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Matrix-assisted laser desorption/ionization mass spectrometry (MALDI MS) has been extensively used in the analysis
of large molecules, such as biomolecules and synthetic polymers, since the late 1980s. Over the years, MALDI MS has
been an indispensible tool in proteomics, genomics, metabolomics, glycomics, lipidomics, MS imaging, etc. However, small
molecules (m/z <1000) analysis is limited in MALDI applications because of the background interference of conventional small
organic matrixes in the low mass range. The present study aims to develop novel interference-free matrixes for the analysis of
small molecules in biological samples, as well as the living biosystem. Some examples, including (1) high salt-tolerant, and low
background N-(1-naphthyl) ethylenediamine dihydrochloride (NEDC), was applied as a matrix to measure the level of glucose
in rat brainmicrodialysates by MALDI-TOF MS in combination with in vivo microdialysis will be shown. By monitoring
the ion signals of [glucose+Cl]
-
in the mass spectra, a low detection limit of 10 �¼M for glucose in 126 mM NaCl, which
is a typical component in artificial cerebrospinal fluid, without prior sample purification was achieved; (2) N-(1-naphthyl)
ethylenediamine dinitrate (NEDN), was employed as a matrix to analyze small molecules such as oligosaccharides, peptides,
metabolites and explosives using negative ion MALDI-TOF MS. For saccharides, the 500 amol LOD was achieved. This matrix
was applies in the structural identification of oligosaccharides with post-source decay MALDI-MS; (3) 1-naphthylhydrazine
hydrochloride (NHHC) has been selected as an ideal matrix to detect small molecules. This salt-tolerant matrix could be
applied for the high sensitive glucose analysis with an ultra-low limit of detection of 1 amol. With NHHC, glucose in serum
and the biomarker homogentisic acid in urine were successfully determined by MALDI-TOF MS in negative ion mode; (4)
2,3,4,5-tetra(3�,4�-dihydroxylphenyl)thiophene (DHPT), was designed and synthesized as the MALDI matrix for the selectively
analysis of small molecular amines in positive ion mode. A wide range of small amines, such as �²-agonists, amino acids,
peptides, alkaloid, vitamine B and aromatic amines was analyzed and the low picomole limit-of-detection was obtained. DHPT
was also applied for the qualitative analysis of the amine metabolites and quantitative determination of creatinine in urine;
(5) Carbon nanodots was applied as a new MALDI matrix in both positive- and negative-ion modes. A wide range of small
molecules including amino acids, peptides, fatty acids, as well as �²-agonists and neutral oligosaccharides were analyzed. The
glucose and uric acid in real samples were quantitatively determined by the internal standard method.
Biography
Zongxiu Nie has completed his PhD from Wuhan Institute of Physics and Mathematics, Chinese Academy of Sciences and postdoctoral studies from Institute of Atomic and Molecular Sciences, Academia Sinica and Department of Chemistry, Purdue University. He is the professor of chemistry in Institute of Chemistry, Chinese Academy of Sciences. He has published more than 42 papers in reputed journals of Mass Spectrometry.
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