Skip to main page content
U.S. flag

An official website of the United States government

Dot gov

The .gov means it’s official.
Federal government websites often end in .gov or .mil. Before sharing sensitive information, make sure you’re on a federal government site.

Https

The site is secure.
The https:// ensures that you are connecting to the official website and that any information you provide is encrypted and transmitted securely.

Access keys NCBI Homepage MyNCBI Homepage Main Content Main Navigation
. 2023 May 13;9(5):e16245.
doi: 10.1016/j.heliyon.2023.e16245. eCollection 2023 May.

Preparation of core-shell MOF@MOF nanoparticle as matrix for the analysis of rhubarb anthraquinones in plasma by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Shi-Jun Yin  1 , Hua Chen  1 , Shengpeng Wang  2 , Yitao Wang  2 , Feng-Qing Yang  1
Affiliations

Preparation of core-shell MOF@MOF nanoparticle as matrix for the analysis of rhubarb anthraquinones in plasma by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry

Shi-Jun Yin et al. Heliyon. .

Abstract

A core-shell structure UiO-66-(OH)2@UiO-66-NH2 (MOF@MOF) nanoparticle was synthesized through a simple hydrothermal method and employed as an adsorbent and laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS) matrix for the quantitative analysis of rhubarb anthraquinones (RAs). The properties of the materials were characterized by field emission scanning electron microscopy, transmission electron microscopy, energy-dispersive X-ray spectroscopy, X-ray powder diffraction, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, thermogravimetric analysis, and Brunauer-Emmett-Teller. The results indicate that MOF@MOF is regular octahedral structure with a size distribution of about 100 nm, having large BET specific surface area (920 m2/g). Using the MOF@MOF as a matrix shows lower background interference, higher sensitivity, and better storage stability than that of traditional matrices. The MOF@MOF matrix exhibits excellent salt tolerance even under a NaCl concentration of 150 mM. Then, the enrichment conditions were optimized, and the adsorption time of 10 min, adsorption temperature of 40 °C and adsorbent amount of 100 μg were selected. In addition, the possible mechanism of MOF@MOF as an adsorbent and matrix was discussed. Finally, the MOF@MOF nanoparticle was employed as a matrix for the sensitive MALDI-TOF-MS analysis of RAs in spiked rabbit plasma, and the recoveries are in the range of 88.3-101.5% with RSD ≤9.9%. In short, the novel MOF@MOF matrix has demonstrated its potential in the analysis of small-molecule compounds in biological samples.

Keywords: Core-shell structure; Laser desorption/ionization; Mass spectrometry analysis; Metal-organic framework; Rhubarb anthraquinone.

PubMed Disclaimer

Conflict of interest statement

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Figures

Fig. 1
Fig. 1
(a) Schematic diagram of the preparation of UiO-66-(OH)2@UiO-66-NH2; SEM images of (b) UiO-66-(OH)2 and (c) UiO-66-(OH)2@UiO-66-NH2; (d) TEM image and (e) elemental mapping images of UiO-66-(OH)2@UiO-66-NH2; EDS results of (f) UiO-66-(OH)2 and (g) UiO-66-(OH)2@UiO-66-NH2.
Fig. 2
Fig. 2
(a) The XRD spectra of UiO-66-(OH)2 and UiO-66-(OH)2@UiO-66-NH2; (b) The FT-IR spectra of UiO-66-(OH)2, UiO-66-NH2, and UiO-66-(OH)2@UiO-66-NH2; The XPS spectra of UiO-66-(OH)2@UiO-66-NH2: (c) full spectrum, (d) C 1s, (e) N 1s, (f) O 1s, (g) Zr 3 d; (h) The TGA result and (i) nitrogen adsorption-desorption isotherm of UiO-66-(OH)2 and UiO-66-(OH)2@UiO-66-NH2.
Fig. 3
Fig. 3
The effect of (a) incubation time, (b) temperature, (c) the amount of material and (d) storage stability of UiO-66-(OH)2@UiO-66-NH2 on the intensity of emodin ([M+H]+ at m/z 271, 250 ng/mL) (n = 3).
Fig. 4
Fig. 4
(a) The calibration plot of EMO ([M+H]+ at m/z 271) after enrichment treatment using UiO-66-(OH)2@UiO-66-NH2 as the adsorbent and matrix (n = 3); Mass spectra of EMO with different concentrations of (b)1000, (c) 500, (d) 250, (e) 125, and (f) 62.5 ng/mL after enrichment treatment. EMO, emodin.
Fig. 5
Fig. 5
Mass spectra of 250 ng/mL of EMO using (a) UiO-66-(OH)2, (d) UiO-66-NH2, and (g) UiO-66-(OH)2@UiO-66-NH2 as adsorbent and matrix; Mass spectra of 250 ng/mL of CHR using (b) UiO-66-(OH)2, (e) UiO-66-NH2, and (h) UiO-66-(OH)2@UiO-66-NH2 as adsorbent and matrix; Mass spectra of 250 ng/mL of PHY using (c) UiO-66-(OH)2, (f) UiO-66-NH2, and (i) UiO-66-(OH)2@UiO-66-NH2 as adsorbent and matrix, respectively. EMO, emodin; CHR, chrysophanol; PHY, physcion.
See this image and copyright information in PMC

References

    1. Levander F., James P. Automated protein identification by the combination of MALDI MS and MS/MS spectra from different instruments. J. Proteome Res. 2005;4(1):71–74. - PubMed
    1. McMillen J., Gutierrez D., Judd A., Spraggins J., Caprioli R. Enhancement of tryptic peptide signals from tissue sections using MALDI IMS post ionization (MALDI-2) J. Am. Soc. Mass Spectrom. 2021;32(10):2583–2591. - PubMed
    1. Nakashima Y., Setou M. Distribution of antisense oligonucleotides in rat eyeballs using MALDI imaging mass spectrometry. Mass Spectrom. 2018;7(1):A0070. - PMC - PubMed
    1. Wang Z.X., Zhang Q.Q., Shen H.L., Yang P.Y., Zhou X.W. Optimized MALDI-TOF MS strategy for characterizing polymers. Front. Chem. 2021;9 - PMC - PubMed
    1. Kim S., Kwon S., Kim Y. Graphene oxide derivatives and their nanohybrid structures for laser desorption/ionization time-of-flight mass spectrometry analysis of small molecules. Nanomaterials. 2021;11(2):288. - PMC - PubMed