金属有机骨架衍生氧化物材料作为MALDI-TOF MS基质用于氨基酸分析

MOF-derived Oxides Used as MALDI-TOF MS Matrix for the Determination of Amino Acids

目的:为了拓展基质辅助激光解吸电离飞行时间质谱(MALDI-TOF MS)在小分子检测领域的应用,本文合成了三种金属有机骨架衍生氧化物,作为MALDI-TOF MS新型基质,用于高效分析氨基酸。方法:本文以三种金属有机骨架材料(MOFs)为前驱体,通过TiO_(2)纳米涂层修饰,并经过煅烧得到其金属氧化物,用作MALDI质谱基质,研究其在氨基酸检测方面的优势,探究基质浓度对检测结果的影响,考察材料的重现性和定量分析能力。结果:三种MOF-衍生金属氧化物材料相比其前驱体MOFs和TiO_(2)NPs,分析氨基酸(Pro、Ile、His和Try)时具有信噪比高、离子强度高和重现性好的优点;其中CrO@TiO_(2)表现最佳,基质浓度为0.1 mg·mL^(-1),定量检测Ile和His时线性范围为0.001~0.1 mg·mL^(-1)。结论:本文制备的MOF-衍生金属氧化物材料作为MALDI-TOF MS基质,实现了对4种氨基酸的同时精确检测,具有在氨基酸及小分子代谢物检测方面进一步的拓展和应用价值。

Objective:To expand the application of matrix assisted laser desorption ionization time of flight mass spectrometry(MALDI-TOF MS)analysis technology in the field of small molecules detection,three metal-organic frameworks(MOFs)derived oxides were synthesized and explored as the novel matrix for efficient analysis of amino acids by MALDI-TOF MS.Methods:Three MOF-derived oxides were synthesized by TiO_(2)nano coating modification and calcination,with MOFs as precursors.When MOF-derived oxides used as MALDI matrix,their advantages in the determination of amino acids were studied,the influence of matrix concentration on detection results was explored,and the reproducibility and quantitative analysis ability of the materials were investigated in this study.Results:MOF-derived oxides exhibited better performances compared with MOFs and TiO_(2)NPs when detection of proline(Pro),isoleucine(Ile),histidine(His)and tyrosine(Try)under the same detection conditions,including high signal to noise ratio,high ion intensity and good reproducibility.Meanwhile,Cr_(2)O_(3)@TiO_(2)performed best in three MOF-derived oxides,it had the advantage of a wide linear range(0.001~0.1 mg·mL^(−1))in quantitative detection of Ile and His,with 0.1 mg·mL^(−1) of matrix concentration.Conclusion:Four amino acids could be simultaneously and accurately detected by MOF-derived oxides synthesized in this work,these materials had the value of further expansion and application for the detection of amino acids and other small etabolites as MALDI-TOF MS matrix.