液相色谱-掺杂辅助大气压光电离质谱测定海洋沉积物中的植物甾醇

引用本文: 王愉宁, 陈军辉, 何秀平, 王九明, 辛明, 王保栋, 王小如. 液相色谱-掺杂辅助大气压光电离质谱测定海洋沉积物中的植物甾醇[J]. 分析化学, 2021, 49(2): 282-291. doi: 10.19756/j.issn.0253-3820.201595 shu

Citation: WANG Yu-Ning, CHEN Jun-Hui, HE Xiu-Ping, WANG Jiu-Ming, XIN Ming, WANG Bao-Dong, WANG Xiao-Ru. Determination of Phytosterols in Marine Sediment by Liquid Chromatography-Dopant-assisted Atmospheric Pressure Photoionization Mass Spectrometry[J]. Chinese Journal of Analytical Chemistry, 2021, 49(2): 282-291. doi: 10.19756/j.issn.0253-3820.201595 shu

液相色谱-掺杂辅助大气压光电离质谱测定海洋沉积物中的植物甾醇

1.
海洋生物资源与环境研究中心, 自然资源部海洋生态环境科学与技术重点实验室, 自然资源部第一海洋研究所, 青岛 266061;
2.
青岛海洋科学与技术国家实验室, 海洋生态与环境科学功能实验室, 青岛 266071;
3.
厦门华厦学院, 厦门 361024

通讯作者: 陈军辉,E-mail:jhchen@fio.org.cn

基金项目:
国家自然科学基金委-山东省联合基金项目（Nos.U1706217，U1606404）资助。

摘要: 海洋沉积物中的植物甾醇生物标志物常被用于指示海洋沉积有机物的来源、反演海洋生态和环境演变过程。本研究采用非水反相液相色谱-大气压光电离质谱联用技术（LC-APPI-MS），建立了一种同步测定海洋沉积物中多种常见植物甾醇类化合物的新方法。首先，阐明了植物甾类化合物的APPI一级质谱分析特征，在正离子模式下，植物甾醇类化合物易于形成稳定的[M+H-H₂O]⁺、[M+H-H₂]⁺和[M+H-2H₂]⁺特征离子峰；在二级质谱分析过程中，主要经过i异裂形成丰富的碎片离子峰。其次，优化了LC-APPI-MS检测条件，采用反相C₁₈柱分离，以纯甲醇为流动相，甲苯作为APPI掺杂剂辅助电离，可实现沉积物中植物甾醇类化合物的高灵敏检测。本方法抗基质干扰能力强，具有良好的线性关系（R²≥0.9990）、回收率（86.4%~94.9%）和重复性（RSDs≤8.3%）。采用本方法对莱州湾表层沉积物中的植物甾醇类化合物进行检测，所有样品中均检出了菜籽甾醇、岩藻甾醇和β-谷甾醇等6种甾醇类化合物，总含量在4.21~12.91 μg/g范围内，其中β-谷甾醇的含量最高。本方法操作简单、灵敏度高，是测定海洋沉积物中植物甾醇类生物标志物的有效方法。

关键词:

English

Determination of Phytosterols in Marine Sediment by Liquid Chromatography-Dopant-assisted Atmospheric Pressure Photoionization Mass Spectrometry

1.
Marine Bioresource and Environment Research Center, Key Laboratory of Marine Eco-Environmental Science and Technology, First Institute of Oceanography, Ministry of Natural Resources, Qingdao 266061, China;
2.
Laboratory for Marine Ecology and Environmental Science, Qingdao National Laboratory for Marine Science and Technology, Qingdao 266071, China;
3.
Xiamen Huaxia University, Xiamen 361024, China

Corresponding author: CHEN Jun-Hui, jhchen@fio.org.cn

Received Date: 10 October 2020
Revised Date: 02 December 2020
Fund Project:
Supported by the National Natural Science Foundation of China-Shandong Joint Fund for Marine Ecology and Environmental Sciences (Nos.U1706217, U1606404).

Abstract: Phytosterol biomarkers in marine sediments are often used to indicate the source of the sedimentary organics in the ocean, and to reflect the evolution of marine ecosystem and environment. In this study, a novel method for simultaneous determination of common phytosterols in marine sediments by non-aqueous reversed-phase liquid chromatography-atmospheric pressure photoionization mass spectrometry (LC-APPI-MS) was established. First, the APPI-MS characteristics of phytosterols were clarified. Under the positive APPI mode, phytosterols tended to produce stable characteristic ion peaks such as[M+H-H₂O]⁺,[M+H-H₂]⁺ and[M+H-2H₂]⁺. In the process of APPI-MS², abundant fragment ion peaks were produced mainly through i-heterolysis. Second, LC-APPI-MS conditions were optimized, and a reversed-phase C₁₈ column was used to separate phytosterols with pure methanol as mobile phase and toluene as APPI ionization dopant, which could realize high sensitivity of detection for phytosterols in sediments. Furthermore, the method showed strong matrix interference resistance ability, good linear relationship (R² ≥ 0.9990), high recovery rate (86.4%-94.9%) and good repeatability (RSDs ≤ 8.3%). Finally, the proposed method was applied to detect common phytosterols in the surface sediment of Laizhou Bay in China, and several sterols, such as brassicasterol, fucosterol and sitosterol, etc., were detected in every sediment sample. The total concentration of sterols was 4.21-12.91 μg/g, among which the concentration of sitosterol was the highest. To sum up, the developed LC-APPI-MS method was a powerful tool for determination of common phytosterols in marine sediments, with easy-operation and high sensitivity.

Key words:

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

液相色谱-掺杂辅助大气压光电离质谱测定海洋沉积物中的植物甾醇

通讯作者: 陈军辉,E-mail:jhchen@fio.org.cn

English

Determination of Phytosterols in Marine Sediment by Liquid Chromatography-Dopant-assisted Atmospheric Pressure Photoionization Mass Spectrometry

Corresponding author: CHEN Jun-Hui, jhchen@fio.org.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

液相色谱-掺杂辅助大气压光电离质谱测定海洋沉积物中的植物甾醇

通讯作者: 陈军辉,E-mail:jhchen@fio.org.cn

English

Determination of Phytosterols in Marine Sediment by Liquid Chromatography-Dopant-assisted Atmospheric Pressure Photoionization Mass Spectrometry

Corresponding author: CHEN Jun-Hui, jhchen@fio.org.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs