色谱

色谱 ›› 2022, Vol. 40 ›› Issue (8): 712-720.DOI: 10.3724/SP.J.1123.2022.04002

• 特别策划:食品安全分离分析-功能性吸附材料专栏 • 上一篇    下一篇

金属有机框架材料UiO-67富集净化牛奶中孕激素残留

商伟伟, 索德成, 李桐, 杜秋玲, 蒋先鸿, 王培龙()   

  1. 中国农业科学院农业质量标准与检测技术研究所, 北京 100081
  • 收稿日期:2022-04-02 出版日期:2022-08-08 发布日期:2022-07-29
  • 通讯作者: 王培龙
  • 基金资助:
    国家自然科学基金(32172325);国家自然科学基金(21777189)

Metal-organic framework UiO-67-based enrichment and purification of progesterone residues in milk

SHANG Weiwei, SUO Decheng, LI Tong, DU Qiuling, JIANG Xianhong, WANG Peilong()   

  1. Institute of Quality Standards and Testing Technology for Agricultural Products, Chinese Academy of Agricultural Science, Beijing 100081, China
  • Received:2022-04-02 Online:2022-08-08 Published:2022-07-29
  • Contact: WANG Peilong
  • Supported by:
    National Natural Science Foundation of China(32172325);National Natural Science Foundation of China(21777189)

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摘要：

该文制备了一种比表面积大、稳定性好的金属有机框架材料(MOF)UiO-67,将其用于复杂牛奶基质中痕量孕激素的富集和净化。结合超高效液相色谱-四极杆/静电场轨道离子阱高分辨质谱(UHPLC-Q-Orbitrap HRMS),建立了同时测定牛奶中7种孕激素残留的检测方法。采用X射线光电子能谱(XPS)对UiO-67吸附孕激素后的元素谱图进行测试分析,通过对比结合能和官能团相对含量的变化证明了UiO-67与孕激素间发生了化学作用,并研究了UiO-67对1 mg/L和5 mg/L孕激素的吸附效果。考察并优化了吸附剂用量、洗脱溶剂类型和pH值等关键参数,评价了基质效应对孕激素质谱信号的影响。优化结果显示,选择吸附剂用量为40 mg,在样品溶液pH值为5时,用5 mL丙酮洗脱目标物就可获得满意的回收率。基质效应在20%之内,可忽略不计。在优化条件下,7种孕激素在1~100 μg/L范围内线性相关性良好,相关系数均达到0.99以上,方法的检出限(LOD)和定量限(LOQ)分别为0.06~0.30 μg/L和0.19~1.0 μg/L;在不同添加水平下,回收率为87.10%~105.58%,相对标准偏差为2.66%~9.64%。方法成功应用于实际牛奶样品中孕激素的测定,结果与SN/T 1980-2007标准得到的结果具有良好的吻合度。相比较已报道的牛奶中孕激素前处理技术和检测方法,该方法具有较高的灵敏度和满意的回收率,为今后这类材料在复杂基质中有毒有害物质的富集检测提供了新的借鉴思路。

关键词: 超高效液相色谱-四极杆/静电场轨道离子阱高分辨质谱, 样品前处理, 固相萃取, 金属有机框架材料, 孕激素

Abstract:

Progesterone functions as an endocrine-disrupting compound. Imitating endogenous hormones disrupt the animals’ hormone levels. The potential hazard of progesterone in milk cannot be neglected. Thus, research has focused on establishing an efficient and convenient pretreatment and analytical approach. In this study, a metal-organic framework (MOF) material UiO-67 was prepared, which possessed a large specific surface area and excellent stability. It was employed to enrich and purify trace progesterones in a complex milk matrix as a filler to integrate the solid phase extraction column. An approach based on MOF was developed using ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS). This approach could simultaneously determine seven kinds of progesterone residues in milk. The element spectra of UiO-67 were first measured and analyzed using X-ray photoelectron spectroscopy. The chemical interaction between UiO-67 and progesterone was proved by comparing the changes in binding energy and relative contents of functional groups, and the adsorption efficiency of 1 mg/L and 5 mg/L progesterones by UiO-67 was studied. The adsorption efficiencies of UiO-67 for 1 mg/L and 5 mg/L progesterones were 99.73%-99.95% and 88.87%-99.23%, respectively, according to the results. It proved the efficient adsorption of UiO-67 to progesterones and ensured that subsequent studies went smoothly. Furthermore, key parameters, such as the amount of sorbent, elution solvent type, and pH value, were examined and optimized to obtain optimal extraction recovery of the progesterones. Spiked concentrations of 50 μg/L were employed for extraction optimization. All experiments were performed three times. It also evaluated the matrix effect on mass spectrum signal of the progesterones. The optimized results showed that the seven progesterones could be satisfactorily recovered when the amount of adsorbent was 40 mg, pH value of the sample solution was 5, and elution solution was 5-mL acetone. Additionally, the matrix effect of progesterone in the milk sample was <20%. The matrix effect could be neglected using the aforementioned approach to extract and purify progesterones in milk. Finally, the seven progesterones showed good linearity between 1 and 100 μg/L under the optimized conditions, with linear correlation coefficients values >0.99. The limits of detection (LODs) ranged from 0.06 to 0.30 μg/L, and limits of quantification (LOQs) ranged from 0.19 to 1.0 μg/L, respectively. At various concentration levels of progesterones in milk, the recoveries were 87.10%-105.58%, with relative standard deviations of 2.66%-9.64%. Most importantly, the approach was successfully employed to determine progesterone levels in milk samples, with results in good agreement with the standard SN/T 1980-2007. The proposed approach had the advantages of high sensitivity and satisfactory accuracy compared with the reported pretreatment and detection approaches of progesterone in milk. Satisfactory experimental results can be obtained without the calibration by isotope inner standard. Meanwhile, considering the excellent performance of MOF materials in reducing matrix interference in complex samples, such the application of materials offers a new approach. It can be employed to enrich and detect hazards in a complex matrix in the future.

Key words: ultra-high performance liquid chromatography-quadrupole/electrostatic field orbitrap high resolution mass spectrometry (UHPLC-Q-Orbitrap HRMS), sample pretreatment, solid phase extraction, metal-organic framework material, progesterone

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