Small biomolecules(m/z<500)are the material basis of organisms and participate in life activities,but their comprehensive and accurate detection in complex samples remains a challenge.Matrix-assisted laser desorpti...Small biomolecules(m/z<500)are the material basis of organisms and participate in life activities,but their comprehensive and accurate detection in complex samples remains a challenge.Matrix-assisted laser desorption/ionization mass spectrometry(MALDI-MS)is a powerful detection tool for molecular analysis with high throughput.The development of a new matrix is essential to improve the efficiency of the MALDI-MS for molecular compound detection.In this work,the sandwich-like gold nanoparticles@mesoporous silica nanocomposite@silver nanoparticles(Au@MSN@Ag)nanospheres were prepared by layer-by-layer super-assembly strategy,and can be used as a novel matrix for the quantitative detection and enrichment of small biomolecules by LDI-MS.The sandwich-like nanospheres form a unique plasma resonant cavity that effectively absorbs the laser energy,while the homogeneous mesoporous structure of MSN can lock the analyte,which is essential for efficient LDI of small molecules.Compared to traditional matrices,Au@MSN@Ag shows the advantages of low background,wide application range,high sensitivity,super high salt and protein tolerance,and good stability.For example,the detection limit of glucose was as low as 5 fmol,and showed a good linear relationship in the range of 1−750μg/mL.Au@MSN@Ag assisted LDI-MS allows the enrichment and detection of small molecules in traditional Chinese medicine(TCM)without derivatization and purification,classification of herbs using the accurate quantitative results oligosaccharides,and identification of gelatin by amino acid content.This research could help in designing more efficient nanostructure matrices and further explored the application of LDI-MS.展开更多
基金the National Key R&D Program of China(Nos.2019YFC1604600,2017YFA0206901,2019YFC1604601,2017YFA0206900,and 2018YFC1602301)the National Natural Science Foundation of China(Nos.21705027,2197402951808328,61903235,42007218,and 51703109)+5 种基金the Major Scientific and Technological Innovation Project of Shandong(Nos.2018CXGC1406,2019JZZY010457 and 2019JZZY020309)The Natural Science Foundation of Shanghai(18ZR1404700)Construction Project of Shanghai Key Laboratory of Molecular Imaging(18DZ2260400)Shanghai Municipal Education Commission(Class II Plateau Disciplinary Construction Program of Medical Technology of SUMHS,2018-2020)The ability establishment of sustainable use for valuable Chinese medicine resources(2060302)The natural Science Foundation of Shandong Province,China(ZR2020QE228).
文摘Small biomolecules(m/z<500)are the material basis of organisms and participate in life activities,but their comprehensive and accurate detection in complex samples remains a challenge.Matrix-assisted laser desorption/ionization mass spectrometry(MALDI-MS)is a powerful detection tool for molecular analysis with high throughput.The development of a new matrix is essential to improve the efficiency of the MALDI-MS for molecular compound detection.In this work,the sandwich-like gold nanoparticles@mesoporous silica nanocomposite@silver nanoparticles(Au@MSN@Ag)nanospheres were prepared by layer-by-layer super-assembly strategy,and can be used as a novel matrix for the quantitative detection and enrichment of small biomolecules by LDI-MS.The sandwich-like nanospheres form a unique plasma resonant cavity that effectively absorbs the laser energy,while the homogeneous mesoporous structure of MSN can lock the analyte,which is essential for efficient LDI of small molecules.Compared to traditional matrices,Au@MSN@Ag shows the advantages of low background,wide application range,high sensitivity,super high salt and protein tolerance,and good stability.For example,the detection limit of glucose was as low as 5 fmol,and showed a good linear relationship in the range of 1−750μg/mL.Au@MSN@Ag assisted LDI-MS allows the enrichment and detection of small molecules in traditional Chinese medicine(TCM)without derivatization and purification,classification of herbs using the accurate quantitative results oligosaccharides,and identification of gelatin by amino acid content.This research could help in designing more efficient nanostructure matrices and further explored the application of LDI-MS.
