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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Derivatization-Assisted Acoustic Ejection Mass Spectrometry for High-Throughput FAHFA Prescreening

Na An,Peng-Cheng Mei,Ao Li,Xiu-Feng Fu,Xin-Ze Wu,Han-Peng Jiang,Quan-Fei Zhu,Yu-Qi Feng

Fatty acid esters of hydroxy fatty acids (FAHFAs) are bioactive lipids with significant structural diversity and potential health benefits, playing crucial roles in metabolic regulation, inflammation, and insulin sensitivity. However, the low abundance of FAHFAs in biological samples (0.1% to 0.001% of free fatty acids) and the wide range of molecular polarities (ClogP values from 0.26 to 18.24) across short-chain to long-chain FAHFAs pose substantial challenges for high-throughput screening. Here, we developed a novel high-throughput prescreening strategy, termed DAEMS (derivatization-assisted acoustic ejection mass spectrometry), which integrates chemical derivatization with acoustic ejection mass spectrometry (AEMS). By leveraging the ultrafast analysis speed of AEMS (1–3 samples per second) and the sensitivity enhancement of N,N-dimethylethylenediamine (DMED) derivatization, DAEMS enables the screening of over 2800 potential FAHFA species in less than 2 h─significantly faster than the conventional LC-MRM MS-based screening approaches. The DAEMS strategy achieved 83% coverage and 79% accuracy in preliminary screening compared to the LC-MRM MS. Furthermore, we also revealed novel oxidized FAHFA species in edible fungi for the first time, suggesting potential biosynthesis involving oxylipins or oxidative modifications. This study demonstrates DAEMS as a promising tool for rapid FAHFA prescreening, and the discovery of oxidized FAHFAs provides new insights into FAHFA diversity and metabolism.

研究领域: 生物化学 · 代谢组学 · 分析化学
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JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY · 2025 · IF 6.2

One-Step Labeling and Purification: Accelerating FAHFA Detection in Vegetable Oils via Chemoselective Probe-Assisted LC–MS

Xin-Ze Wu,Kai-Wen Tan,Xu Zhang,Jun-Jie Tan,Na An,Fang Cong,Wenbin Wu,Azamat Temerdashev,Quan-Fei Zhu,Hong Wang,Yu-Qi Feng

Fatty acid esters of hydroxy fatty acids (FAHFAs) are emerging bioactive lipids in edible oils, but their trace-level presence and matrix complexity hinder accurate analysis. Here, we designed a novel chemoselective probe piperazine-modified silica (SiO2-PP) that specifically captures FAHFAs while removing almost totally triglycerides in a one-step labeling reaction. The probe enabled single-batch sample pretreatment within 30 min, integrating capture, purification, and signal amplification. Coupled with liquid chromatography–mass spectrometry, the method achieved high sensitivity (LOD: 0.0039–0.033 ng/mL) and enabled quantification of 47 FAHFA isomers in 47 vegetable oil samples, with concentrations ranging from 0.56 to 1.76 × 104 ng/g. Five dominant isomers (e.g., 10-OAHSA) were identified, with olive and peanut oils exhibiting the highest FAHFA concentrations. This approach provides a promising platform for high-throughput functional lipid profiling, effectively overcoming the inefficiencies of traditional methods while significantly enhancing the assessment of vegetable oil quality.

研究领域: 分析化学 · 脂质组学 · 食品科学 · 生物活性脂质 · 质谱分析
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MICROCHEMICAL JOURNAL · 2026 · IF 5.2

A three-tier screening strategy-based targeted UPLC-ESI-MS/MS platform delineates the FAHFA landscape in lipid extracts of fruit seeds and pits

Long Xu,Xiang Liang,Mengqing Xiao,Walter Vetter,Shuaishuai Yang,Kai Chen,Fashan Wei,Xiaoling Yu,Xia Shen,Mingjiang Zhu

A 3-tier screening strategy-based LC-MS/MS profiles FAHFAs in fruit seeds and pits. • Fruit seed oils contain significantly higher total FAHFA levels than pit oils. • Bayberry seed oil is the richest FAHFA source (168 ng/g) among all samples. • OAHOA and PAHOA are identified as predominant FAHFA species in fruit seeds. Fatty acid esters of hydroxy fatty acids (FAHFAs) are bioactive lipids with anti-inflammatory and antidiabetic properties, but their occurrence in fruit seeds and pits remain largely unexplored. Here, untargeted lipidomics and fatty acid profiling were firstly employed to characterize the overall lipid landscape and precursor pools. Subsequently, a targeted platform was established by integrating solid-phase extraction (SPE) enrichment, N , N -dimethylethylenediamine (DMED) derivatization, and UPLC-ESI-MS/MS in multiple reaction monitoring (MRM) mode. Using a predictive MRM database covering 2116 theoretical FAHFA species and a three-tier screening strategy (two MRM filtering rounds followed by retention time and signal-to-noise evaluation), 49 endogenous species were identified in 17 fruit seeds and 4 fruit pits. It was found that fruit seed oils contained significantly higher total FAHFA levels than pit oils (3–168 vs. 1–35 ng/g), with bayberry seed oil showing the highest content (168 ng/g). Predominant species included OAHOA, LAHLA, PAHOA, and OAHSA. This first comprehensive FAHFA profile, achieved via the three-tier strategy, establishes seed oils as notable dietary sources of these lipids and offers a robust platform for discovering bioactive lipids in complex plant matrices. Download: Download high-res image (113KB) Download: Download full-size image

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