title: Magnetite/Ceria-Codecorated Titanoniobate Nanosheet: A 2D Catalytic Nanoprobe for Efficient Enrichment and Programmed Dephosphorylation of Phosphopeptides.
abstract: Global characterization and in-depth understanding of phosphoproteome based on mass spectrometry (MS) desperately needs a highly efficient affinity probe during sample preparation. In this work, a ternary nanocomposite of magnetite/ceria-codecorated titanoniobate nanosheet (MC-TiNbNS) was synthesized by the electrostatic assembly of Fe3O4 nanospheres and in situ growth of CeO 2 nanoparticles on pre-exfoliated titanoniobate and eventually utilized as the probe and catalyst for the enrichment and dephosphorylation of phosphopeptides. The two-dimensional (2D) structured titanoniobate nanosheet not only promoted the efficacy of capturing phosphopeptides with enlarged surface area, but also functioned as a substrate for embracing the magnetic anchor Fe3O4 to enable magnetic separation and mimic phosphatase CeO2 to produce identifying signatures of phosphopeptides. Compared to single-component TiNbNS or CeO2 nanoparticles, the ternary nanocomposite provided direct evidence of the number of phosphorylation sites while maintaining the enrichment efficiency. Moreover, by altering the on-sheet CeO2 coverage, the dephosphorylation activity could be fine-tuned, generating continuously adjustable signal intensities of both phosphopeptides and their dephosphorylated tags. Exhaustive detection of both mono- and multiphosphorylated peptides with precise counting of their phosphorylation sites was achieved in the primary mass spectra in the cases of digests of standard phosphoprotein and skim milk, as well as a more complex biological sample, human serum. With the resulting highly informative mass spectra, this multifunctional probe can be used as a promising tool for the fast and comprehensive characterization of phosphopeptides in MS-based phosphoproteomics.
authors: †State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
authors: Qianhao
authors: Q
authors: Min
authors: †State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
authors: Siyuan
authors: S
authors: Li
authors: †State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
authors: Xueqin
authors: X
authors: Chen
authors: §Petrochemical Research Chair, Chemistry Department, College of Science, King Saud University, P.O. Box 2455, Riyadh 11451, Saudi Arabia.
authors: E S
authors: ES
authors: Abdel-Halim
authors: †State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
authors: Li-Ping
authors: LP
authors: Jiang
authors: †State Key Laboratory of Analytical Chemistry for Life Science, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
authors: Jun-Jie
authors: JJ
authors: Zhu
mesh_terms: D000818:Animals; D002364:Caseins / Q000737:chemistry; D002384:Catalysis; D002417:Cattle; D002563:Cerium / Q000737:chemistry*; D052203:Ferrosoferric Oxide / Q000737:chemistry*; D006801:Humans; D053758:Nanoparticles / Q000737:chemistry / Q000648:ultrastructure; D009556:Niobium / Q000737:chemistry*; D010748:Phosphopeptides / Q000378:metabolism*; D010750:Phosphoproteins / Q000737:chemistry / Q000378:metabolism; D010766:Phosphorylation; D056951:Photoelectron Spectroscopy; D059027:Recycling; D019032:Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; D013056:Spectrophotometry, Ultraviolet; D013696:Temperature; D014025:Titanium / Q000737:chemistry*
chemical_list: D002364:Caseins; D010748:Phosphopeptides; D010750:Phosphoproteins; D009556:Niobium; C009495:titanium dioxide; D002563:Cerium; C030583:ceric oxide; D014025:Titanium; D052203:Ferrosoferric Oxide
keywords: 2D nanosheet; dephosphorylation; enrichment; phosphopeptide; ternary nanocomposite