Nanocomposites of boronic acid-functionalized magnetic multi-walled carbon nanotubes with flexible branched polymers as a novel desorption/ionization matrix for the capture and direct detection of cis-diol-flavonoid compounds coupled with MALDI-TOF-MS

Abstract

Novel boronic acid-functionalized magnetic multi-walled carbon nanotubes with flexible branched polymer (Fe₃O₄@MWCNTs@ε-PL@BA) nanocomposites were fabricated and applied as the desorption/ionization matrix for the MALDI-TOF-MS determination of low molecular weight flavonoids. The prepared nanocomposite was systematically characterized by various techniques. Compared to the traditional organic matrix, the proposed Fe₃O₄@MWCNTs@ε-PL@BA matrix has excellent ionization efficiency and low-background noise interference due to the MWCNTs unique electron-phonon interaction and the high introduction density of boronic acid functional groups. Good sensitivity and ultra-high salt tolerance of the Fe₃O₄@MWCNTs@ε-PL@BA-assisted MALDI-TOF-MS were permitted for the determination and quantification of flavonoids in actual samples. Noticeably, the limits of detection (LODs) for the target flavonoids were in the range 17-33 nM. The relative standard deviations (RSDs) of spot-to-spot and sample-to-sample (n = 10) were ≤ 9.8% and ≤ 10.1%, respectively. Furthermore, the wide linear ranges (0.1 - 500 µg/mL) and satisfactory calibration plot coefficients (R² > 0.99) of flavonoids were achieved by MALDI-TOF-MS with the Fe₃O₄@MWCNTs@ε-PL@BA matrix. Good recoveries (92-105.5%) were achieved for the target flavonoids in practical food samples. Hence, the prepared Fe₃O₄@MWCNTs@ε-PL@BA nanocomposites have applications in the selective and efficient capture of target flavonoids active biomolecules coupled with MALDI-TOF-MS determination in actual samples.

Keywords: Boronic acid; Flavonoids; MALDI-TOF-MS; Nanocomposite; Small biomolecules.