基于电喷雾静电场轨道阱质谱的24个邻苯二甲酸酯碎片离子解析

麻能轩, 吴梦雪, 杨宝海, 顾晨晨, 赵楠楠

doi:10.16155/j.0254-1793.2023.09.12

药物分析杂志 >

2023 , Vol. 43 >Issue 9: 1543 - 1552

DOI: https://doi.org/10.16155/j.0254-1793.2023.09.12

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基于电喷雾静电场轨道阱质谱的24个邻苯二甲酸酯碎片离子解析

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江苏豪森药业集团有限公司研究院,连云港 222069

第一作者 Tel:15061360717;E-mail:manx@hspharm.com

收稿日期: 2022-09-29

网络出版日期: 2024-06-24

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Fragment ions analysis of 24 phthalates based on electrospray electrostatic orbitrap mass spectrometry

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Research Institute of Jiangsu Hansoh Pharmaceutical Group Co., Ltd., Lianyungang 222069, China

Received date: 2022-09-29

Online published: 2024-06-24

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摘要

目的: 基于相容性研究中未知提取物和浸出物的结构鉴定需求,利用电喷雾静电场轨道阱质谱的分辨率优势,对24个邻苯二甲酸酯类化合物质谱信息进行采集,并对各碎片离子的结构形态及裂解途径进行解析。方法: 采用超高效液相色谱-四极杆/静电场轨道阱质谱法进行定性测定。色谱柱为Agilent Proshell 120EC-C₁₈色谱柱(100 mm×4.6 mm,2.7 μm);流动相A为0.1%乙酸水溶液,流动相B为甲醇,流动相C为乙腈;梯度洗脱。ESI正电离模式;喷雾电压3 500 V;鞘气流速7 L·min^-1,辅助气流速12 L·min^-1;离子传输管温度325 ℃;离子源温度320 ℃;采用一级全扫描和二级子离子扫描的数据采集模式。设置扫描分辨率120 000,全质量扫描范围m/z 50~1 000。结果: 24个邻苯二甲酸酯类化合物一级质谱响应良好,[M+H]⁺离子显著可见;二级碎片离子在高、中、低质荷比分布均匀,显示有强的m/z 149的特征峰,并不同程度伴生m/z 167、121、111、93等特征离子。在此基础上对样品溶液中检出的邻苯二甲酸酯类化合物完成了解析归属。结论: 本研究利用静电场轨道阱质谱的高分辨率优势,较为全面的阐明了典型的邻苯二甲酸酯的电喷雾质谱特征离子及其形态和来源,并以常见相容性研究材质检出组分为例证进行分析,进一步说明了深入了解邻苯二甲酸酯类质谱特征的重要性,因此能够从理论分析和实际应用2个方面为相容性研究中未知的提取物和浸出物的定性,尤其是邻苯二甲酸酯类未知杂质的结构鉴定提供了可靠的参考依据。

关键词： 包材相容性; 增塑剂; 邻苯二甲酸酯; 二级碎片离子; 质谱解析; 电喷雾静电场轨道阱质谱

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麻能轩, 吴梦雪, 杨宝海, 顾晨晨, 赵楠楠 . 基于电喷雾静电场轨道阱质谱的24个邻苯二甲酸酯碎片离子解析[J]. 药物分析杂志, 2023 , 43(9) : 1543 -1552 . DOI: 10.16155/j.0254-1793.2023.09.12

Abstract

Objective: Based on the structural identification requirements of unknown extracts and leachables in compatibility studies, the mass spectrometry information of 24 phthalate compounds was collected. The structure, morphology and fragmentation pathway of each fragment ion were analyzed in view of the advantage of high resolution orbitrap mass spectrometry. Methods: The qualitative determination was carried out by ultra-high performance liquid chromatography-quadrupole/electrostatic orbitrap mass spectrometry. The column was Agilent Proshell 120EC-C₁₈ column (100 mm×4.6 mm, 2.7 μm), and the mobile phase A was 0.1% acetic acid aqueous solution, B was methanol, C was acetonitrile. Gradient elution with flow rate 1.0 mL·min^-1 was used. Ionization mode was ESI+ and spray voltage was 3 500 V. Meanwhile, sheath gas flow rate was 7 L·min^-1 and auxiliary gas flow rate was 12 L·min^-1. The temperature of ion transfer tube and ion source were 325 ℃ and 320 ℃, respectively. The resolution was 120000. Results: The 24 phthalate compounds had good primary mass spectrometry responses, and [M+H]⁺ ions were clearly visible. Secondary fragment ions were evenly distributed at high, medium and low mass-to-charge ratios. Strong characteristic peak of m/z 149 was accompanied by other ions such as m/z 167, 121, 111, and 93. Benefiting from the systematic summary of fragment ions of single reference solution, the structure analysis of phthalates detected in the sample solution was completed. Conclusion: In this study, the advantage of high-resolution electrospray electrostatic orbitrap mass spectrometry was used to comprehensively elucidate the characteristic ions of typical phthalates, as well as their forms and sources. The detected unknown extracts and leachables in the materials of common compatibility studies showed the importance of in-depth understanding of the mass spectrometry characteristics of phthalates. It could provide a reliable reference for the characterization of unknown extracts and leachables in compatibility studies from both theoretical analysis and practical applications, especially the structural identification of unknown impurities of phthalates.

Key words： packaging compatibility; plasticizer; phthalates; secondary fragment ion; mass spectrometry analysis; electrospray electrostatic orbitrap mass spectrometry

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