and plasma metanephrine and normetanephrine were quantitatively analyzed to further verify the feasibility and universality of the algorithm．This algorithm has self-adaptability，reduces optimization time，improves the automation level of spectral data processing，and can provide tools for the detection and diagnosis of clinically related diseases．

Keyword_Chinese:液相色谱-三重四极杆质谱(LC-MS/MS)；谱峰识别算法；定量分析；维生素D

Keywords_English:liquid chromatography triple quadrupole mass spectrometry(LC-MS/MS)；peak identification algorithm；quantita-tive analysis；vitamin D


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