TY - JOUR
T1 - Synergistic Effect of Metal-Organic Framework/Gallic Acid in Enhanced Laser Desorption/Ionization Mass Spectrometry
AU - Wu, Jie
AU - Ouyang, Dan
AU - He, Yanting
AU - Su, Hang
AU - Yang, Baichuan
AU - Li, Jing
AU - Sun, Qianqian
AU - Lin, Zian
AU - Cai, Zongwei
N1 - Funding Information:
This work was supported from the National Natural Science Foundation of China (21675025, 21974021, and 91843301) and the Natural Science Foundation of Fujian Province (2018J01683).
Publisher copyright:
© 2019 American Chemical Society
PY - 2019/10/16
Y1 - 2019/10/16
N2 - Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has become an indispensable tool for high-throughput analysis of macromolecules, but many challenges still remain in detection of small molecules due to the severe matrix-related background interference in the low-molecular-weight ranges (MW < 700 Da). Herein, a gallic acid (GA)-functionalized zirconium 1,4-dicarboxybenzene metal-organic framework (MOF) (denoted as UiO-66-GA) was designed to serve as a new substrate, and a novel strategy on the basis of the synergistic effect of MOF and GA was developed to enhance the LDI process. In comparison with conventional organic matrices, the UiO-66-GA substrate showed superior LDI performance in the analysis of a wide variety of molecules including amino acids, unsaturated fatty acids, bisphenols (BPs), oligosaccharides, peptides, protein, and polyethylene glycol (PEG) of various average molecular weights from 200 to 10000. Perfluorooctanoic sulfonate (PFOS) was used to evaluate the ability of quantitative analysis, and its corresponding limit of detection as low as 1 fmol was achieved. High sensitivity and good salt tolerance of the UiO-66-GA-assisted LDI-MS were allowed to determine ultratrace PFOS in the spiked human urine and serum samples. In addition, the synergistic mechanism of MOF and GA in the enhanced LDI process was investigated by comprehensively comparing GA-and its analogue-functionalized UiO-66, and the results revealed that two aspects contributed to the enhanced LDI process: (1) an enhancement in the metal-phenolic coordination system of UiO-66-GA promoted laser absorption and energy transfer; (2) introduction of carboxyl and hydroxyl groups of GA onto UiO-66 facilitated the LDI process in both positive and negative ion modes. This work expands a new domain for the MOF applications and provides a promising alternative for various molecule analyses.
AB - Matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) has become an indispensable tool for high-throughput analysis of macromolecules, but many challenges still remain in detection of small molecules due to the severe matrix-related background interference in the low-molecular-weight ranges (MW < 700 Da). Herein, a gallic acid (GA)-functionalized zirconium 1,4-dicarboxybenzene metal-organic framework (MOF) (denoted as UiO-66-GA) was designed to serve as a new substrate, and a novel strategy on the basis of the synergistic effect of MOF and GA was developed to enhance the LDI process. In comparison with conventional organic matrices, the UiO-66-GA substrate showed superior LDI performance in the analysis of a wide variety of molecules including amino acids, unsaturated fatty acids, bisphenols (BPs), oligosaccharides, peptides, protein, and polyethylene glycol (PEG) of various average molecular weights from 200 to 10000. Perfluorooctanoic sulfonate (PFOS) was used to evaluate the ability of quantitative analysis, and its corresponding limit of detection as low as 1 fmol was achieved. High sensitivity and good salt tolerance of the UiO-66-GA-assisted LDI-MS were allowed to determine ultratrace PFOS in the spiked human urine and serum samples. In addition, the synergistic mechanism of MOF and GA in the enhanced LDI process was investigated by comprehensively comparing GA-and its analogue-functionalized UiO-66, and the results revealed that two aspects contributed to the enhanced LDI process: (1) an enhancement in the metal-phenolic coordination system of UiO-66-GA promoted laser absorption and energy transfer; (2) introduction of carboxyl and hydroxyl groups of GA onto UiO-66 facilitated the LDI process in both positive and negative ion modes. This work expands a new domain for the MOF applications and provides a promising alternative for various molecule analyses.
KW - LDI-MS
KW - macromolecules
KW - small molecules
KW - synergistic effect
KW - UiO-66-GA
UR - http://www.scopus.com/inward/record.url?scp=85073012584&partnerID=8YFLogxK
U2 - 10.1021/acsami.9b11100
DO - 10.1021/acsami.9b11100
M3 - Journal article
C2 - 31529951
AN - SCOPUS:85073012584
SN - 1944-8244
VL - 11
SP - 38255
EP - 38264
JO - ACS Applied Materials and Interfaces
JF - ACS Applied Materials and Interfaces
IS - 41
ER -