Citation: LIANG Qian, LI Shu-Ming, GUAN Xi-Liang, DANG Fu-Quan, ZHANG Zhi-Qi, ZHANG Jing. A Covalent Organic Framework Material Decorated with Gold Nanoparticles as Novel Matrix for Matrix-assisted Laser Desorption/Ionization Mass Spectrometry Analysis of Small Organic Molecules[J]. Chinese Journal of Analytical Chemistry, ;2021, 49(10): 1713-1721. doi: 10.19756/j.issn.0253-3820.211162 shu

A Covalent Organic Framework Material Decorated with Gold Nanoparticles as Novel Matrix for Matrix-assisted Laser Desorption/Ionization Mass Spectrometry Analysis of Small Organic Molecules

Key Laboratory of Bioanalytical Chemistry of Shaanxi Province, School of Chemistry & Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China

Corresponding author: ZHANG Jing, zhangjing8902@snnu.edu.cn
Received Date: 4 March 2021
Revised Date: 17 July 2021

Fund Project: Supported by the National Natural Science Foundation of China (No.22074086), the Fundamental Research Funds for the Central Universities, China (No.gk202005003) and the Science and Technology Plan of Xi'an, China (No.GXYD5.3).

Matrix-assisted laser desorption/ionization mass spectrometry (MALDI-MS) has become a promising analytical technology for large molecular weight molecules compounds, however, the interference of matrix-related ion peaks from the conventional matrix restricts the application of MALDI-MS in low molecular weight (LMW) organs (<500 Da). Although multiple exploration has been conducted in this region, it is still difficult to directly detect some molecules, such as low-molecular carbohydrate, which is a challenge to direct analysis without any enrichment because of its neutral property and difficulty in ionization. Herein, the in-situ Au nanoparticles (AuNPs) covalently embedded covalent organic frameworks (COFs) with sulfide cantilever (TTB-COF) were applied as a novel kind of matrix for direct analysis of various small organic molecules by MALDI-MS. The advantages of COFs such as abundant π-π periodic structure, suitable pore distribution, and increasing strong adsorption in the near UV region enable COFs be employed for various LMW organic analytes in cimprison with conventional matrix α-cyano-4-hydroxycinnamic acid (CHCA). Secondly, the addition of AuNPs not only facilitated the energy adsorption and desorption/ionization efficiency, but also provided an enrichment detection of sulfide molecules (LODs of thiabendazole as 5.0 nmol/L). Additionally, the synergistic effect between spatial confined COFs with sulfide cantilever and in-situ homogeneously distributed AuNPs solved the aggregation problem of inorganic nanoparticles during the evaporation preparation, which guaranteed the low background signals and improved the desorption/ionization efficiency. Therefore, after optimization of the synthetic conditions, Au-TTB-COF as a new matrix had an extremely low detection limit for small saccharides molecules as 11.0 nmol/L. Furthermore, Au-TTB-COF with strong salt tolerance and good reproducibility was applied to direct analysis of LMW molecules in the complex samples, such as glucose in serum samples, lactose in milk and thiabendazole in soft drinks. These results indicated that this metal-organic composites as MALDI-MS matrix had great potential in sensitive and specific detection of LMW organic chemicals in complex samples.
- Covalent organic frameworks,
- Gold nanoparticles,
- Matrix,
- Small saccharides molecule,
- Mass spectrometry
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