Metal–Organic Framework-Derived Hollow and Hierarchical Porous Multivariate Metal-Oxide Microspheres for Efficient Phosphoproteomics Analysis

Abstract

Pre-enrichment of the biological samples is a crucial step in phosphoproteomics research. At present, metal-oxide affinity chromatography (MOAC) is one of the most recognized enrichment strategy. Therefore, the design and preparation of a MOAC-based affinity material with better enrichment properties will be of great significance for the phosphoproteomics study. In this work, we obtained a novel multivariate metal-oxide microsphere (NiFe 2 O 4 @C@TiO 2 ) with a hollow and hierarchical porous structure through pyrolysis of TiO 2-modified Fe/Nibased metal−organic frameworks (MOFs). After pyrolysis, the carbon matrix derived from the MOFs provided support and porous properties. Meanwhile, multivariate metal oxides endowed the microspheres with an excellent magnetic response property and superior enrichment performance for phosphorylated biomolecules. The unique hollow and hierarchical porous structure greatly enhanced the diffusion of phosphorylated biomolecules. Therefore, the microspheres exhibited excellent enrichment performance for phosphorylated biomolecules: a large adsorption capacity (124 μmol g −1 ), excellent selectivity (αcasein/BSA, 1:5000, m/m), perfect size-exclusion performance (α-casein digests/α-casein/BSA, 1:500:500), and extremely low detection limit (2 fmol). Furthermore, the microspheres showed excellent enrichment performance in a series of real biological samples, such as nonfat milk, serum, saliva, rat brain tissue, and plasma exosomes of patients with esophageal cancer, which further demonstrated its huge application potential in MS-based phosphoproteomics research.

Modular preparation of functional bimetallic spinels from metal–organic frameworks: a deep exploration from macro and micro perspectives

“…[28][29][30] Pleasingly, special adjustability of MOFs allows them to be used as templates for synthesizing bimetallic spinels. 31,32 This synthesis method brings some advantages, mainly reected in the following points: rstly, the preparation strategy using MOFs as precursors is relatively simple, requires low energy consumption, and provides a rich variety of precursors compared to traditional preparation methods. Secondly, compared to other preparation methods, MOF-derived bimetallic spinels can obtain more stable metal sites, reducing the metal leaching rate during the reaction process.…”

Hydrophilic magnetic host–guest Ti–phenolic networks: a promising material for the highly sensitive enrichment of glycopeptides and phosphopeptides

“…Significant efforts have been made to construct efficient enrichment strategies for capturing glycopeptides and phosphopeptides. 8,[12][13][14][15][16][17] For glycopeptide enrichment, hydrophilic interaction chromatography (HILIC) is one of the most favorable strategies owing to its high reproducibility and excellent biocompatibility, among which glutathione (GSH) with good hydrophilicity has been widely used to prepare the HILIC materials towards glycopeptide capture. [18][19][20][21][22] For instance, in our previous study, we successfully designed an efficient b-cyclodextrin (b-CD)-based HILIC glycopeptide enrichment material engineered by host-guest interactions (b-CD as host and GSH derived adamantine as a guest) and metal-phenolic interactions.…”