尖端Fe_(2)O_(3)纳米棒驱动的高性能质谱分析用于构建PM_(2.5)暴露鼠的代谢指纹图谱

Tip Fe_2O_(3) Nanorods Driven High-performance Mass Spectrometry Analysis for Constructing Metabolic Fingerprint of PM_(2.5)-exposed Mice

激光解吸电离质谱(LDI MS)对复杂样本中代谢物的检测受限于基质材料的选择和设计.结构调控可以进一步提高基质材料的检测性能.尖端结构能够有效增强电荷转移和光热转换效率,有望提升纳米材料在LDI MS代谢物检测中的电离和解吸能力.因此,本文构建了基于尖端结构Fe_(2)O_(3)纳米棒(Nr-Fe_(2)O_(3))的LDI MS平台.Nr-Fe_(2)O_(3)具有纳米表面粗糙、光吸收强、可增强电离能力和光热转换等特性,显著提高了LDI MS对代谢物检测的选择性和灵敏度[与Fe_(2)O_(3)纳米颗粒(Np-Fe_(2)O_(3))相比,信号增强3~10倍;与商业化有机基质相比,信号增强10~15倍)].在实际样本检测中,将基质材料Nr-Fe_(2)O_(3)用于直径<2.5μm的大气颗粒物(PM_(2.5))暴露前后大鼠的血清代谢指纹图谱采集,并联合T检验成功筛选了暴露前后具有显著波动的差异性代谢特征值.本文方法为后续设计高性能基质材料提供了新思路,也为PM_(2.5)暴露毒理学研究提供了一定的理论支撑.

The performance of laser desorption/ionization mass spectrometry(LDI MS) is greatly limited by the choice and design of the matrix.Structural design of the matrix can further improve the detection performance.The sharper corner can effectively enhance charge transfer and photothermal conversion efficiency,thereby improving the ionization and desorption ability in LDI MS.Therefore,we constructed an LDI MS platform based on tip Fe_2O_(3) nanorods(Nr-Fe_2O_3).The nanoscale surface roughness,strong light absorption,enhanced ionization ability,and photothermal conversion properties of Nr-Fe_2O_(3) have improved the selectivity and sensitivity of LDI-MS for metabolite detection[3—10 fold signal enhancement compared with Fe_2O_(3) nanoparticles(Np-Fe_2O_3),10—15 fold signal enhanced compared to commercial organic matrices].In the serum samples,the Nr-Fe_2O_(3) was used to collect serum metabolic fingerprints of fine particulate matter(PM_(2.5))-exposed mice,and screen the fluctuating features by T-test.Our approach guides us in matrix design for LDI MS metabolic analysis and provides the theoretical support for subsequent PM_(2.5) exposure toxicology research.