基于四极杆-双压线形离子阱质谱的同步碎裂和累积技术研究  

Research on Simultaneous Fragmentation and Accumulation Technique Based on Quadrupole-Dual Pressure Linear Ion Trap Mass Spectrometer

作　　者：李畅[1] 谢洁 刘梅英[2,3] 黄泽建 戴新华[2] 江游 方向[2] 田地 LI Chang;XIE Jie;LIU Mei-Ying;HUANG Ze-Jian;DAI Xin-Hua;JIANG You;FANG Xiang;TIAN Di(College of Instrumentation&Electrical Engineering,Jilin University,Changchun 130061,China;Center for Advanced Measurement Science,National Institute of Metrology,Beijing 100029,China;Technology Innovation Center of Mass Spectrometry for State Market Regulation,Beijing 100029,China)

机构地区：[1]吉林大学仪器科学与电气工程学院,长春130061 [2]中国计量科学研究院前沿计量科学中心,北京100029 [3]国家市场监管技术创新中心(质谱),北京100029

出　　处：《分析化学》2023年第2期269-275,共7页Chinese Journal of Analytical Chemistry

基　　金：国家重点研发计划项目(No.2020YFF01014603);国家自然科学基金项目(No.21927812);中国计量科学研究院基本业务费项目(No.AKY1934)资助。

摘　　要：四极杆-线形离子阱(Quadrupole-linear ion trap,Q-LIT)串联质谱结合同步碎裂和累积技术(简称同步技术)相比于离子阱质谱具有更高的灵敏度和定量准确性。本研究针对离子阱在相同气压条件下无法同时使阱内离子的捕获与检测效率达到最佳的问题,研制了四极杆-双压线形离子阱(Quadrupole-dual pressurelinear ion trap,Q-DPLIT)串联质谱,并结合同步技术,进一步提高了灵敏度和准确性。此仪器由一个四极杆与两个双曲线形离子阱轴向串联,四极杆筛选前体离子进入离子阱Ⅰ,同时在离子阱Ⅰ上施加复合波形,使得前体离子的碎裂、产物离子的隔离和累积同时进行,产物离子被传输到离子阱Ⅱ中检测。改变引入离子阱Ⅰ的氦气流量,研究不同流量条件下离子阱捕获离子的能力,筛选最佳的分析条件。结果表明,Q-DPLIT和Q-LIT分别处于最佳条件时,Q-DPLIT捕获利血平产物离子的数量是Q-LIT的4.2倍;使用Q-DPLIT检测以100μg/mL VVFFGG肽段(m/z=625.3 amu)为基质的10~100 ng/mL GVFGVF目标肽段(m/z=625.3 amu)时,离子累积时间为0.1~10 s,使用同步技术测得目标产物离子(m/z=460.3 amu)信号强度相比于未使用此技术提升至1.3~10倍,线性相关系数从0.6693~0.9449提升至0.9942~0.9994。结合Q-DPLIT和同步技术可进一步提高灵敏度,降低基质的干扰,在复杂基质中痕量物质的分析应用中具有良好的应用前景。In this work,a quadrupole-dual pressure linear ion trap(Q-DPLIT)tandem mass spectrometer was developed and combined with a simultaneous technique to further improve the sensitivity and accuracy.The instrument consisted of a quadrupole and two hyperbolic ion traps in axial series.The precursor ions were filtered by the quadrupole into the linear ion trapⅠ(LITⅠ).At the same time,a composite waveform was applied to the LITI,so that the fragmentation of the precursor ions,isolation and accumulation of product ions occurred simultaneously.Then,the product ions were transferred to the linear ion trapⅡ(LITⅡ)for detection.By changing the helium flux introduced into LITⅠ,the ion trapping ability of the ion trap under different fluxes was investigated,and the optimal analysis condition was obtained.The results showed that the number of reserpine ions trapped by Q-DPLIT was 4.2 times as that of Q-LIT under the respective optimal conditions.The target peptide GVFGVF in concentrations ranging from 10 to 100 ng/m L with 100μg/m L VVFFGG as the matrix was detected by Q-DPLIT.The mass-to-charge ratios(m/z)of VVFFGG and GVFGVF were both 625.3 amu.The ion accumulation time was 0.1–10 s.The signal intensity of the target product ion(m/z=460.3 amu)measured by the simultaneous technique was improved by 1.3–10 times compared with that without this technique,and the linear correlation coefficient was increased from 0.6693–0.9449 to 0.9942–0.9994.The combination of Q-DPLIT and simultaneous technique could further improve the sensitivity and reduced the interferences of matrices.It was expected to achieve better analytical results in the analysis of trace substances in complex matrices in the future.

关 键 词：质谱 四极杆-双压线形离子阱 同步碎裂和累积技术 同分异构体 

分 类 号：O657.63[理学—分析化学]